02055nas a2200217 4500008004100000022001400041245014600055210006900201260007900270300001200349490000600361520118200367653002601549653002201575653001801597653002301615100002101638700003001659700002201689856012601711 2005 eng d a1388-248100aElectrochemical studies of poly (3,4-ethylenedioxythiophene) PEDOT/VS2 nanocomposite as a cathode material for rechargeable lithium batteries0 aElectrochemical studies of poly 34ethylenedioxythiophene PEDOTVS a360 PARK AVE SOUTH, NEW YORK, NY 10010-1710 USAbELSEVIER SCIENCE INCcFEB a213-2180 v73 a

Here, we demonstrate the electrochemical characterization of a new type of layered poly (3,4-ethylenedioxythiophene) PEDOT/ VS2 nanocomposite. It has been prepared via flocculation of delaminated VS2 with subsequent in situ oxidative polymerization of 3,4-ethylenedioxythiophene (EDOT) with VS2 as a host material in the presence of an external oxidizing agent. The interlayer spacing Of VS2 expands from 5.71 to 14.01 A and this interlayer separation is consistent with the existence of a monolayer of PEDOT in the VS2 framework. X-ray diffraction, XPS and TEM studies have been;shown the change in interlayer separation is consistent with the existence of two phases of organic and inorganic species in the nanocomposites corresponding to the intercalation of PEDOT in the VS2 framework. The application potential of the nanocomposite as a cathode material for rechargeable lithium batteries is also demonstrated by the electrochemical intercalation of lithium into the PEDOT/VS2 nanocomposite, where a significant enhancement in the discharge capacity is observed (similar to130 mAh/g) compared to that (80 mAh/g) for pristine VS2. (C) 2004 Published by Elsevier B.V.

10alayered nanocomposite10alithium batteries10apolythiophene10avanadium disulfide1 aMurugan, Vadivel1 aGopinath, Chinnakonda, S.1 aVijayamohanan, K. uhttp://library.ncl.res.in/content/electrochemical-studies-poly-34-ethylenedioxythiophene-pedotvs2-nanocomposite-cathode-001761nas a2200193 4500008004100000022001400041245015200055210006900207260012500276300001100401490000700412520090600419100002101325700002201346700001601368700003001384700002201414856013101436 2005 eng d a0003-695100aEnhancement of double-layer capacitance behavior and its electrical conductivity in layered poly (3, 4-ethylenedioxythiophene)-based nanocomposites0 aEnhancement of doublelayer capacitance behavior and its electric aCIRCULATION & FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USAbAMER INST PHYSICScDEC a2435110 v873 a

In this letter, we report on the enhanced double-layer capacitance of a layered poly (3, 4-ethylene dioxythiophene) PEDOT-MoO3 nanocomposite, which has been synthesized by a novel microwave irradiation method. The x-ray photoelectron spectroscopy analysis shows the changes in electron density and the shift in binding energy suggesting charge transfer from sulfur atoms upon PEDOT intercalation between MoO3 layers. The room-temperature conductivity for the PEDOT-MoO3 composite is found to be 1.82x10(-1) S cm(-1), which is four orders of magnitude higher than that of the pristine oxide (3.78x10(-5) S cm(-1)). The enhanced double-layer capacitance of the PEDOT-MoO3 nanocomposite (similar to 300 F g(-1)) compared to that (similar to 40 mF g(-1)) of pristine MoO3 is attributed to higher electronic conductivity, enhanced bidimensionality, and increase in surface area of the nanocomposite.

1 aMurugan, Vadivel1 aViswanath, A., K.1 aCampet, Guy1 aGopinath, Chinnakonda, S.1 aVijayamohanan, K. uhttp://library.ncl.res.in/content/enhancement-double-layer-capacitance-behavior-and-its-electrical-conductivity-layered-poly-302701nas a2200337 4500008004100000022001400041245012800055210006900183260007300252300001200325490000700337520156900344653003201913653002601945653001601971653001701987653001402004653001302018653001702031653002302048653001702071653003002088653002002118653000802138100001302146700001502159700001802174700001502192700003002207856012602237 2005 eng d a0926-337300aIn situ XPS investigations of Cu1-xNixZnAl-mixed metal oxide catalysts used in the oxidative steam reforming of bio-ethanol0 aIn situ XPS investigations of Cu1xNixZnAlmixed metal oxide catal aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcFEB a287-2990 v553 a

A series of CuNiZnAl-multicomponent mixed metal oxide catalysts with various Cu/Ni ratios were prepared by the thermal decomposition of Cu1-xNixZnAl-hydrotalcite-like precursors and tested for oxidative steam reforming of bio-ethanol. Dehydrogenation of EtOH to CH3CHO is favored by Cu-rich catalyst. Introduction of Ni leads to C-C bond rupture and producing CO, CO2 and CH4. H-2 yield (selectivity) varied between 2.6-3.0 mol/mol of ethanol converted (50-55%) for all catalysts at 300 degreesC. The above catalysts were subjected to in situ XPS studies to understand the nature of active species involved in the catalytic reaction. Core level and valence band XPS as well as Auger electron spectroscopy revealed the existence of Cu2+, Ni2+ and Zn2+ ions on calcined materials. Upon in situ reduction at reactions temperatures, the Cu2+ was fully reduced to Cu-0. while Ni2+ and Zn2+ were partially reduced to Ni-0 and Zn-0, respectively. On reduction, the nature of ZnO on Cu-rich catalyst changes from crystalline to amorphous, relatively inert and highly stabilized electronically. Relative concentration of the Ni-0 and Zn-0 increases upon reduction with decreasing Cu-content. Valence band results demonstrated that the overlap between 3d bands of Cu and Ni was marginal on calcined materials, and no overlap due to metallic clusters formation after reduction. Nonetheless, the density of states at Fermi level increases dramatically for Ni-rich catalysts and likely this influences the product selectivity. (C) 2004 Elsevier B.V. All rights reserved.

10aauger electron spectroscopy10aAutothermal reforming10aBio-ethanol10acopper oxide10afuel cell10aHydrogen10ahydrotalcite10amixed metal oxides10anickel oxide10aoxidative steam reforming10aSteam reforming10aXPS1 aVelu, S.1 aSuzuki, K.1 aVijayaraj, M.1 aBarman, S.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/situ-xps-investigations-cu1-xnixznal-mixed-metal-oxide-catalysts-used-oxidative-steam-002716nas a2200301 4500008004100000022001400041245010700055210006900162260007300231300001200304490000800316520171400324653001202038653001802050653002302068653001002091653000702101653001302108653002002121653001802141653002302159100001802182700001602200700002802216700001802244700003002262856012202292 2005 eng d a1381-116900aInsight into the mechanism of selective mono-N-methylation of aniline on Cu1-xZnxFe2O4: a DRIFTS study0 aInsight into the mechanism of selective monoNmethylation of anil aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcAPR a169-1800 v2313 a

Mechanism of selective mono-N-methylation of aniline with methanol on Cu1-xZn2FeO4 catalysts was investigated in detail. The interaction of reactants (aniline. methanol and methanol: aniline) and possible products (N-methylaniline (NMA), N,N-dimethylaniline (DMA) and o-toluidine (OT)) on catalysts surface was studied by temperature-dependent in situ FTIR spectroscopy. Methanol adsorbs dissociatively over catalysts surface at 373 K as methoxy species and is oxidized to formate species at high temperature through dioxymethylene and/or formaldehyde as a surface intermediate species. On the other hand, adsorption of aniline:methanol mixtures shows that methanol oxidation was completely hindered in the presence of aniline. Aniline adsorbs on the Lewis acid sites at <= 373 K with phenyl ring oriented in a perpendicular manner to the catalyst surfaced however, N-H bond scission occurs above 373 K. A comparison of adsorbed NMA and methanol: am line (3:1) mixture on Cu0.5Zn0.5Fe2O4 shows NMA forms from the reaction mixture at 473 K. However, maximum activity at 573 K in catalytic reaction studies suggests that desorption limits the methylation kinetics. FTIR study displays stable aniline and methyl species on ZnFe2O4 even at 573 K; however. no methyl species is detected on Cr0.95Zn0.05Fe2O4 at 473 K due to methanol reforming reaction and that limits the overall reaction and hence low catalytic activity. It is proposed that methanol is protonated on catalysts surface by the labile H+ due to N-H bond scission. Co-adsorption of acidity probes with aniline and methanol indicates that aniline methylation takes place at single acid-base site. (c) 2005 Elsevier B.V. All rights reserved.

10aAniline10aCu1-xZnxFe2O410adesorption limited10aDRIFT10aIR10aMethanol10aN-methylaniline10aN-methylation10areaction mechanism1 aVijayaraj, M.1 aMurugan, B.1 aUmbarkar, Shubhangi, B.1 aHegde, S., G.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/insight-mechanism-selective-mono-n-methylation-aniline-cu1-xznxfe2o4-drifts-study-001855nas a2200181 4500008004100000022001400041245012200055210006900177260007100246300001600317490000800333520112200341100002401463700002001487700001401507700003001521856012201551 2005 eng d a1520-610600aIsothermal kinetic study of nitric oxide adsorption and decomposition on Pd(111) surfaces: molecular beam experiments0 aIsothermal kinetic study of nitric oxide adsorption and decompos a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUL a13283-132900 v1093 a

The kinetics of NO adsorption and dissociation on Pd(111) surfaces and the NO sticking coefficient (S-NO) were probed by isothermal kinetic measurements between 300 and 525 K using a molecular beam instrument. NO dissociation and N-2 productions were observed in the transient state from 425 K and above on Pd(l 11) surfaces with selective nitrogen production. Maximum nitrogen production was observed between 475 and 500 K. It was found that, at low temperatures, between 300 and 350 K, molecular adsorption occurs with a constant initial SNO of 0.5 until the Pd(I 11) surface is covered to about 70-80% by NO. Then SNO rapidly decreases with further increasing NO coverage, indicating typical precursor kinetics. The dynamic adsorption-desorption equilibrium on Pd(I 11) was probed in modulated beam experiments below 500 K. CO titration experiments after NO dosing indicate the diffusion of oxygen into the subsurface regions and beginning surface oxidation at >= 475 K. Finally, we discuss the results with respect to the rate-limiting character of the different elementary steps of the reaction system.

1 aThirunavukkarasu, K1 aThirumoorthy, K1 aLibuda, X1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/isothermal-kinetic-study-nitric-oxide-adsorption-and-decomposition-pd111-surfaces-001385nas a2200241 4500008004100000022001400041245008900055210006900144260009500213300001200308490000800320520046100328653002500789653003600814653002800850653003000878100001700908700001800925700003000943700001900973700002600992856012501018 2005 eng d a0021-951700aMCM-41-supported platinum carbonyl cluster-derived asymmetric hydrogenation catalyst0 aMCM41supported platinum carbonyl clusterderived asymmetric hydro a525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USAbACADEMIC PRESS INC ELSEVIER SCIENCEcJAN a298-3020 v2293 a

Anionic platinum carbonyl cluster has been ion paired with cinchonidium groups that are chemically bound to the surface of MCM-41 and fumed silica. In the hydrogenation of methyl pyruvate or acetophenone the fumed silica-based catalyst gives zero enantioselectivity, but under optimum conditions enantiomeric excesses of >90 and similar to40%, respectively, are obtained with the MCM-41-based catalyst. (C) 2004 Elsevier Inc. All rights reserved.

10aasymmetric catalysis10afunctionalized inorganic oxides10ahydrogenation catalysts10aplatinum carbonyl cluster1 aBasu, Susmit1 aPaul, Himadri1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar uhttp://library.ncl.res.in/content/mcm-41-supported-platinum-carbonyl-cluster-derived-asymmetric-hydrogenation-catalyst-001838nas a2200181 4500008004100000022001400041245007200055210006900127260007100196300001600267490000800283520118100291100002401472700002001496700001401516700003001530856009601560 2005 eng d a1520-610600aMolecular beam study of the NO plus CO reaction on Pd(111) surfaces0 aMolecular beam study of the NO plus CO reaction on Pd111 surface a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUL a13272-132820 v1093 a

Nitric oxide (NO) reduction with carbon monoxide (CO) on the Pd(111) surface was studied under isothermal conditions by molecular beam techniques as a function of temperature, NO:CO beam composition, and beam flux. Systematic experiments were performed under transient and steady state conditions. Displacement of adsorbed CO by NO in the transient state of the reaction was observed at temperatures between 375 and 475 K for all the NO: CO compositions studied. NO accumulation occurs on Pd(l 11) surface under steady state conditions, below 475 K, due to stronger chemisorption of NO. The steady state reaction rates attain a maximum at about 475 K, nearly independent of beam composition. N-2 was found to be the major product of the reduction, along with a minor production of N2O. The production of N2 and N2O indicates molecular and dissociative adsorption of NO on Pd(l 11) at temperatures up to 525 K. Postreaction TPD measurements were performed in order to determine the nitrogen coverage under steady-state conditions. Finally, the results are discussed with respect to the rate-controlling character of the different elementary steps of the reaction system.

1 aThirunavukkarasu, K1 aThirumoorthy, K1 aLibuda, J1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/molecular-beam-study-no-plus-co-reaction-pd111-surfaces-002820nas a2200169 4500008004100000022001400041245017300055210006900228260007100297300001600368490000800384520205600392100001902448700002502467700003002492856012802522 2005 eng d a1520-610600aMolecular origins of wettability of hydrophobic poly(vinylidene fluoride) microporous membranes on poly(vinyl alcohol) adsorption: Surface and interface analysis by XPS0 aMolecular origins of wettability of hydrophobic polyvinylidene f a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUL a13941-139470 v1093 a

irreversible adsorption of poly(vinyl alcohol) (PVA) on hydrophobic, porous poly(vinylidene fluoride) (PVDF) membranes was carried out using aqueous PVA solution. Water permeation was observed in PVDF microporous membranes after PVA adsorption, and maximum permeability was obtained after treatment with 4% PVA solution. Water permeability increased linearly with increasing PVA concentration up to 4%, and then a marginal decrease with a further increase in PVA concentration occurred. PVA adsorbed PVDF membranes were subjected to intense physicochemical analysis, especially with XPS. XPS results display the presence of an interface between PVA and PVDF, and the binding energy (BE) of the interface is low for the PVDF membranes treated with 4% PVA. Carbon from CF2-groups and F 1s core level clearly showed a decrease in its content on the surface after PVA adsorption and showed a minimum fluorine content at 4% PVA. F Is BE shifts by 0.5 eV upon PVA adsorption and is independent of PVA concentration. EDAX analysis indicates that the bulk oxygen content remains within 4.5 +/- 0.6% and is independent of the PVA concentration. Nonetheless, a large amount of surface atom percentage of oxygen (20 +/- 4%) from 0 Is core level shows an increase in PVA content on the surface of PVDF, and it is restricted mostly to the surface. The 4% PVA treated PVDF membrane clearly shows a broadening of O 1s core level to lower BE and indicates the interaction between PVDF and PVA which is significantly different compared to any other compositions. A new valence band feature at low BE, which is nonexistent on PVDF, develops after PVA adsorption. This indicates that the shift in the nature of the highest occupied molecular orbital (HOMO) derived mostly from oxygen; simultaneously, a suppression in the PVDF derived band indicates the change in nature of the PVA adsorbed surfaces from hydrophobic to hydrophilic. The above observations also suggest an irreversible electronic interaction between PVA and PVDF, possibly through charge transfer.

1 aGholap, S., G.1 aBadiger, Manohar, V.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/molecular-origins-wettability-hydrophobic-polyvinylidene-fluoride-microporous-membranes-002571nas a2200193 4500008004100000022001400041245011300055210006900168260007100237300001400308490000700322520181500329100001602144700002202160700001702182700003002199700001802229856013002247 2005 eng d a0897-475600aNature of manganese species in Ce1-xMnxO2-delta solid solutions synthesized by the solution combustion route0 aNature of manganese species in Ce1xMnxO2delta solid solutions sy a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUL a3983-39930 v173 a

A series of manganese-cerium oxide composites with Mn concentrations in the range of 1-20 mol % in ceria was prepared by the solution combustion technique using urea as fuel. The nature, type, and oxidation state of Mn species in ceria were investigated by X-ray diffraction (XRD), diffuse reflectance UV-visible spectroscopy, electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy, and temperature-programmed reduction techniques. The study reveals that the method of preparation significantly influences the type of manganese species in ceria. Wet-impregnation, coprecipitation, and solid-state synthesis techniques lead to clustered MnOx-like species in the ceria matrix, while the present method of preparation (solution combustion route) yields a highly dispersed form of Mn species. In the reported series of samples, Mn is present mainly in +2 and +3 oxidation states and there is no evidence for the presence of Mn 41 species. Powder X-ray diffraction studies at variable temperatures (298-1323 K) indicate the formation of Ce1-xMnxO2-delta Solid solutions. No separate MnOx-type phase was detected even at 1323 K. EPR studies reveal that the isolated Mn2+ and Mn2+ species are present in at least three different structural locations: species A, Mn ions in ceria-lattice defect sites; species B, Mn ions in framework Ce4+ locations; and species C, Mn ions in interstitial locations and at the surface of ceria. The Mn3+ ions in ceria exhibit a facile reduction and reoxidation behavior when exposed to dry hydrogen and subsequently to air at elevated. temperatures. A highly dispersed state of Mn3+ and Mn2+ in ceria, facile redox behavior, and a synergistic Mn-ceria interaction are some of the unique properties of this material prepared by the solution combustion procedure.

1 aMurugan, B.1 aRamaswamy, A., V.1 aSrinivas, D.1 aGopinath, Chinnakonda, S.1 aRamaswamy, V. uhttp://library.ncl.res.in/content/nature-manganese-species-ce1-xmnxo2-delta-solid-solutions-synthesized-solution-combustion-002622nas a2200301 4500008004100000022001400041245014300055210006900198260009500267300001200362490000800374520152800382653002701910653001201937653001701949653001801966653003001984653001802014653001202032653001202044100001802056700002102074700002602095700003002121700001602151700002602167856012702193 2005 eng d a0021-951700aOxidative dehydrogenation of ethylbenzene over vanadia-alumina catalysts in the presence of nitrous oxide: structure-activity relationship0 aOxidative dehydrogenation of ethylbenzene over vanadiaalumina ca a525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USAbACADEMIC PRESS INC ELSEVIER SCIENCEcMAR a484-4920 v2303 a

A series of vanadia-alumina catalysts with different vanadia contents were prepared by a wet impregnation method. The influence of the local structure of vanadia in these catalysts on the oxidative dehydrogenation of ethylbenzene with nitrous oxide was investigated. The use of N2O as a co-feed remarkably enhanced the styrene yield compared with the use of N-2. Characterization of these vanadia catalysts by XRD, FTIR, UV-vis, TPR, XPS, and V-51 NMR techniques suggests that the nature of the VOx species depends on the vanadia loading: the predominant species are monomeric vanadia at lower loadings, two-dimensional polyvanadates at intermediate loadings, and bulk-like V2O5 and AlVO4 at higher loadings. The rate of oxidative dehydrogenation (ODH) of ethylbenzene per vanadium atom increases with vanadia loading and reaches a maximum at 10 wt%, the loading at which the surface predominantly contains polyvanadate species. The observed variation in the selectivity of products with vanadium loading indicates that the monomeric V5+ species favors dehydrogenation, whereas bulk-like V2O5 preferentially participates in the dealkylation of ethylbenzene. The vanadium species remains at a higher oxidation state in the presence of N2O, leading to a higher styrene yield. than in a N-2 atmosphere. The ODH turnover rates increased with decreasing energy of the absorption edge in the UV-vis spectrum, at low VOx coverages of less than one monolayer on the Al2O3 surface. (c) 2005 Elsevier Inc. All rights reserved.

10aabsorption edge energy10aAlumina10aethylbenzene10aNitrous oxide10aoxidative dehydrogenation10apolyvanadates10astyrene10avanadia1 aShiju, N., R.1 aAnilkumar, Mettu1 aMirajkar, Subhash, P.1 aGopinath, Chinnakonda, S.1 aRao, B., S.1 aSatyanarayana, C., V. uhttp://library.ncl.res.in/content/oxidative-dehydrogenation-ethylbenzene-over-vanadia-alumina-catalysts-presence-nitrous-001524nas a2200181 4500008004100000022001400041245011900055210006900174260007100243300001400314490000700328520079600335100001501131700001901146700001801165700003001183856012901213 2005 eng d a0897-475600aSynthesis, characterization, electronic structure, and photocatalytic activity of nitrogen-doped TiO2 nanocatalyst0 aSynthesis characterization electronic structure and photocatalyt a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcDEC a6349-63530 v173 a

Nitrogen-doped TiO2 (N-TiO2)) nanocatalyst with spherical shape and homogeneous size has been synthesized through a chemical method using TiCl3 as precursor. The light absorption onset shifts from 380 nm on pure TiO2 to the visible region at 550 nm with N-TiO2. A clear decrease in the band gap and the nitrogen 2p states on the top of the valence band on N-TiO2 (compared to TiO2) is deduced from the optical absorption spectroscopy results. The chemical nature of N has been evolved as N-Ti-O in the anatase TiO2 lattice as identified by X-ray photoelectron spectroscopy (XPS). Photocatalytic decomposition of methylene blue has been carried out both in the UV and in the visible region and N-TiO2 shows higher activity than the Degussa P25 TiO2 photocatalyst in the visible region.

1 aSathish, M1 aViswanathan, B1 aViswanath, RP1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/synthesis-characterization-electronic-structure-and-photocatalytic-activity-nitrogen-doped02226nas a2200265 4500008004100000022001400041245014400055210006900199260009500268300001000363490000800373520126800381653001201649653001201661653002001673653001801693653001101711653001501722653002501737653000801762653000801770100002401778700003001802856012801832 2006 eng d a0021-951700aOn the ``Active spacer and stabilizer'' role of Zn in Cu1-xZnxFe2O4 in the selective mono-N-methylation of aniline: XPS and catalysis study0 aActive spacer and stabilizer role of Zn in Cu1xZnxFe2O4 in the s a525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USAbACADEMIC PRESS INC ELSEVIER SCIENCEcJUL a83-950 v2413 a

A systematic catalytic methylation study on ferrospinel materials led to the selective production of N-methylaniline (NMA) with Cu1-xZnxFe2O4. Aniline methylation was carried out on Cu1-xZnxFe2O4 with a feed composition of CH3OH:PhNH2:H2O = 3:1:1 at 513-633 K. NMA was formed selectively on all of the catalyst compositions, with trace amounts of secondary products under most of the conditions. Cu0.5Zn0.5Fe2O4 composition showed high catalytic activity and stability up to 100 h. Although the Cu2+ was responsible for methylation activity, Zn2+ enhanced the overall stability of the catalyst system. XPS investigations revealed that the degree of Cu2+ reduction decreased dramatically from x = 0.05/0.25 to 0.5/0.75 on spent catalysts. TPR studies indicated that the reducibility of Cu2+ decreased from fully reducible at 523 K with Cu-rich compositions to partially reducible at 573 K on x = 0.5. Stable activity observed on Cu0.5Zn0.5Fe2O4 can be attributed to the highly heterogeneous distribution of metal ions. This heterogeneous distribution indicates an important role of zinc, likely as an ``active spacer cum stabilizee' that hinders the reduction of active Cu2+ and contributes to prolonged activity. (c) 2006 Elsevier Inc. All rights reserved.

10aAniline10aFerrite10aN-methylaniline10aN-methylation10aspacer10astabilizer10asurface distribution10aTPR10aXPS1 aVijayaraj, Munusamy1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/active-spacer-and-stabilizer-role-zn-cu1-xznxfe2o4-selective-mono-n-methylation-aniline-102579nas a2200169 4500008004100000022001400041245014400055210006900199260007100268300001400339490000700353520184400360100002502204700003002229700003002259856012002289 2006 eng d a0897-475600aAutoreduction of cyanoferrate(III) ions in a polymer electrolyte membrane: all solid state electrochemical and spectroscopic investigations0 aAutoreduction of cyanoferrateIII ions in a polymer electrolyte m a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcOCT a5244-52520 v183 a

The effect of dielectric confinement on proton-coupled electron-transfer behavior and spectroscopic properties of cyanoferrate ions in a polymer electrolyte membrane (Nafion) has been investigated in an ``all-solid-state'' electrochemical cell, using techniques such as cyclic voltammetry, zero current chronopotentiometry, electrochemical impedance, diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), UV-visible spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron spin resonance spectroscopy (ESR). From the above investigations, we found that cyanoferrate(III) ions undergo autoreduction in the ionomer matrix, for which a sulfonate-coupled mechanism has been proposed. This report demonstrates the effectiveness of the micellar interface in tuning the redox potential of the confined ions. A systematic analysis of the cyclic voltammetry and impedance data for the [Fe(CN)(6)](4)(-)- containing Nafion membrane enables the estimation of a standard rate constant for [Fe(CN) 6](4-) oxidation, k(o), as 5.44 x 10(-6) cm/s and a diffusion coefficient, D-o, as 1.3 x 10(-12) cm(2)/s. A similar calculation yields a value of 4.8 x 10(-12) cm(2)/s for the diffusion coefficient of protons and 9.1 x 10(-6) cm/s for the standard rate constant for hydrogen oxidation. The similarity in mass-transfer coefficients calculated for protons and [Fe(CN)(6)](4-) ions suggests a proton-coupled electron-transfer mechanism for the [Fe(CN)(6)](4-)/[Fe(CN)(6)](3-) couple. The results of the above investigations could have direct technological relevance for deciding catalyst materials having redox compatibility with the polymer electrolyte, especially in the preparation of catalyst-coated membranes (wherein the fuel-cell catalyst is directly coated onto the polymer membrane instead of on the carbon support).

1 aParthasarathy, Meera1 aGopinath, Chinnakonda, S.1 aPillai, Vijayamohanan, K. uhttp://library.ncl.res.in/content/autoreduction-cyanoferrateiii-ions-polymer-electrolyte-membrane-all-solid-state-100609nas a2200133 4500008004100000022001400041245010100055210006900156260007100225300001400296490000800310100003000318856012700348 2006 eng d a1520-610600aComment on ``Photoelectron spectroscopic investigation of nitrogen-doped titania nanoparticles''0 aComment on Photoelectron spectroscopic investigation of nitrogen a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcAPR a7079-70800 v1101 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/comment-photoelectron-spectroscopic-investigation-nitrogen-doped-titania-nanoparticles-102689nas a2200313 4500008004100000022001400041245011600055210006900171260009500240300001200335490000800347520155000355653003601905653002801941653001101969653003001980653002002010653001802030653000802048100001902056700001702075700001702092700003502109700002702144700003002171700001902201700002602220856012902246 2006 eng d a0021-951700aEffect of spacer groups on the performance of MCM-41-supported platinum cluster-derived hydrogenation catalysts0 aEffect of spacer groups on the performance of MCM41supported pla a525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USAbACADEMIC PRESS INC ELSEVIER SCIENCEcSEP a332-3390 v2423 a

MCM-41 was functionalized with (EtO)(3)SiCH2Cl, (MeO)(3)SiCH2CH2CH2Cl, and (CH3)Cl2SiCH2Cl. The functionalized materials were characterized by solid-state NMR (CPMAS, Si-29 and C-13) and XPS. The NMR data indicate that three new silicon environments were created by(EtO)(3)SiCH2Cl and (MeO)(3)SiCH2CH2CH2Cl, whereas with (CH3)Cl2SiCH2Cl, two new silicon environments were obtained. XPS results from Si 2p core level and the valence band from the material functionalized by (MeO)(3)Si(CH2)(3)Cl was found to be the same as that of the corresponding fresh catalyst (1a), in contrast to that of the materials functionalized by the other two silane reagents. After further functionalization with triethylamine, these materials were used as inorganic anion exchangers to support the cluster anion [Pt-12(CO)(24)](2-). Solid-state NMR (29Si, C-13, N-15) was used to establish the presence of the quaternary ammonium group in the cluster-supported species. Analogous materials were also created using fumed silica as the support, and all of the cluster-supported materials were tested as catalysts for the hydrogenation of methyl pyruvate, acetophenone, nitrobenzene, benzonitrile, ethylacetoacetate, 4-nitrotoluene, cyclohexanone, allyl alcohol, and styrene. The best activity was obtained for the catalyst that had MCM-41 as the support and chloropropyl as the spacer group. TEM showed that the supports and the spacer groups had observable effects on the platinum crystallite size of the catalysts. (c) 2006 Elsevier Inc. All rights reserved.

10afunctionalized inorganic oxides10ahydrogenation catalysts10aMCM-4110aplatinum carbonyl cluster10aSolid-state NMR10aspacer groups10aXPS1 aMaity, Niladri1 aBasu, Susmit1 aMapa, Maitri1 aRajamohanan, Pattuparambil, R.1 aGanapathy, Subramanian1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar uhttp://library.ncl.res.in/content/effect-spacer-groups-performance-mcm-41-supported-platinum-cluster-derived-hydrogenation-101772nas a2200265 4500008004100000022001400041245015000055210006900205260007300274300001200347490000800359520077200367653002101139653002201160653000901182653003601191653002201227100002101249700001601270700002101286700001601307700003001323700002201353856013101375 2006 eng d a0378-775300aExfoliation-induced nanoribbon formation of poly(3,4-ethylene dioxythiophene) PEDOT between MoS2 layers as cathode material for lithium batteries0 aExfoliationinduced nanoribbon formation of poly34ethylene dioxyt aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJUN a615-6190 v1563 a

A new type of layered nanocomposite synthesized by delaminated MoS2 nanosheets and poly(3,4-ethylenedioxythiophene) (PEDOT) are restacked to produce alternate polymer nanoribbons between layers Of MoS2 with an interlayer distance of similar to 1.38 nm. The unique properties of resulting nanocomposite are investigated by powder XRD, XPS, SEM, TEM, and four-probe conductivity measurements. The obtained nanocomposite can be used as a cathode material for a small power rechargeable lithium battery as demonstrated by the electrochemical insertion of lithium into the PEDOT/MoS2 nanocomposite. A significant enhancement in the discharge capacity (100 mAh g(-1)) is observed compared with that (40 mAh g(-1)) for MoS2. (c) 2005 Elsevier B.V All rights reserved.

10acathode material10alithium batteries10aMoS210aorganic-inorganic nanocomposite10aPEDOT-nanoribbons1 aMurugan, Vadivel1 aQuintin, M.1 aDelville, M., H.1 aCampet, Guy1 aGopinath, Chinnakonda, S.1 aVijayamohanan, K. uhttp://library.ncl.res.in/content/exfoliation-induced-nanoribbon-formation-poly34-ethylene-dioxythiophene-pedot-between-mos2-002066nas a2200181 4500008004100000022001400041245015200055210006900207260012500276300002300401490000800424520122300432100002101655700003101676700003001707700002201737856012501759 2006 eng d a0021-897900aHighly efficient organic-inorganic poly(3,4-ethylenedioxythiophene)-molybdenum trioxide nanocomposite electrodes for electrochemical supercapacitor0 aHighly efficient organicinorganic poly34ethylenedioxythiophenemo aCIRCULATION & FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USAbAMER INST PHYSICScOCT aArticle No. 0743190 v1003 a

In this paper, we report a highly efficient organic-inorganic nanocomposite electrode with enhanced double layer capacitance, which has been synthesized using 3,4-ethylenedioxythiophene and crystalline molybdenum trioxide (MoO3) in the presence of an external oxidizing agent. The interlayer spacing of MoO3 upon intercalation expands from 6.93 to 13.46 A and is followed by an exfoliation and restacking process. The resulting nanocomposite is characterized by powder x-ray diffraction, scanning electron microscopy, transmission electron microscopy, x-ray photoelectron spectroscopy, and four probe conductivity measurements. The application potential of this nanocomposite as an electrode material for electrochemical supercapacitors has been investigated, highlighting the unusual enhancement of double layer capacitance of poly(3,4-ethylenedioxythiphene) (PEDOT-MoO3) nanocomposites (similar to 300 F g(-1)) compared to that of pristine MoO3 (similar to 40 mF g(-1)). The improved electrochemical performance is attributed to the intercalation of electronically conducting PEDOT between MoO3 layers with enhanced bidimensionality and an increase in the surface area. (c) 2006 American Institute of Physics.

1 aMurugan, Vadivel1 aViswanath, Annamraju, Kasi1 aGopinath, Chinnakonda, S.1 aVijayamohanan, K. uhttp://library.ncl.res.in/content/highly-efficient-organic-inorganic-poly34-ethylenedioxythiophene-molybdenum-trioxide-102187nas a2200265 4500008004100000022001400041245012200055210006900177260009500246300001200341490000800353520115600361653004001517653002301557653002601580653002801606653003001634100001701664700001701681700003001698700001801728700001901746700002601765856013001791 2006 eng d a0021-951700aMCM-41-supported platinum carbonyl cluster-derived catalysts for asymmetric and nonasymmetric hydrogenation reactions0 aMCM41supported platinum carbonyl clusterderived catalysts for as a525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USAbACADEMIC PRESS INC ELSEVIER SCIENCEcAPR a154-1610 v2393 a

Anionic platinum carbonyl Cluster ([Pt-12(CO)(24)](2-)) was ion-paired with the 3-chloropropyltrimethoxysilyl-ammonium group chemically bound to the surface of MCM-41. The materials undergo quick decarbonylation and have been characterized before decarbonylation by IR and UV-vis spectroscopy and after decarbonylation by XPS and TEM. They have been used as catalysts for the hydrogenations of methyl pyruvate, acetophenone, nitrobenzene, benzonitrile, and ethylacetoacetate. The support and the quaternary ammonium groups have significant effects on surface platinum concentration, crystallite size, and observed activity. In the hydrogenation of the prochiral substrates methyl pyruvate or acetophenone, the cinchonidine-based catalyst gives significant enantioselectivity under optimum conditions. A kinetic model that includes an enantioselective product-formation step and a hydrogen pressure-dependent step for the deactivation of the enantioselective sites gives reasonable agreement between predicted and observed enantioselectivity. The model is also in accordance with the XPS and TEM data. (c) 2006 Elsevier Inc. All rights reserved.

10aasymmetric/non-asymmetric catalysis10aEnantioselectivity10afunctionalized MCM-4110ahydrogenation catalysts10aplatinum carbonyl cluster1 aBasu, Susmit1 aMapa, Maitri1 aGopinath, Chinnakonda, S.1 aDoble, Mukesh1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar uhttp://library.ncl.res.in/content/mcm-41-supported-platinum-carbonyl-cluster-derived-catalysts-asymmetric-and-nonasymmetric-102676nas a2200253 4500008004100000022001400041245010700055210006900162260009500231300001200326490000800338520173800346653000602084653001402090653002102104653002802125653002102153653002302174653001202197100002502209700003002234700003302264856012502297 2006 eng d a0021-951700aSelective ortho-methylation of phenol with methanol over copper manganese mixed-oxide spinel catalysts0 aSelective orthomethylation of phenol with methanol over copper m a525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USAbACADEMIC PRESS INC ELSEVIER SCIENCEcOCT a278-2910 v2433 a

Methylation of phenol with methanol as an alkylating agent to produce 2,6-xylenol was investigated over copper manganese mixed oxide spinels, CuxMn3-xO4 (x = 0, 0.25, 0.5, 0.75, and 1) prepared through co-precipitation. The catalytic activity strongly depends on the composition, acid-base properties, and structural stability. Various parameters, including catalyst composition, reaction temperature, feed composition, and durability of the catalyst during methylation, were investigated. Mainly o-cresol and 2,6-xylenol, along with small amounts of mesitol, were found in the product. A high ortho-selectivity of 100%, with 2,6-xylenol selectivity of 74%, was observed over Cu0.25Mn2.75O4 at 673 K. These catalysts were investigated using various techniques, including BET surface area, XRD, DRS UV-vis, TPD of NH3 and CO2, TPR, and X-ray photoemission spectroscopy (XPS). Powder XRD of the catalysts revealed the formation of copper-manganese spinels with hausmannite (Mn3O4) tetragonal structure, for x = 0-0.5, whereas an increase in copper content (x > 0.5) led to the formation of cubic Cu1.5Mn1.5O4 phase. DRS UV-vis, and FTIR further supported the changes in structural phases observed by XRD. Temperature-programmed desorption Of CO2 and NH3 showed that the catalysts have strong basicity along with weak acidity when x = 0 and 0.25. XPS and XAES analysis revealed the presence of only Cu2+ ions in fresh sample with x = 0.25, whereas for x = 1.0, both Cu1+ and Cu2+ were observed. The deactivation of the catalysts is attributed to structural changes occurring during the reaction. Catalytic activity is correlated with structure, as well as with acid-base properties. (c) 2006 Elsevier Inc. All rights reserved.

10a210a6-xylenol10aacidity-basicity10acopper-manganese oxides10aortho-alkylation10aphenol methylation10aSpinels1 aReddy, Satyanarayana1 aGopinath, Chinnakonda, S.1 aChilukuri, Satyanarayana, V. uhttp://library.ncl.res.in/content/selective-ortho-methylation-phenol-methanol-over-copper-manganese-mixed-oxide-spinel-002462nas a2200253 4500008004100000022001400041245009700055210006900152260009500221300001200316490000800328520157000336653002201906653002101928653001001949653001801959653000801977653001801985653002102003653000802024100002402032700003002056856012202086 2006 eng d a0021-951700aSelective production of methoxyphenols from dihydroxybenzenes on alkali metal ion-loaded MgO0 aSelective production of methoxyphenols from dihydroxybenzenes on a525 B ST, STE 1900, SAN DIEGO, CA 92101-4495 USAbACADEMIC PRESS INC ELSEVIER SCIENCEcOCT a376-3880 v2433 a

Selective O-methylation of dihydroxybenzenes (DHBs; catechol, resorcinol, and hydroquinone) to methoxyphenols (MPs) was carried out with dimethylcarbonate on MgO and alkali metal ion (Li, K, and Cs)-loaded MgO between 523 and 603 K. Catalytic activity and product selectivity varied with respect to DHB substrates. Selectivity for O-methylated products increased with increasing basicity of alkali ions; however, K-MgO showed high and stable activity toward MPs. Selectivity for MPs obtained from three substrates increased in the following order: catechol < resorcinol < hydroquinone. The mode of interaction of substrates on the catalysts surface influenced reactivity and product selectivity. It is likely that the low reaction temperatures used (< 603 K) kinetically control and favor high MP selectivity from DHBs. Calcined and spent catalysts were characterized by XRD, surface area, SEM, thermal analysis, NMR, and XPS. XRD analysis revealed the formation of alkali oxide phases on alkali-loaded MgO. Crystallite size and surface area of the catalysts decreased after methylation reactions, except on K-MgO. TGA showed 4060 wt% coke deposition on spent catalysts. TGA in N-2 followed by air and C-13 CP-MAS NMR measurements indicated the nature of deposited carbon to be molecular species, graphite, MgCO3 and polyaromatics. XPS revealed the nature and availability of active sites on the spent catalysts, as well as the same changes with reaction conditions and correlated with catalytic activity. (c) 2006 Elsevier Inc. All rights reserved.

10aalkali-loaded MgO10adihydroxybenzene10aK-MgO10amethoxyphenol10aMgO10aO-methylation10athermal analysis10aXPS1 aVijayaraj, Munusamy1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/selective-production-methoxyphenols-dihydroxybenzenes-alkali-metal-ion-loaded-mgo-002225nas a2200241 4500008004100000022001400041245013800055210006900193260007300262300001000335490000600345520129000351653002601641653003201667653003201699653002001731653001801751100001801769700003001787700002101817700002101838856012401859 2007 eng d a1567-173900aElectrochromic device (ECD) cell characterization on electron beam evaporated MoO3 films by intercalating/deintercalating the H+ ions0 aElectrochromic device ECD cell characterization on electron beam aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJAN a76-860 v73 a

Thin films of molybdenum oxide (MoO3) is one of the most interesting layered intercalation materials because of its excellent application in solid state batteries, large-area window and display systems. In recent years there has been considerable interest in variable transmittance electrochromic devices (ECD) based on Li+, H+ and K+ intercalation in transition metal oxide (MoO3) thin films. In the present investigation, thin films of MoO3 were prepared by electron beam evaporation technique on microscopic glass and fluorine doped tin oxide (FTO) coated glass substrates for the application in electrochromic device cells. The compositional stoichiometry of the films was studied by X-ray photoelectron spectroscopy (XPS). The electrochromic nature of the films has been analyzed by inserting H+ ions from the H2SO4 electrolyte solution using the cyclic-voltammetry (CV) technique. We studied the electrochromic device cells (ECD) incorporating an evaporated MoO3 thin films as electrochromic layers. The devices exhibit good optical properties with low transmittance values in the colored state, which make them suitable for large-area window applications. The maximum coloration efficiency of the cell was observed at about 70 cm(2)/c. (c) 2005 Published by Elsevier B.V.

10acoloration efficiency10aelectrochromic device cells10amolybdenum oxide thin films10aoptical density10astoichiometry1 aSivakumar, R.1 aGopinath, Chinnakonda, S.1 aJayachandran, M.1 aSanjeeviraja, C. uhttp://library.ncl.res.in/content/electrochromic-device-ecd-cell-characterization-electron-beam-evaporated-moo3-films-001986nas a2200229 4500008004100000022001400041245013900055210006900194260006100263300001000324490000800334520112700342653002001469653001401489653001301503653001901516653001701535653001201552100003201564700003001596856013001626 2007 eng d a1011-372X00aFabrication of an effusive molecular beam instrument for surface reaction kinetics - CO oxidation and NO reduction on Pd(111) surfaces0 aFabrication of an effusive molecular beam instrument for surface a233 SPRING STREET, NEW YORK, NY 10013 USAbSPRINGERcNOV a50-580 v1193 a

A simple molecular beam instrument (MBI) was fabricated for measuring the fundamental parameters in catalysis such as, sticking coefficient, transient and steady state kinetics and reaction mechanism of gas/vapor phase reactions on metal surfaces. Important aspects of MBI fabrication are given in detail. Nitric oxide (NO) decomposition and NO reduction with carbon monoxide (CO) on Pd(111) surfaces were studied. Interesting results were observed for the above reactions and they support the efficiency of the MBI to derive the fundamental parameters of adsorption and catalysis. Sustenance of CO oxidation at 400 K is dependent mostly on the absence of CO-poisoning; apparently, CO + O recombination is the rate determining step <= 400 K. NO adsorption measurements on Pd(111) surface clearly indicating a typical precursor kinetics. Displacement of the chemisorbed CO by NO on Pd(111) surfaces was observed directly with NO + CO beams in the transient kinetics. It is also relatively easy to identify the rate-determining step directly from the MBI data and the same was demonstrated for the above reactions.

10acarbon monoxide10acatalysis10akinetics10amolecular beam10anitric oxide10aPd(111)1 aThirunavukkarasu, Kandasamy1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/fabrication-effusive-molecular-beam-instrument-surface-reaction-kinetics-co-oxidation-and-002409nas a2200217 4500008004100000022001400041245007200055210006900127260007300196300001000269490000800279520165000287653002301937653002001960653001801980653002801998653001102026100002402037700003002061856010002091 2007 eng d a0926-860X00aSelective mono-N-methylation of aniline substrates on Cu1-xZnxFe2O40 aSelective monoNmethylation of aniline substrates on Cu1xZnxFe2O4 aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcMAR a64-680 v3203 a

Selective mono-N-methylation of substituted anilines (o-, m- and p-toluidines, 2,6-xylidine, p-anisidine and p-aminoacetophenone) was carried out with methanol as methylating agent under vapor phase reaction conditions on Cu1-xZnxFe2O4 systems. The catalytic reactions with each aniline substrate were carried out at optimum reaction conditions (MeOH:anilines:water = 3: 1: 1, space velocity = 3.58 h(-1)) between 543 and 603 K. The presence of a ring-directing group did not have any significant influence on the N-methylaniline(s) selectivity, which remains very high; the same initial conversion/yield was observed for at least 11 h. Electronic effects due to different groups in the above aniline substrates influence the reactivity of the substrates in terms of conversion and yield. Toluidine reactivity varies with respect to the position (ortho, meta and para) of the methyl group on the phenyl ring. Para-substituted anilines (p-toluidine and p-anisidine) exhibit comparable catalytic activity, while p-aminoacetophenone shows higher conversion. The perpendicular orientation of toluidine substrates on catalyst surfaces influences the conversion and N-methyltoluidine yield. Increased crowding at ortho-position and hence steric hindrance (aniline > o-toluidine > 2,6-xylidine) restrict the substrates interaction with the catalyst surface, and 2,6-xylidine shows no reactivity. The best catalytic activity observed with Cu0.5Zn0.5Fe2O4 was due to a heterogeneous distribution of metal ions on the surface with Zn serving as active spacer group as well as methyl species source. (c) 2007 Elsevier B.V. All rights reserved.

10amono-N-methylation10aN-methylaniline10aN-methylation10aselective N-methvlation10aspinel1 aVijayaraj, Munusamy1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/selective-mono-n-methylation-aniline-substrates-cu1-xznxfe2o402066nas a2200253 4500008004100000022001400041245013000055210006900185260010600254300001400360490000700374520107300381653002501454653001301479653001901492653002801511653004301539100001601582700002201598700001701620700003001637700002001667856012501687 2008 eng d a1359-645400aEffect of fuel and its concentration on the nature of Mn in Mn/CeO2 solid solutions prepared by solution combustion synthesis0 aEffect of fuel and its concentration on the nature of Mn in MnCe aTHE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLANDbPERGAMON-ELSEVIER SCIENCE LTDcAPR a1461-14720 v563 a

Nano and microcrystalline, Mn/CeO2 solid solutions (5 mol.% Mn) have been prepared by solution combustion synthesis using urea, glycine or polyethylene glycol (PEG) as fuel. The nature of the fuel and its concentration (fuel to metal mole ratio, F/M have a strong influence on the physical and chemical characteristics of the resulting Mn/CeO2 solid solutions. The variations in the physicochemical properties are attributed to differences in (i) the adiabatic/real flame temperature realized with these fuels at different F/M ratios; (ii) the sustenance of the temperature or the quenching effect of the fuel at higher F/M ratios; (iii) combustion or decomposition of the precursors as the main course of the reaction; and (iv) the generation of gaseous products during combustion. Since the addition of the fuel to the initial precursor solution does not change the pH of the medium, the differences in the type of Mn species formed are mainly attributed to the combustion process. (C) 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

10aCombustion synthesis10aMn-ceria10aNanocomposites10aX-ray diffraction (XRD)10aX-ray photoelectron spectroscopy (XPS)1 aMurugan, B.1 aRamaswamy, A., V.1 aSrinivas, D.1 aGopinath, Chinnakonda, S.1 aRamaswamy, Veda uhttp://library.ncl.res.in/content/effect-fuel-and-its-concentration-nature-mn-mnceo2-solid-solutions-prepared-solution-001547nas a2200205 4500008004100000022001400041245009600055210006900151260007100220300001400291490000800305520074500313100001901058700003501077700002701112700003001139700001901169700002601188856012701214 2008 eng d a1932-744700aMCM-41-supported organometallic-derived nanopalladium as a selective hydrogenation catalyst0 aMCM41supported organometallicderived nanopalladium as a selectiv a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUN a9428-94330 v1123 a

Palladium nanocatalysts have been prepared by anchoring (eta(3)-C(3)H(5))(2)Pd(2)Cl(2) onto dian-tine-functionalized MCM-41 supports followed by reaction with hydrogen under catalytic conditions. The catalyst precursor and used catalyst have been studied by solid-state NMR ((13)C, (29)Si), XPS, and TEM. The organometallic-derived catalyst exhibits the best performance (activity and selectivity) to date toward the selective hydrogenation of industrially relevant o- and m-chloronitrobenzene to the corresponding chloroaniline derivatives and is distinctly superior to 5% Pd/C. Grazing angle XPS studies reveal that conversion of the tethered molecular species to the nanoparticles of palladium produces a core-shell nanostructure.

1 aMaity, Niladri1 aRajamohanan, Pattuparambil, R.1 aGanapathy, Subramanian1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar uhttp://library.ncl.res.in/content/mcm-41-supported-organometallic-derived-nanopalladium-selective-hydrogenation-catalyst-001232nas a2200265 4500008004100000022001400041245010500055210006900160260007300229300001200302490000800314520025000322653002500572653002600597653002800623653001700651653003100668100001900699700001700718700002900735700003000764700001900794700002600813856012700839 2008 eng d a0926-860X00aMCM-41-supported ruthenium carbonyl cluster-derived catalysts for asymmetric hydrogenation reactions0 aMCM41supported ruthenium carbonyl clusterderived catalysts for a aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJUL a124-1300 v3443 a

{The anionic ruthenium carbonyl cluster [Ru-4(mu-H)(3)(CO)(12)](-) has been ion-paired with (3-chloropropyl)-trimethoxysilyl-cinchonidium or sparteinium groups chemically bound to the surfaces of MCM-41 [(MCM-41-)(-O)(3)SiCH2CH2CH2NR3+Cl-

10aasymmetric catalysis10afunctionalized MCM-4110ahydrogenation catalysts10ananocatalyst10aruthenium carbonyl cluster1 aIndra, Arindam1 aBasu, Susmit1 aKulkarni, Dhanashree, G.1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar uhttp://library.ncl.res.in/content/mcm-41-supported-ruthenium-carbonyl-cluster-derived-catalysts-asymmetric-hydrogenation-002264nas a2200181 4500008004100000022001400041245010000055210006900155260011000224300001200334490000700346520151600353100002101869700003001890700001901920700002601939856011701965 2009 eng d a1463-926200aApplications of a high performance platinum nanocatalyst for the oxidation of alcohols in water0 aApplications of a high performance platinum nanocatalyst for the aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcFEB a554-5610 v113 a

Nanoparticles of platinum (NP-Pt), have been synthesized by supporting high nuclearity anionic carbonyl cluster (Chini cluster) on a water soluble anion exchanger, and the performance of this material, 1, as an oxidation catalyst for alcohols in water has been studied. The E-factor for the synthesis of NP-Pt by this method has been calculated and compared with that of other NP-Pt recently reported in the literature. With 1 as a catalyst, oxidations of a variety of primary and secondary alcohols by dioxygen are achieved and high turnover numbers and selectivities are obtained. The performances of 1 in the oxidation of benzyl alcohol and 1-phenylethanol are compared with those of three other platinum catalysts. These are platinum nanoparticles 2 prepared by the hydrogen reduction of [PtCl6](2-) supported on the same water soluble polymer, 5% Pt on carbon, and 5% Pt on alumina, designated as 3 and 4, respectively. 1 has been found to be considerably more active than 2- 4 and also other reported water soluble platinum nanocatalysts. After many turnovers (similar to 1000 and similar to 165 for benzyl alcohol and 1-phenyl ethanol, respectively) partial deactivation (similar to 40%) is observed, but the deactivated catalyst can be fully regenerated by treatment with dihydrogen. The TEM data of fresh, deactivated and regenerated 1 show a correlation between the particle size and activity. A mechanism consistent with this and other experimental observations including XPS data is proposed.

1 aMaity, Prasenjit1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar uhttp://library.ncl.res.in/content/applications-high-performance-platinum-nanocatalyst-oxidation-alcohols-water-001986nas a2200157 4500008004100000022001400041245009000055210006900145260007100214300001200285490000700297520137400304100001701678700003001695856010301725 2009 eng d a0897-475600aCombustion synthesis of triangular and multifunctional ZnO1-xNx (x <= 0.15) materials0 aCombustion synthesis of triangular and multifunctional ZnO1xNx x a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJAN a351-3590 v213 a

The preparation and characterization of multifunctional ZnO1-xNx (x <= 0.15) via a simple solution combustion method is reported. ZnO1-xNx exhibits visible light absorption, thermal stability, nanometer-/ micrometer-sized triangular particles, and catalytic properties. X-ray diffraction studies of ZnO1-xNx, demonstrate that the lattice oxygen in ZnO is replaced by nitrogen without any major change in the wurtzite structure; however, charge compensation occurs, because of interstitial Zn atoms, as well as oxygen vacancies. Microscopic studies reveal the dominance of nanometer- and micrometer-sized triangles of ZnO1-xNx. UV-visible and Raman spectra indicate a midgap state, derived from N 2p states, and direct Zn-N interaction, respectively. Secondary ion mass spectrometry studies show the presence of N and ZnN species in the bulk and support the direct Zn-N interaction. Electron paramagnetic resonance (EPR) studies indicate the presence of a small amount of defects. Photocatalytic decomposition of rhodamine B, and anisole acylation at room temperature, highlights the effectiveness of ZnO1-xNx to catalysis applications. The aforementioned multifunctional characteristics suggest that ZnO1-xNx might be used in place of conventional ZnO for better control and that it might be explored for further applications in catalysis and optoelectronics.

1 aMapa, Maitri1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/combustion-synthesis-triangular-and-multifunctional-zno1-xnx-x-002313nas a2200241 4500008004100000022001400041245011900055210006900174260008900243300001200332490000800344520137100352653002601723653002801749653001901777653001401796653001201810653002501822100003201847700003201879700003001911856013001941 2009 eng d a0169-433200aElectronic decoupling of surface layers from bulk and its influence in oxidation catalysis: a molecular beam study0 aElectronic decoupling of surface layers from bulk and its influe aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbInst Phys; Indian Assoc Cutivat ScicOCT a443-4480 v2563 a

Interactions between oxygen and Pd-surfaces have important implications, especially towards oxidation reactions, and influence of subsurface oxygen to oxidation reactions is the focus of the present study. In our efforts to understand the above aspects, CO oxidation reactions have been carried out with mixed molecular beam (MB), consisting CO and O(2), on Pd(1 1 1) surfaces under a wide variety of conditions (T = 400-900 K, CO: O(2) = 7: 1 to 1: 10). A new aspect of the above reaction observed in the transient kinetics regime is the evidence for oxygen diffusion into Pd subsurface layers, and its significant influence towards CO oxidation at high temperatures (>= 600 K). Interesting information derived from the above studies is the necessity to fill up the subsurface layers with oxygen atoms to a threshold coverage (theta(O-sub)), above which the reactive CO adsorption occurs on the surface and simultaneous CO(2) production begins. There is also a significant time delay (G) observed between the onset of oxygen adsorption and CO adsorption (and CO(2) production). Above studies suggest an electronic decoupling of oxygen covered surface and subsurface layers, which is slightly oxidized, from the metallic bulk, which induces CO adsorption at high temperatures and simultaneous oxidation to CO(2). (C) 2009 Elsevier B.V. All rights reserved.

10aElectronic decoupling10aheterogeneous catalysis10amolecular beam10aOxidation10aPd(111)10aSubsurface diffusion1 aThirunavukkarasu, Kandasamy1 aNagarajan, Sankaranarayanan1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/electronic-decoupling-surface-layers-bulk-and-its-influence-oxidation-catalysis-molecular-001616nas a2200241 4500008004100000022001400041245007700055210006900132260007100201300001400272490000700286520077800293100001701071700002101088700001901109700002901128700001801157700002201175700001901197700002401216700003001240856010401270 2009 eng d a0897-475600aElectronic structure and catalytic study of solid solution of GaN in ZnO0 aElectronic structure and catalytic study of solid solution of Ga a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUL a2973-29790 v213 a

Solid solutions of GaN in ZnO (Zn1-zGaz)(O1-xNx) (x and z <= 0.15) have been prepared by simple solution combustion method, Except for minor changes in the lattice contraction, no significant change in the Wurtzite structure was observed. Raman and secondary ion mass spectrometry results show the direct Zn-N and Ga-N bonds in (Zn1-zGaz)(O1-xNx). Visible light absorption and XPS results demonstrate that N 2p states of nitride occupy the states above the O 2p valence band, and hence a change in optical band gap reduction occurs to similar to 2.5 eV from 3.37 eV for ZnO. Significant nitrogen fixation catalytic activity through NH3 formation has been observed at ambient pressure oil virgin (Zn1-zGaz)(O1-xNx) material, indicating its potential as a catalyst.

1 aMapa, Maitri1 aThushara, K., S.1 aSaha, Biswajit1 aChakraborty, Purushottam1 aJanet, C., M.1 aViswanath, R., P.1 aNair, Madhavan1 aMurty, K., V. G. K.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/electronic-structure-and-catalytic-study-solid-solution-gan-zno-001618nas a2200229 4500008004100000022001400041245012400055210006900179260007700248300001000325490000600335520074600341653001501087653001301102653001401115653001401129653002101143100003001164700003201194700003201226856013001258 2009 eng d a1861-472800aKinetic evidence for the influence of subsurface oxygen on palladium surfaces towards CO oxidation at high temperatures0 aKinetic evidence for the influence of subsurface oxygen on palla aPO BOX 10 11 61, D-69451 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcOCT a74-800 v43 a

Transient state kinetics of the catalytic oxidation of CO with 0, on Pd-surfaces has been measured under isothermal conditions by using a molecular beam approach. Systematic studies were carried out as a function of reaction temperature and CO+O(2) composition. With sufficient kinetic evidence, we have demonstrated the positive influence of subsurface oxygen towards CO-adsorption and oxidation to CO, at high temperatures (600-900 K) on Pd-surfaces, and the likely electronic nature of the surface changes with oxygen in the subsurface. These studies also provide a direct proof for CO-adsorption with a significantly reactive sticking coefficient at high temperatures on Pd-surfaces exhibiting a significant subsurface O-coverage.

10aAdsorption10akinetics10aOxidation10aPalladium10asurface analysis1 aGopinath, Chinnakonda, S.1 aThirunavukkarasu, Kandasamy1 aNagarajan, Sankaranarayanan uhttp://library.ncl.res.in/content/kinetic-evidence-influence-subsurface-oxygen-palladium-surfaces-towards-co-oxidation-high-001070nas a2200205 4500008004100000022001400041245010800055210006900163260007100232300001400303490000800317520026600325100002100591700001800612700003200630700002400662700001900686700003000705856012900735 2009 eng d a1932-744700aMgCl2 center dot 4(CH3)(2)CHOH: a new molecular adduct and super active polymerization catalyst support0 aMgCl2 center dot 4CH32CHOH a new molecular adduct and super acti a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcMAY a8556-85590 v1133 a

A new molecular adduct, MgCl(2 center dot)4(CH3)(2)CHOH, has been synthesized and characterized for structural aspects and demonstrated for super active ethylene polymerization activity with TiCl4 to ultrahigh molecular weight polyethylene in high yield.

1 aThushara, K., S.1 aMathew, Renny1 aAjithkumar, Thalasseril, G.1 aRajamohanan, P., R.1 aBhaduri, Sumit1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/mgcl2-center-dot-4ch32choh-new-molecular-adduct-and-super-active-polymerization-catalyst-001661nas a2200205 4500008004100000022001400041245008600055210006900141260007100210300001400281490000800295520088700303100003201190700003201222700003001254700002301284700001701307700002001324856011101344 2009 eng d a1932-744700aNitric oxide reduction with ethanol on palladium surfaces: a molecular beam study0 aNitric oxide reduction with ethanol on palladium surfaces a mole a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUN a9814-98190 v1133 a

Nitric oxide (NO) reduction with ethanol has been carried out with molecular beam instruments in order to understand the influence of ethanol blended gasoline on NO reduction. Maximum NO reduction and nitrogen production was observed between 500 and 600 K. Oxidation products, CO, CO(2), and H(2)O were also observed. Beam switching experiments have been performed between fuel-rich and fuel-lean compositions to demonstrate that the NO reduction can be managed under net oxidizing conditions on Pd surfaces. Nitrogen production only occurs transiently on the relatively clean Pd surface in the oxygen-rich condition due to slow build up and blockage of the reaction by surface oxygen atoms. This shows the need to maintain relatively oxygen free surfaces to manage NO reduction under net-oxidizing conditions by beam oscillation between fuel-rich and fuel-lean compositions.

1 aNagarajan, Sankaranarayanan1 aThirunavukkarasu, Kandasamy1 aGopinath, Chinnakonda, S.1 aCounsell, Jonathan1 aGilbert, Lee1 aBowker, Michael uhttp://library.ncl.res.in/content/nitric-oxide-reduction-ethanol-palladium-surfaces-molecular-beam-study-002218nas a2200229 4500008004100000022001400041245009200055210006900147260009200216300001200308490000600320520138900326653001301715653001801728653001101746653000901757653002901766100001601795700002201811700003001833856012501863 2009 eng d a1533-488000aN,S-Co-doped TiO2 Nanophotocatalyst: synthesis, electronic structure and photocatalysis0 aNSCodoped TiO2 Nanophotocatalyst synthesis electronic structure  a26650 THE OLD RD, STE 208, VALENCIA, CA 91381-0751 USAbAMER SCIENTIFIC PUBLISHERScJAN a423-4320 v93 a

N,S-co-doped anatase-phase TiO2 (N,S-TiO2) nanophotocatalysts were prepared from either benzothiazoline or aminothiol with titanium isopropoxide followed by a systematic thermal decomposition. The chemical nature of S and N in N,S-TiO2 have been identified by XPS to be sulfate and NO-like, respectively. A significant band broadening and red-shift in the UV-visible absorption spectrum of N,S-TiO2 suggests a band gap reduction compared to TiO2. A maximum band-gap narrowing of 0.22 +/- 0.02 eV was observed on N,S-TiO2. Higher energy width observed on N,S-TiO2 is in contrast to 0.13 eV from N-doped TiO2 indicating the sulfate-like species might play a major role in narrowing the band-gap to a Higher level. It is confirmed that the oxidation of N and S to NO and SO42- occurs in the final stage of preparation of N,S-TiO2, during calcination in air. It is predicted that the oxygen associated with sulfate and NO structural features could be crucial in bringing down the energy gap and red shift in optical absorption and the role of sulfur is to facilitate the above. Photocatalytic decomposition of methylene blue has been carried out on N,S-TiO2 shows higher activity than the commercial TiO2 in the visible region. However, sulfate species seems to enhance the activity of N,S-TiO2 marginally compared to N-TiO2, and possible suggestions are given to improve the same.

10anitrogen10aPhotocatalyst10aSulfur10aTiO210aVisible Light Absorption1 aSathish, M.1 aViswanath, R., P.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/ns-co-doped-tio2-nanophotocatalyst-synthesis-electronic-structure-and-photocatalysis-003128nas a2200169 4500008004100000022001400041245006100055210005900116260007100175300001400246490000800260520250700268100003202775700003202807700003002839856008902869 2009 eng d a1932-744700aRevisit to carbon monoxide oxidation on Pd(111) surfaces0 aRevisit to carbon monoxide oxidation on Pd111 surfaces a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcAPR a7385-73970 v1133 a

Carbon monoxide (CO) oxidation on Pd(111) surfaces has been studied by molecular beam methods with mixed molecular beams (CO + O(2)) between 400 and 900 K and a CO:O(2) ratio of 7:1 to 1:10. A new aspect of the above reaction observed in the transient kinetics regime is the evidence for oxygen diffusion into Pd(111) subsurface layers and its significant influence toward CO oxidation at high temperatures (>= 600 K). An overall influence of subsurface oxygen on the kinetics of the CO oxidation reaction is addressed. Interesting information derived from the above studies is the necessity to fill up the subsurface layers with oxygen atoms to a threshold coverage (theta(Osub)), above which the reactive CO adsorption occurs on the surface with subsequent CO(2) production. The above observation Was demonstrated with CO-rich reactant compositions (CO + O(2)) above 600 K via instant oxygen adsorption on Pd surfaces; however, onset of CO adsorption as well as CO(2) production occurs after a time delay. theta(Osub) and the time delay in CO adsorption (and CO(2) production) increase with increasing temperature and with CO-rich compositions. theta(Osub) was measured up to 0.3 monlayer (ML) between 500 and 850 K before the onset of CO adsorption; however, theta(Osub) increases from an insignificant value at <500 K to 0.4 ML at 900 K with a pure O(2) beam. Onset of CO adsorption with a significant sticking coefficient on the Pd surfaces, that is, covered with significant subsurface oxygen, underscores a change in the electronic state of Pd surfaces toward mildly oxidized (or Pd(delta+)), and an electronic decoupling occurs between the bulk and the surface. The jellium model is invoked to demonstrate the changes observed. A similar observation with polycrystalline Pd surfaces suggests the defect sites is one of the channels for oxygen diffusion into subsurfaces. Initial sticking coefficient (s(0)) measurements demonstrate that there is no significant competition between CO and O(2) adsorption from the CO + O(2) mixture between 400 and 600 K, and indeed they are largely independent of each other. The maximum steady-state CO(2) formation rate was observed for a 1:1 CO/O(2) beam composition between 500 and 550 K. However, with a significant theta(Osub) the rate of CO(2) Production in the steady state is considerable even at high temperatures (700-850 K), and a broadening of the active CO oxidation regime to high temperature is observed with O(2)-rich compositions.

1 aNagarajan, Sankaranarayanan1 aThirunavukkarasu, Kandasamy1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/revisit-carbon-monoxide-oxidation-pd111-surfaces-001911nas a2200241 4500008004100000022001400041245010200055210006900157260009200226300001200318490000600330520101100336653001301347653002301360653001801383653001501401653001201416100002901428700002101457700003101478700003001509856013001539 2009 eng d a1533-488000aTemplate free synthesis of mesoporous TiO2 with high wall thickness and nanocrystalline framework0 aTemplate free synthesis of mesoporous TiO2 with high wall thickn a26650 THE OLD RD, STE 208, VALENCIA, CA 91381-0751 USAbAMER SCIENTIFIC PUBLISHERScJAN a371-3770 v93 a

A simple procedure to prepare nanocrystalline mesoporous titania (meso-TiO2) is reported without any templating agent and it possesses a high BET surface area and a large pore wall thickness (11.3 nm) than that of meso-TiO2 prepared by other methods. Nanocrystalline meso-TiO2 also has been synthesized with hexadecylamine template for comparison through known procedure. The meso-TiO2 materials were characterized by X-ray diffraction, FT-IR, UV-Vis absorbance spectra, thermal analysis, SEM, HRTEM and textural properties through N-2 adsorption-desorption isotherms. Spherical shape particles in a range of few hundred nanometers are obtained in the template free method. Above systematic characterization provides direct indications toward the mechanism of formation of meso-TiO2 in the template free method. A comparison of the physical and textural properties indicates a possibility of coarse-tuning of the textural characteristics of mesoporous TiO2 by adopting different preparation methods.

10aMesopore10aMesopore Formation10aTemplate-Free10aThick Wall10atitania1 aKulkarni, Dhanashree, G.1 aMurugan, Vadivel1 aViswanath, Annamraju, Kasi1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/template-free-synthesis-mesoporous-tio2-high-wall-thickness-and-nanocrystalline-framework-001449nas a2200217 4500008004100000022001400041245005000055210004800105260007100153300001400224490000800238520074200246100002000988700002301008700002201031700001701053700001801070700003201088700003001120856008101150 2010 eng d a1932-744700aCarbon dissolution and segregation in Pd(110)0 aCarbon dissolution and segregation in Pd110 a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcMAR a5060-50670 v1143 a

The bulk-surface diffusion of carbon in Pd(110) has been investigated using Molecular beams to examine the clean-off of carbon with gas-phase oxygen. The dominant product of the reaction above 600 K is CO CO, is only produced at much lower temperatures where the lifetime of adsorbed CO is significant. The segregation from the bulk Only Occurs at a measurable rate at >750 K, while loss of carbon into the bulk call occur at much lower temperatures. The reaction of carbon at high temperatures shows two regimes: (i) a non steady-state evolution of CO due to the clean-off of surface carbon already present on the surface, followed by (ii) a near steady-state reaction due to the continuous diffusion of carbon to the surface.

1 aBowker, Michael1 aCounsell, Jonathan1 aEl-Abiary, Kareem1 aGilbert, Lee1 aMorgan, Chris1 aNagarajan, Sankaranarayanan1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/carbon-dissolution-and-segregation-pd110-002253nas a2200301 4500008004100000022001400041245012100055210006900176260013200245300001200377490000600389520113200395653003001527653002001557653001601577653001601593653002701609653002301636653001901659653001401678100001701692700001901709700001901728700002401747700002101771700003001792856012901822 2010 eng d a1475-743500aFabrication of homogeneous nanoparticle/nanoneedle BaTiO3 and Ba0.8Sr0.2TiO3 smooth thin films by simple dip coating0 aFabrication of homogeneous nanoparticlenanoneedle BaTiO3 and Ba0 aWORLD TRADE CENTER BLDG, 29 ROUTE DE PRE-BOIS, CASE POSTALE 896, CH-1215 GENEVA, SWITZERLANDbINDERSCIENCE ENTERPRISES LTDcDEC a919-9310 v73 a

Ferroelectric BaTiO3 (BTO) and Ba0.8Sr0.2TiO3 (BSTO) thin film materials have been successfully prepared by sol-gel processing and simple dip coating on glass and silicon supports. Above thin films were characterised by x-ray diffraction (XRD), Raman spectroscopy, photoelectron spectroscopy, thermal analysis, atomic force microscopy (AFM) and spectroscopic ellipsometry. Phase identification of BaTiO3 and Ba0.8Sr0.2TiO3 was performed by XRD. XRD and Raman spectroscopy investigations demonstrate that thc Ba0.8Sr0.2TiO3 film exhibits tetragonal structure. AFM analysis demonstrates the elongated nanospherical particles on glass substrate and nanowires on silicon substrate, which represent a strong influence of the crystallinity of underlying substrate on the grain morphology in this technique. The thin films on both the substrates are uniformly coated without any pinhole to significant area (similar to 2.5 cm(2)), and this method might be extended to large area uniform coating. Spectroscopic ellipsometric measurements reveal the exact thickness, refractive index and extinction coefficient of the thin films.

10abarium strontium titanate10abarium titanate10adip coating10afabrication10aferroelectric material10alarge area coating10ananotechnology10athin film1 aSaini, Mamta1 aVivekanand, K.1 aPoddar, Pankaj1 aMurty, K., V. G. K.1 aThushara, K., S.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/fabrication-homogeneous-nanoparticlenanoneedle-batio3-and-ba08sr02tio3-smooth-thin-films-001642nas a2200169 4500008004100000022001400041245012100055210006900176260007100245300001600316490000800332520093300340100002101273700001901294700003001313856012901343 2010 eng d a1932-744700aFacile synthesis of N- and S-incorporated nanocrystalline TiO2 and direct solar-light-driven photocatalytic activity0 aFacile synthesis of N and Sincorporated nanocrystalline TiO2 and a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcNOV a19473-194820 v1143 a

Sulfur- and nitrogen-incorporated mesoporous TiO2 (SNT) nanocomposites have been synthesized by a template-free homogeneous coprecipitation technique. The above nanocomposites have been thoroughly characterized by physicochemical and spectroscopy methods to explore the structural, electronic, and optical properties. The photocatalytic activities of the catalysts were evaluated for the degradation of methyl orange and phenol under direct solar light. SNT shows about a 2-fold higher photocatalytic activity than singly N-doped or S-doped mesoporous TiO2 and 3-fold higher than Degussa P25. The higher activity might be attributed to the synergetic interaction of sulfate and nitrogen with the TiO2 lattice. N-Ti-O and O-Ti-N-O environments are responsible for a red shift, and the sulfate group on TiO2 acts as a cocatalyst, for increasing surface acidity as well as for sustaining the redox cycles for high stability.

1 aNaik, Brundabana1 aParida, K., M.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/facile-synthesis-n-and-s-incorporated-nanocrystalline-tio2-and-direct-solar-light-driven-002122nas a2200217 4500008004100000022001400041245011900055210006900174260007100243300001200314490000700326520126200333100001701595700003301612700002001645700001901665700002901684700003101713700003001744856013001774 2010 eng d a0897-475600aStructure, electronic structure, optical, and dehydrogenation catalytic study of (Zn1-zInz)(O1-xNx) solid solution0 aStructure electronic structure optical and dehydrogenation catal a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJAN a565-5780 v223 a

Indium and nitrogen codoping in ZnO leads to a solid solution of InN in ZnO with I composition of(Zn1-zInz)(O1-xNx). A simple solution combustion method has been adopted to prepare the above materials in less than 10 min with metal nitrates as the metal loll source and urea as fuel. With reference to ZnO, significant increase in lattice parameters was observed with increasing In-content. However, the In2O3 phase was Observed along with InN for]it content >= 10%. Optical absorption extended into the Visible region, at least LIP to 550 nm, demonstrates an effective reduction of optical band gap due to the formation of solid Solution. A new feature observed just above O2p valence band in X-ray photoelectron spectroscopy (XPS) suggests the creation of N 2p states from InN; the N Is core level XPS result too confirms nitride contribution. Raman spectroscopy and secondary ion mass spectrometry results show direct In-N, Zn-N. and In-N-Zn fragments in (Zn1-zInz)(O1-x,N-x). Catalytic activity explored for Oxidation of 2-butanol to ethyl methyl ketone demonstrates a high selectivity at 350 and 400 degrees C. All of the above characteristics suggest the multifunctional nature of (Zn1-zInz)(O1-xNx) and its potential for other applications.

1 aMapa, Maitri1 aSivaranjani, Kumarsrinivasan1 aBhange, Deu, S.1 aSaha, Biswajit1 aChakraborty, Purushottam1 aViswanath, Annamraju, Kasi1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/structure-electronic-structure-optical-and-dehydrogenation-catalytic-study-zn1-zinzo1-xnx-001754nas a2200181 4500008004100000022001400041245011700055210006900172260007100241300001600312490000800328520099400336100003201330700003201362700003001394700002501424856012301449 2011 eng d a1932-744700aKinetics of nitric oxide adsorption on Pd(111) surfaces through molecular beam experiments: a quantitative study0 aKinetics of nitric oxide adsorption on Pd111 surfaces through mo a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcAUG a15487-154950 v1153 a

A detailed kinetic picture derived by molecular beam studies of the adsorption-desorption of the NO/Pd(111) system is presented. Numerical simulations and detailed kinetic analysis show that the precursor state model of adsorption provides a valid picture of the sticking coefficient variation with surface coverage, especially at low temperatures. At higher temperatures, the precursor model gives way to the Langmuir molecular model of adsorption. All the parameters of the precursor state model have been quantified. Temperature programmed desorption (TPD) studies further show that there is a slight repulsive interaction between adsorbed NO molecules and there is only a negligible fraction of dissociated molecules on the surface for temperatures less than 500 K, as the Pd(111) surface is defect free. A Bragg-Williams (BW) lattice gas model with repulsive interactions, within the framework of mean field approach (MFA), is shown to describe the TPD spectra reasonably well.

1 aNagarajan, Sankaranarayanan1 aThirunavukkarasu, Kandasamy1 aGopinath, Chinnakonda, S.1 aPrasad, Sudarsan, D. uhttp://library.ncl.res.in/content/kinetics-nitric-oxide-adsorption-pd111-surfaces-through-molecular-beam-experiments-002639nas a2200253 4500008004100000022001400041245022900055210006900284260006900353300001200422490000800434520157900442653001902021653001402040653002702054653002902081100003302110700002202143700002602165700001902191700003002210700002002240856012502260 2011 eng d a0020-169300aLigand dynamics controlled reverse spin cross over in bis pyrazolyl pyridine based Fe(II) complex cation with metallodithiolato anions with an example of a ferromagnetic 2:1 cocrystal of mixed Ni(III)/Ni(II) oxidation states0 aLigand dynamics controlled reverse spin cross over in bis pyrazo aPO BOX 564, 1001 LAUSANNE, SWITZERLANDbELSEVIER SCIENCE SAcAUG a586-6000 v3743 a

We report here the crystal and molecular structures of three compounds [FeL(2)] [Ni(mnt)(2)] (1), [FeL(2)](2) [Ni(mnt)(2)](3)center dot 2H(2)O (2) and [FeL(2)] [Cu(mnt)(2)]center dot 2CH(3)CN (3) where L = 2,6-bis(3,5-dimethylpyrazol-1-ylmethyl) pyridine and mnt = maleonitriledithiolate, and their detailed spectroscopic and magnetic properties using variable temperature Mssbauer, EPR, susceptibility studies, along with room temperature electron spectroscopy for chemical analysis (ESCA) studies. The observed temperature dependant high spin/low spin (HS/LS) ratios of [FeL(2)](2+) cations in these lattices, exhibiting `reverse spin cross-over' measured unequivocally by Mssbauer, have been interpreted as resulting from differing amount of `void space' in the lattice, a measure of the ease of lattice dynamics originating from ligand L. Differential scanning calorimetric data points this HS/LS transition to order-disorder type of second order phase transitions. While trying to test this lattice dynamics controlled property of [FeL(2)](2+) cations an unusual behavior of cocrystallization of two planar complex anions of the same type in two different oxidation states, viz. [Ni(mnt)(2)](2) and [Ni(mnt)(2)] , was observed in [FeL(2)](2+) [Ni(mnt(2))](3), supported by crystallography, ESCA chemical shifts of Ni 2p(3/2) and EPR. The susceptibility data in combination with ESCA chemical shifts of S 2p(3/2) and Ni 2p(3/2) on all the compounds reveal the importance of charge transfer between the two counter ions. (C) 2011 Elsevier B.V. All rights reserved.

10aIron complexes10aMagnetism10aReverse-spin crossover10aX-ray crystal structures1 aManoharan, Periakaruppan, T.1 aSambandam, Balaji1 aAmsarani, Ramamoorthy1 aVarghese, Babu1 aGopinath, Chinnakonda, S.1 aNomura, Kiyoshi uhttp://library.ncl.res.in/content/ligand-dynamics-controlled-reverse-spin-cross-over-bis-pyrazolyl-pyridine-based-feii-001845nas a2200229 4500008004100000022001400041245015600055210006900211260011000280300001600390490000700406520088500413100002601298700002101324700002001345700001801365700003201383700002401415700001901439700003001458856012701488 2011 eng d a1477-922600aMgCl2 center dot 6PhCH(2)OH - a new molecular adduct as support material for ziegler-natta catalyst: synthesis, characterization and catalytic activity0 aMgCl2 center dot 6PhCH2OH a new molecular adduct as support mate aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcSEP a10936-109440 v403 a

Benzyl alcohol has been used to prepare a single phase MgCl2 center dot 6BzOH molecular adduct as a support for an ethylene polymerization catalyst (Ziegler catalyst). The structural, spectroscopic and morphological aspects of the MgCl2 center dot 6BzOH molecular adduct and the Ziegler catalyst have been thoroughly studied by various physicochemical characterization techniques. The presence of MgO6 octahedrons due to the interaction of Mg2+ with six -OH groups of the benzyl alcohol is confirmed from a Raman feature at 703 cm(-1), and structural studies. The supported catalyst activity has been evaluated for the ethylene polymerization reaction. The lower polymerization activity of the titanated Ziegler-Natta catalyst compared with a standard catalyst is attributed to the strong interaction of titanium chloride with the support and associated electronic factors.

1 aGnanakumar, Edwin, S.1 aThushara, K., S.1 aBhange, Deu, S.1 aMathew, Renny1 aAjithkumar, Thalasseril, G.1 aRajamohanan, P., R.1 aBhaduri, Sumit1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/mgcl2-center-dot-6phch2oh-new-molecular-adduct-support-material-ziegler-natta-catalyst-001836nas a2200157 4500008004100000022001400041245009500055210006900150260011000219300001400329490000700343520114000350100003301490700003001523856012501553 2011 eng d a0959-942800aPorosity driven photocatalytic activity of wormhole mesoporous TiO2-xNx in direct sunlight0 aPorosity driven photocatalytic activity of wormhole mesoporous T aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJAN a2639-26470 v213 a

Results obtained by combining four important factors simultaneously, namely, wormhole mesoporosity with low diffusion length for charge carriers, high surface area, nanoparticles with high crystallinity, and visible light absorption due to N-doping, in titania (meso-TiO2-xNx) are reported. Meso-TiO2-xNx materials have been prepared by a combustion method within 10 min and by varying urea : Ti(NO3)(4) between 1 (UT1) and 10 (UT10). All of the prepared materials have been thoroughly characterised. Nanocrystalline anatase phase with high surface area (234 m(2) g(-1)), and type-IV H-3-mesoporosity is observed with UT10. Photocatalytic rhodamine-B degradation was employed to screen for the activity of the materials, and p-anisyl alcohol oxidation to p-anisaldehyde was carried out successfully in aqueous solution under direct sunlight. High photocatalytic activity of UT10 in direct sunlight, in spite of high band gap (3.24 eV), is attributed to the better utilization of holes due to the low charge diffusion barrier associated with wormhole mesoporosity along with highly crystalline, however, nanoparticulate TiO2-xNx.

1 aSivaranjani, Kumarsrinivasan1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/porosity-driven-photocatalytic-activity-wormhole-mesoporous-tio2-xnx-direct-sunlight-002257nas a2200169 4500008004100000022001400041245013600055210006900191260007100260300001600331490000800347520150700355100003201862700003201894700003001926856013101956 2011 eng d a1932-744700aPossible deNO(x) management under net oxidizing conditions: a molecular beam study of (NO)-N-15+CO+O-2 reaction on Pd(111) surfaces0 aPossible deNOx management under net oxidizing conditions a molec a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcNOV a21299-213100 v1153 a

Isothermal kinetic measurements of (NO)-N-15 reduction with CO on Pd(111) surfaces were carried out under net-oxidizing conditions with (NO)-N-15 + CO + O-2, using a molecular beam instrument (MBI). Transient state (TS) and steady state (SS) kinetic details of the above reaction were obtained for a wide range of temperature and beam compositions, especially with O-2-rich compositions. Increasing O-2 content, generally, suppresses (NO)-N-15 reduction in the SS; nonetheless, irrespective of O-2 content, N-15(2) was produced in TS, and to a significant extent under SS conditions too. Sustainable N-2 production between 450 and 600 K and with low to moderate amount of oxygen was observed, and the extent of NO decomposition was also quantified. The ratio of N-15(2): (N2O)-N-15 was generally found to be around 8:1 under most of the reaction conditions. Maxima in the SS reaction rates of all products were observed between 500 and 600 K. Compared to other elementary reaction steps, a slow decay observed with N + N -> N-2 step under SS beam oscillation conditions demonstrates its contribution to the rate limiting nature of the overall reaction. Fast beam switching experiments have been performed alternately between O-2-lean and -rich conditions, thus highlighting the effectiveness of (NO)-N-15 reduction in TS, irrespective of the beam composition. Possibly in a future technology initiative, this aspect could be exploited to manage more (NO)-N-15 reduction on Pd-based catalysts.

1 aNagarajan, Sankaranarayanan1 aThirunavukkarasu, Kandasamy1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/possible-denox-management-under-net-oxidizing-conditions-molecular-beam-study-no-n-15coo-2-001984nas a2200253 4500008004100000022001400041245011600055210006900171260007300240300001200313490000800325520103000333653002401363653002401387653002701411653001101438653002801449100001901477700003501496700003001531700001901561700002601580856012401606 2011 eng d a0926-860X00aSelective hydrogenation of chloronitrobenzenes with an MCM-41 supported platinum allyl complex derived catalyst0 aSelective hydrogenation of chloronitrobenzenes with an MCM41 sup aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcMAY a117-1250 v3993 a

A platinuin precatalyst (1) has been prepared by reacting [(eta(3)-C3H5)(4)Pt4Cl4] with surface functionalized MCM-41 with pendant -(CH2)(3)NH(CH2)(2)NH2 groups. For the hydrogenation of o-, m- and p-chloronitrobenzenes to the corresponding chloroanilines, 1 is found to be a highly active catalyst with good selectivities for them-and p-isomers. Its performance is superior to that of its palladium analogue and far superior to that of commercial (5%) Pt/C or (5%) Pt/Al2O3. Comparison of solid state and solution NMR data and other evidences indicate that on treatment with the functionalized MCM-41 support; [(eta(3)-C3H5)(4)Pt4Cl4] loses the ally! ligand. XPS data show that in the fresh catalyst Pt is present in the 2+ oxidation state. Based on these and analytical data, co-ordination by surface diamine and hydroxo groups to Pt2+ in 1 is suggested. In the used catalyst both Pt2+ and Pt are present but the amount of metallic platinum is similar to 16% of the total. (C) 2011 Elsevier B.V. All rights reserved.

10aChloronitrobenzenes10aDehydrohalogenation10aheterogeneous catalyst10aMCM-4110aSelective hydrogenation1 aIndra, Arindam1 aRajamohanan, Pattuparambil, R.1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar uhttp://library.ncl.res.in/content/selective-hydrogenation-chloronitrobenzenes-mcm-41-supported-platinum-allyl-complex-002023nas a2200253 4500008004100000022001400041245014100055210006900196260007100265300001400336490000800350520104100358100002101399700002601420700001801446700002401464700003201488700002401520700001901544700002601563700001901589700003001608856013101638 2011 eng d a1932-744700aToward an understanding of the molecular level properties of ziegler-natta catalyst support with and without the internal electron donor0 aToward an understanding of the molecular level properties of zie a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcFEB a1952-19600 v1153 a

Two Ziegler-Natta catalysts supported on molecular adducts, namely, MgCl2 center dot 6EtOH (ME) and MgCl2 center dot 5EtOH center dot EtOOCPh (Est-ME), have been prepared. A systematic effort has been made to unravel the molecular level structure property relationships of the catalysts and adducts. Ethylbenzoate is an internal electron donor, and its in situ formation through EtOH+PhCOCl coupling is successfully achieved. The above adduct has been treated with TiCl4, and the resultant catalyst (Ti/Est-ME) is evaluated for ethylene polymerization activity. Rand C-13 CP/MAS NMR of Est-ME (Ti/Est-ME) show carbonyl features at 1730 (1680) cm(-1) and 169 (170) delta, respectively, providing direct support for the presence of ester as an integral part. In spite of low surface area, Ti/Est-ME gives higher yield for ethylene polymerization than the one derived from ME. The results indicate that electronic environment is more important than surface area or any other single factor in determining the polymerization activity.

1 aThushara, K., S.1 aGnanakumar, Edwin, S.1 aMathew, Renny1 aJha, Ratnesh, Kumar1 aAjithkumar, Thalasseril, G.1 aRajamohanan, P., R.1 aSarma, Krishna1 aPadmanabhan, Sudhakar1 aBhaduri, Sumit1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/toward-understanding-molecular-level-properties-ziegler-natta-catalyst-support-and-without-001400nas a2200181 4500008004100000022001400041245009200055210006900147260007100216300001400287490000800301520068900309100002600998700002601024700003001050700001801080856012001098 2012 eng d a1932-744700aEvidence of cationic Pt active for water-gas shift reaction: Pt-doped BaCeO3 perovskite0 aEvidence of cationic Pt active for watergas shift reaction Ptdop a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcMAY a9526-95320 v1163 a

Precious metal incorporated into stable lattices like perovskites can be envisaged as an alternative catalysts to address deactivation problems. Here we report the barium cerate perovskite doped with varying amounts of Pt as catalysts for the water-gas shift reaction whereby ionic Pt is evidenced to be active. It is found that maximum CO conversion occurs above 325 degrees C and increases more than 2-fold after the first cycle. XPS analysis shows that after the first cycle, more ionic Pt species are present on the surface of the catalyst. X-ray and neutron diffraction studies also indicate the presence of oxygen vacancies that increases with increasing Pt substitution.

1 aRajesh, Thattarathody1 aRajarajan, Anakot, K.1 aGopinath, Chinnakonda, S.1 aDevi, Nandini uhttp://library.ncl.res.in/content/evidence-cationic-pt-active-water-gas-shift-reaction-pt-doped-baceo3-perovskite-003049nas a2200205 4500008004100000022001400041245013800055210006900193260011000262300001600372490000700388520217100395100001902566700003302585700002602618700001902644700002502663700003002688856012502718 2012 eng d a0959-942800aGamma-Al2-xMxO3 +/- y (M = Ti4+ through Ga3+): potential pseudo-3D mesoporous materials with tunable acidity and electronic structure0 aGammaAl2xMxO3 y M Ti4 through Ga3 potential pseudo3D mesoporous  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcAPR a13484-134930 v223 a

A simple and highly efficient surfactant-free sol-gel process has been developed to obtain nanocrystalline mesoporous gamma-Al2O3 and metal ion incorporated mesoporous gamma-Al2O3 with general formula gamma-Al2-xMxO3 +/- y (where M = Ti4+ through Ga3+). Any one of the first row transition metal (TM) ions along with Ga3+ could be introduced into the gamma-Al2O3 framework in a direct one-pot synthesis process. The generality of the present synthesis recipe for metal ion incorporation in gamma-Al2O3 was demonstrated by preparation of an Al-Ga-M ternary oxide system with the metal ion composition of general formula Al9GaTM (TM = Ti4+ to Zn2+) and their characterization through various physicochemical and spectroscopic techniques. The mesoporous gamma-Al2-xMxO3 +/- y materials showed a BET surface area in the range of 200-400 m(2) g(-1) with a narrow pore size distribution. Wormhole mesoporosity makes the material pseudo-3D (p3D) with a small pore depth of few nm (<10 nm). Metal ions in gamma-Al2O3 lead to changes in the acidity and electronic environment. XRD, TEM, and Al-27 MAS NMR studies demonstrate that the sol-gel process and the disordered mesoporous structure allow Ga and TM ions to be highly distributed and integrated in the gamma-Al2O3 framework. The efficacy of these materials in catalysis has been successfully evaluated for steam reforming of dimethylether: Ni, Cu and Zn containing Al9GaTM oxides showed high activity and stability. The smaller mesochannel depth (<10 nm) and pseudo-3D characteristics that arise due to the wormhole-type disordered mesoporous framework of these alumina materials facilitate mass transport through them without any leaching of metal ions out of the lattice and pore blocking during the reaction, which makes them attractive in catalysis. This preparation method is versatile enough to be used for a reproducible synthesis of metal ion incorporated mesoporous gamma-Al2O3 by varying the metal content and their combinations, and it is expected that many other metal ions could be introduced into the lattice framework for a variety of applications by tuning acidity and electronic structure.

1 aMathew, Thomas1 aSivaranjani, Kumarsrinivasan1 aGnanakumar, Edwin, S.1 aYamada, Yusuke1 aKobayashi, Tetsuhiko1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/gamma-al2-xmxo3-y-m-ti4-through-ga3-potential-pseudo-3d-mesoporous-materials-tunable-001977nas a2200217 4500008004100000022001400041245013400055210006900189260011000258300001600368490000700384520106800391100002101459700002601480700001801506700003201524700002401556700001901580700003001599856013001629 2012 eng d a1477-922600aMgCl2 center dot 4((CH3)(2)CHCH2OH): a new molecular adduct for the preparation of TiClx/MgCl2 catalyst for olefin polymerization0 aMgCl2 center dot 4CH32CHCH2OH a new molecular adduct for the pre aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJUL a11311-113180 v413 a

A new molecular adduct of MgCl2 with isobutanol, namely MgCl2 center dot 4((CH3)(2)CHCH2OH) (MgiBOH), has been prepared as a precursor to the supporting material for an olefin polymerization catalyst. The MgiBOH adduct and final titanated Ziegler-Natta catalysts have been thoroughly characterized by powder XRD, thermal analysis, Raman spectroscopy and solid-state NMR for structural and spectroscopy aspects. A peak observed at 712 cm(-1) in the Raman spectra of MgiBOH indicates the characteristic Mg-O-6 breathing mode and the formation of the adduct. The diffraction feature at 2 theta = 7.8 degrees (d = 11.223 angstrom) in the XRD confirms the adduct formation and the layered structure. The aim of the present article is to study how the insertion of a bulky isobutanol moiety affects the structural and electronic properties of the MgCl2 isobutanol molecular adduct. Indeed, the focus of the present study is to explore how the presence of isobutanol, in the initial molecular adduct, influences the final Z-N catalyst properties and its activity.

1 aThushara, K., S.1 aGnanakumar, Edwin, S.1 aMathew, Renny1 aAjithkumar, Thalasseril, G.1 aRajamohanan, P., R.1 aBhaduri, Sumit1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/mgcl2-center-dot-4ch32chch2oh-new-molecular-adduct-preparation-ticlxmgcl2-catalyst-olefin-002011nas a2200229 4500008004100000022001400041245009200055210006900147260007100216300001600287490000800303520114700311100002601458700002101484700002501505700002201530700003201552700002401584700002601608700003001634856011701664 2012 eng d a1932-744700aMgCl2 center dot 6C(6)H(11)OH: a high mileage porous support for ziegler-natta catalyst0 aMgCl2 center dot 6C6H11OH a high mileage porous support for zieg a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcNOV a24115-241220 v1163 a

A new and single phase molecular adduct of MgCl2 with six cyclohexanol molecules MgCl2 center dot 6C(6)H(11)OH (MgCyOH) has been synthesized. Structural insight to this adduct was obtained by a variety of physicochemical methods. C-13 CPMAS spectrum and single pulse MAS spectra with high power proton decoupling recorded at different relaxation time showed the presence of two different sets of magnetically unequal cylcohexanol molecules present around Mg2+. A Raman feature of MgCyOH at 712 cm(-1) confirms that cylcohexanol molecules are present around Mg2+ in an octahedral environment. MgCyOH has been used as support material to prepare Ziegler-Natta (Z-N) active catalyst. Textural property of above Z-N catalyst exhibits high surface area (236 m(2)/g) with high porosity. Above active catalyst has been screened for ethylene polymerization. Depending on the cocatalyst employed (Me3Al, Et3Al, and iso-Bu3Al) and ethylene pressure, polyethylene yield varies an order of magnitude, from 378 to 3570 g/g catalyst, indicating a possible creation of different active sites and different interaction between cocatalyst and catalyst.

1 aGnanakumar, Edwin, S.1 aThushara, K., S.1 aGowda, Ravikumar, R.1 aRaman, Sumesh, K.1 aAjithkumar, Thalasseril, G.1 aRajamohanan, P., R.1 aChakraborty, Debashis1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/mgcl2-center-dot-6c6h11oh-high-mileage-porous-support-ziegler-natta-catalyst-002141nas a2200169 4500008004100000022001400041245011400055210006900169260011000238300001200348490000700360520139400367100003301761700001801794700003001812856012901842 2012 eng d a1463-926200aMolecular oxygen-assisted oxidative dehydrogenation of ethylbenzene to styrene with nanocrystalline Ti1-xVxO20 aMolecular oxygenassisted oxidative dehydrogenation of ethylbenze aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcDEC a461-4710 v143 a

Oxidative dehydrogenation of ethylbenzene to styrene has been studied with vanadium-incorporated mesoporous nanocrystalline titania (Ti1-xVxO2) and molecular oxygen between 440 and 530 degrees C. Incorporation of V in TiO2 lattice framework has been achieved by simple solution combustion method. Incorporation of V in TiO2 lattice has been confirmed by X-ray diffraction, XPS and Raman spectra and other physicochemical analysis. High ethyl benzene conversion and stable styrene yield has been observed with 10% V-containing rutile phase titania at 500 degrees C. However, stable but relatively lower styrene yield has been observed with 2 and 5% V-containing catalysts between 440 and 500 degrees C. Highest selectivity is observed with lower vanadium content. Comparable activity has been observed under similar experimental conditions with four times higher air-flow than that of O-2. In order to understand the structure activity relationship, spent catalysts were analyzed by all physico-chemical methods. Although there is a phase change from anatase to rutile Ti1-xVxO2 within 1 h of reaction, higher activity is primarily attributed to the ionic V5+ in Ti1-xVxO2 lattice, which prevents agglomeration to V2O5. It is to be underscored the reactivity is retained at the cost of textural properties and phase change from anatase to rutile, which is essential for the reaction.

1 aSivaranjani, Kumarsrinivasan1 aVerma, Akrati1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/molecular-oxygen-assisted-oxidative-dehydrogenation-ethylbenzene-styrene-nanocrystalline-001510nas a2200229 4500008004100000022001400041245008800055210006900143260007300212300001000285490000800295520067000303653002200973653001700995653001901012653002201031100002501053700003301078700003001111700001801141856012101159 2012 eng d a0920-586100aSimple one pot synthesis of nano gold-mesoporous silica and its oxidation catalysis0 aSimple one pot synthesis of nano goldmesoporous silica and its o aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcDEC a92-970 v1983 a

A simple one pot synthesis strategy using a non ionic triblock copolymer P123 as reducing as well as templating agent has been employed to prepare nano gold particles incorporated in the pores of mesoporous silica catalyst. The catalyst is characterized by XRD, nitrogen adsorption desorption isotherms at 77 K and TEM. The presence of small gold nanopartilces (similar to 2-4 nm) clearly demonstrated that this strategy can be effective in incorporating Au inside mesochannels. The catalyst reduced at 300 degrees C in H-2 was found to be active for oxidation reactions, such as CO oxidation, and benzyl alcohol. (C) 2012 Elsevier B. V. All rights reserved.

10aAlcohol oxidation10aCO oxidation10aGold catalysis10aMesoporous silica1 aSekhar, A., C. Sunil1 aSivaranjani, Kumarsrinivasan1 aGopinath, Chinnakonda, S.1 aVinod, C., P. uhttp://library.ncl.res.in/content/simple-one-pot-synthesis-nano-gold-mesoporous-silica-and-its-oxidation-catalysis-002144nas a2200181 4500008004100000022001400041245015800055210006900213260007100282300001400353490000800367520134000375100003301715700002401748700002901772700003001801856013101831 2012 eng d a1932-744700aToward a quantitative correlation between microstructure and DSSC efficiency: a case study of TiO2-xNx nanoparticles in a disordered mesoporous framework0 aToward a quantitative correlation between microstructure and DSS a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJAN a2581-25870 v1163 a

The efficiency (eta) of a dye-sensitized solar cell (DSSC) depends on various parameters, the critical factors being a fast charge carrier transport and a slow rate of electron-hole recombination. The present article describes a simple combustion synthesis method to prepare TiO2-xNx with following four important features that directly influences eta: (1) a disordered mesoporous structural framework with high surface area to give high dye-loading and a small diffusion length for charge carriers allowing rapid movement to the surface; (2) electrically interconnected nanocrystalline TiO2-xNx particles with good necking and predominant (101) anatase facets to minimize electron-hole recombination; (3) low charge storage capacity in the titania framework; and (4) surface unsaturation assisting all the above factors. The pseudo-three-dimensional nature of mesoporous TiO2-xNx with the above features demonstrates the importance of textural features, and porosity allows faster diffusion of charge carriers to surface and their utilization to generate power. A quantitative correlation between interconnected nanoparticles over larger distances in a mesoporous framework and eta is demonstrated. This study also demonstrates an inexpensive and rapid method of producing the photoanode material with high eta in about 10 min.

1 aSivaranjani, Kumarsrinivasan1 aAgarkar, Shruti, A.1 aOgale, Satishchandra, B.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/toward-quantitative-correlation-between-microstructure-and-dssc-efficiency-case-study-tio2-001824nas a2200181 4500008004100000022001400041245013600055210006900191260011000260300001600370490000600386520101500392100002701407700003301434700003001467700002201497856012301519 2013 eng d a2046-206900aAminosilicate sol-gel stabilized N-doped TiO2-Au nanocomposite materials and their potential environmental remediation applications0 aAminosilicate solgel stabilized Ndoped TiO2Au nanocomposite mate aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcMAY a13390-133980 v33 a

A facile chemical reduction method to synthesize amine functionalized silicate sol-gel-supported gold-deposited nitrogen-doped Degussa-TiO2 nanocomposite materials (APS/(N-P25-Au)(NCM)) is reported and the materials are characterized by DRS, PL, XRD, TEM, Raman, XPS and BET surface area analysis. The application of the synthesized APS/(N-P25-Au)(N)CM towards environmental remediation processes are investigated by studying the catalytic oxidation of carbon monoxide (CO) and photocatalytic reduction of toxic mercuric (Hg(II)) ions. The catalytic and photocatalytic activity of the prepared catalysts are found to be in the order of APS/(N-P25-Au)(NCM) >> APS/(P25-Au)(NCM) > N-P25 > P25. The enhanced catalytic and photocatalytic activities of the APS/(N-P25-Au)(NCM) can be attributed to the synergistic effect of Au-nps and N-doped P25. The catalytic activities of the APS/(N-P25-Au)(NCM) are very promising in the field of green technology for the environmental cleaning applications.

1 aPandikumar, Alagarsamy1 aSivaranjani, Kumarsrinivasan1 aGopinath, Chinnakonda, S.1 aRamaraj, Ramasamy uhttp://library.ncl.res.in/content/aminosilicate-sol-gel-stabilized-n-doped-tio2-au-nanocomposite-materials-and-their-001835nas a2200169 4500008004100000022001400041245019100055210006900246260007100315300001400386490000800400520106600408100001501474700001801489700003001507856012801537 2013 eng d a1932-744700aDesign and performance aspects of a custom-built ambient pressure photoelectron spectrometer toward bridging the pressure gap: oxidation of Cu, Ag, and Au surfaces at 1 mbar O-2 pressure0 aDesign and performance aspects of a custombuilt ambient pressure a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcMAR a4717-47260 v1173 a

The critical features of a custom-built laboratory version ambient pressure photoelectron spectrometer (Lab-APPES) are presented. A double front cone differential pumping arrangement and an aperture free design employed in the electrostatic lens regime improve the data collection and data quality. In contrast to the conventional X-ray photoelectron spectrometers (XPS) operating at ultrahigh vacuum (UHV), it is possible to explore the electronic structure of solid surfaces under working conditions or closer to working conditions with Lab-APPES. Especially surface-dependent phenomena can be explored up to 1 mbar pressure and up to 873 K by conventional heating methods and at least up to 1273 K by a laser heating method. Simultaneous XPS and reaction kinetic measurements on solid surfaces make the Lab-APPES an important tool to measure the dynamic electronic structure changes on material surfaces under reaction conditions. The interaction of O-2 with polycrystalline foils of Cu, Ag, and Au from UHV to 1 mbar and up to 773 K has been studied.

1 aRoy, Kanak1 aVinod, C., P.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/design-and-performance-aspects-custom-built-ambient-pressure-photoelectron-spectrometer-001750nas a2200265 4500008004100000022001400041245008800055210006900143260007300212300001200285490000800297520080800305653002201113653002501135653002801160653002201188653002001210653001801230653001401248100002401262700003301286700002201319700003001341856011301371 2013 eng d a0926-860X00aDisordered mesoporous V/TiO2 system for ambient oxidation of sulfides to sulfoxides0 aDisordered mesoporous VTiO2 system for ambient oxidation of sulf aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcFEB a132-1380 v4523 a

High sulfide conversion and predominant sulfoxide yield has been observed with 0.1% vanadium doped disordered mesoporous Ti1-xVxO2 material at ambient and sub ambient temperatures using environmentally green H2O2 oxidant. Ti1-xVxO2 materials were prepared by one-pot solution combustion method in less than 15 min and thoroughly characterized by X-ray diffraction, HRTEM, Raman spectra and other physicochemical techniques. Different sulfides, such as, phenylsulfide, methyl-p-tolylsulfide, ethylsulfide, thioanisole, were converted into the corresponding sulfoxide. Isolated V5+ incorporated in the TiO2 lattice is likely to be the active species for the sulfide oxidation reaction. Catalyst recycling studies indicates the robustness of the catalyst. (c) 2012 Elsevier B.V. All rights reserved.

10aAmbient oxidation10aCombustion synthesis10aheterogeneous catalysis10aHydrogen peroxide10aMesoporous TiO210aSulfoxidation10aSulfoxide1 aNegi, Sanjay, Singh1 aSivaranjani, Kumarsrinivasan1 aSingh, Anand, Pal1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/disordered-mesoporous-vtio2-system-ambient-oxidation-sulfides-sulfoxides-001895nas a2200253 4500008004100000022001400041245008800055210006900143260009200212300001400304490000700318520097300325653001201298653001701310653002801327653003001355653001801385653002201403100002601425700001901451700002601470700003001496856011501526 2013 eng d a1533-488000aFunctional and disordered meso-macroporous gamma-Al2-xMxO3 +/- y (M = Cu and/or Ce)0 aFunctional and disordered mesomacroporous gammaAl2xMxO3 y M Cu a a26650 THE OLD RD, STE 208, VALENCIA, CA 91381-0751 USAbAMER SCIENTIFIC PUBLISHERScAPR a2682-26880 v133 aDisordered meso-macro porous Cu-Ce-Al2O3 nanocomposite (gamma-Al2-xMxO3 +/- y, M = Cu and or Ce) with different compositions has been synthesized. In situ templated sol-gel method has been adopted with simple EDTA ethylenediamine tetra aceticacid and ethylenediamine molecules to prepare gamma-Al2-xMxO3 +/- y, (M = Cu and or Ce). Above meso-macro porous materials were characterized by structural, spectroscopy, microscopy and textural techniques. Detailed characterization indicates that Cu2+ ions are introduced into the ceria and alumina lattice positions. Nano composite nature of the gamma-Al2-xMxO3 +/- y has been confirmed by detailed microscopy investigations. Catalytic activity of the above nanocomposite materials have been screened for environmentally important CO oxidation reaction. 30% Ce-60% Al and 10% Cu containing material shows the best activity among other meso-nnacroporous material with (50%) 100% CO oxidation at (107 degrees C) 145 degrees C.10aAlumina10aCO oxidation10aheterogeneous catalysis10aMeso-Macroporous Material10aNanocomposite10aSol-gel synthesis1 aGnanakumar, Edwin, S.1 aJohn, Jino, C.1 aRaja, Thirumalaiswamy1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/functional-and-disordered-meso-macroporous-gamma-al2-xmxo3-y-m-cu-andor-ce-002133nas a2200181 4500008004100000022001400041245011000055210006900165260011000234300001400344490000600358520136900364100001901733700003001752700001901782700002601801856012401827 2013 eng d a2044-475300aHydroxyapatite supported palladium catalysts for suzuki-miyaura cross-coupling reaction in aqueous medium0 aHydroxyapatite supported palladium catalysts for suzukimiyaura c aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcMAR a1625-16330 v33 a

Supported palladium catalyst 1 has been prepared by the immobilisation of [Pd(COD)Cl-2] (COD = 1,5-cyclooctadiene) on hydroxyapatite. Catalyst 2 has been prepared by subsequent reduction of catalyst 1 with sodium borohydride in ethanol. Under similar reaction conditions, catalyst 1 with Pd2+, is found to be almost five times more active than 2. Using 1 as the catalyst and water as the solvent, reaction conditions for Suzuki-Miyaura cross-coupling reactions have been optimised under aerobic conditions. The best catalytic activities are observed in the presence of potassium carbonate as the base and tetrabutylammonium bromide as a promoter. Catalyst 1 has been tested for catalytic cross-coupling reactions with sixteen different, electronically neutral, electron rich, electron poor and sterically hindered aryl boronic acids, and several different aryl halides including aryl chlorides. More than thousand turnovers and high selectivities to the hetero-coupled products have been observed in most cases. For many substrates the turnovers with 1 are notably more than what has been reported with other supported catalysts in water. The recyclability and scale-up potential of catalyst 1 have been tested and found to be satisfactory. A negligible drop in activity is observed over ten recycles with an accumulated turnover number of similar to 30000.

1 aIndra, Arindam1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar uhttp://library.ncl.res.in/content/hydroxyapatite-supported-palladium-catalysts-suzuki-miyaura-cross-coupling-reaction-002538nas a2200277 4500008004100000022001400041245012100055210006900176260007100245300001200316490000600328520150200334653002801836653001001864653002101874653002601895653002701921100002601948700002501974700002101999700003202020700002402052700002602076700003002102856012802132 2013 eng d a2155-543500aMgCl2 center dot 6CH(3)OH: a simple molecular adduct and its influence as a porous support for olefin polymerization0 aMgCl2 center dot 6CH3OH a simple molecular adduct and its influe a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcMAR a303-3110 v33 a

A single phase molecular adduct, MgCl2 center dot 6CH(3)OH has been synthesized using MgCl2 and the simplest alcohol, methanol. Structural, spectroscopic, and morphological studies have been carried out for a better understanding of the single phase MgCl2 center dot 6CH(3)OH adduct. C-13 CPMAS solid state NMR studies show all six methanol molecules are magnetically equivalent and present in a single environment around the Mg2+ center. Raman spectral analysis of the characteristic peak at 708 cm(-1) substantiates octahedral coordination of six CH3OH molecules around Mg2+. Solid state C-13 NMR measurements, made after heat treatment at different temperatures, have been utilized to understand the variations in CH3OH stoichiometry and coordination around Mg2+ with temperature. A titanated active catalyst, TiCl4 on MgCl2 center dot 6CH(3)OH, has also been synthesized and subjected to detailed characterizations. The active catalyst shows high surface area (102 m(2)/g) and mesoporosity. The titanated catalyst has been screened for ethylene polymerization reactions using different cocatalysts (R3Al; R= -CH3, -CH2CH3, and -CH2CH(CH3)(2)). A total of 7.25 kg of polyethylene per gram of catalyst has been obtained with Me3Al cocatalyst, which is six times higher in activity compared with commercial Me3Al/TiCl4/MgCl2 center dot 6EtOH-supported orted catalystAlthough porosity influences the catalytic activity, other factors also seem to contribute to the total catalytic activity.

10aheterogeneous catalysis10aMgCl210aMolecular adduct10aolefin polymerization10aZiegler-Natta catalyst1 aGnanakumar, Edwin, S.1 aGowda, Ravikumar, R.1 aKunjir, Shrikant1 aAjithkumar, Thalasseril, G.1 aRajamohanan, P., R.1 aChakraborty, Debashis1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/mgcl2-center-dot-6ch3oh-simple-molecular-adduct-and-its-influence-porous-support-olefin-001293nas a2200229 4500008004100000022001400041245006100055210006100116260011000177300001200287490000700299520048600306653001700792653001800809653001600827653002700843100002500870700002200895700001900917700003000936856009700966 2013 eng d a0008-404200aPalladium chloride catalyzed photochemical heck reaction0 aPalladium chloride catalyzed photochemical heck reaction a65 AURIGA DR, SUITE 203, OTTAWA, ON K2E 7W6, CANADAbCANADIAN SCIENCE PUBLISHING, NRC RESEARCH PRESScMAY a348-3510 v913 a

PdCl2 catalyzed carbon-carbon bond formation (Heck reaction) between substituted aryl halides and olefins was carried out without a ligand, under irradiation with UV-visible light. The results demonstrated that UV-visible light accelerated the rate of the reaction, leading to an excellent yield of corresponding products. The recovered palladium nanoparticles could be thermally recycled several times. PdCl2 gave excellent conversion up to the fifth addition of substrate.

10aC-C coupling10aHeck reaction10aiodobenzene10aphotochemical reaction1 aWaghmode, Suresh, B.1 aArbuj, Sudhir, S.1 aWani, Bina, N.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/palladium-chloride-catalyzed-photochemical-heck-reaction-001297nas a2200205 4500008004100000022001400041245013100055210006900186260011000255300001600365490000700381520043700388100002800825700002600853700002000879700001600899700003000915700001900945856012700964 2013 eng d a1359-734500aRationally designed CuFe2O4-mesoporous Al2O3 composite towards stable performance of high temperature water-gas shift reaction0 aRationally designed CuFe2O4mesoporous Al2O3 composite towards st aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJUL a11257-112590 v493 a

High temperature water-gas shift reaction was demonstrated for the first time on a CuFe2O4-mesoporous alumina nanocomposite between 350 and 550 degrees C with 70-80% CO-conversion using simulated waste derived syngas under realistic conditions. Despite high Al-content, the catalyst exhibited stable activity, which was attributed to the nano-architectured robust porous nature of alumina integrated with surrounding CuFe2O4.

1 aSubramanian, Vijayanand1 aGnanakumar, Edwin, S.1 aJeong, Dae-Woon1 aHan, Won-Bi1 aGopinath, Chinnakonda, S.1 aRoh, Hyun-Seog uhttp://library.ncl.res.in/content/rationally-designed-cufe2o4-mesoporous-al2o3-composite-towards-stable-performance-high-001146nas a2200193 4500008004100000022001400041245010100055210006900156260011000225300001400335490000600349520035800355100002500713700001800738700002800756700003000784700001800814856012000832 2013 eng d a2044-475300aSynthesis and catalytic activity of monodisperse gold-mesoporous silica core-shell nanocatalysts0 aSynthesis and catalytic activity of monodisperse goldmesoporous  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcFEB a1190-11930 v33 a

Core-shell nanostructures, where gold nanoparticles of sub 10 nm size are successfully encapsulated inside porous silica spheres, have been prepared. The detailed characterization of the catalyst shows a high surface area and good mesoporosity. The sinter resistance of the catalyst under repeated cycles of the CO oxidation reaction is observed.

1 aSekhar, A., C. Sunil1 aMeera, C., J.1 aZiyad, Kottavarithottil1 aGopinath, Chinnakonda, S.1 aVinod, C., P. uhttp://library.ncl.res.in/content/synthesis-and-catalytic-activity-monodisperse-gold-mesoporous-silica-core-shell-002319nas a2200217 4500008004100000022001400041245009500055210006900150260011000219300001400329490000700343520144200350100002601792700002601818700002101844700003201865700002401897700002601921700003001947856012401977 2014 eng d a1477-922600a9-Fluorenemethanol: an internal electron donor to fine tune olefin polymerization activity0 a9Fluorenemethanol an internal electron donor to fine tune olefin aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcMAR a9143-91510 v433 a

A new MgCl2 based molecular adduct has been synthesized with 9-fluorenemethanol (9FM) as a novel internal electron donor (IED), along with ethanol (EtOH) (MgCl2 center dot n9FM center dot xEtOH). The above molecular adduct has been subjected to a variety of structural, spectroscopic and morphological characterization techniques. The results of the solid state C-13 CPMAS NMR technique suggests the coordination of 9FM to MgCl2. Observation of a low angle diffraction peak at 2 theta = 5.7 degrees (d = 15.5 angstrom) underscores the coordination of 9FM along the z-axis, and ethanol in the molecular adduct. Active Ziegler-Natta catalysts were prepared by two different synthesis methods; the conventional method to obtain a high surface area active catalyst, and other one with 9FM as an integral part of the active catalyst in order to study the influence of 9FM as an IED over the active sites. The active catalysts were also characterized thoroughly with different analytical tools. The XRD results show (003) facets of delta-MgCl2 (alpha-MgCl2) for the conventional (non-conventional) titanated catalyst. Results of the ethylene polymerization activity study reveals that the conventionally prepared highly porous active catalyst shows 1.7-2.5 times higher activity than the non-conventional prepared catalyst; however, the latter shows a low molecular weight distribution and confirms the role of the Lewis base as an IED.

1 aGnanakumar, Edwin, S.1 aChokkapu, Eswara, Rao1 aKunjir, Shrikant1 aAjithkumar, Thalasseril, G.1 aRajamohanan, P., R.1 aChakraborty, Debashis1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/9-fluorenemethanol-internal-electron-donor-fine-tune-olefin-polymerization-activity-002152nas a2200241 4500008004100000022001400041245009600055210006900151260007100220300001400291490000600305520132100311653001401632653001101646653001901657653002201676653001201698653001301710100002201723700002201745700003001767856011301797 2014 eng d a2155-543500aAmbient oxidation of benzene to phenol by photocatalysis on Au/Ti0.98V0.02O2: role of holes0 aAmbient oxidation of benzene to phenol by photocatalysis on AuTi a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcSEP a2844-28530 v43 a

A potential photocatalyst with 2 atom % vanadium incorporated into the 1 lattice of disordered mesoporous titania, Ti0.98V0.02O2, (TV2) was synthesized. Au was deposited on TV2 (Au/TV2) through a photodeposition method. Structural, microscopy, and spectroscopy techniques support the incorporation of vanadium into the TiO2 lattice, and Au was deposited on the surfaces of TV2. Photocatalytic oxidation of benzene was conducted at ambient temperature under UV and/or visible light to demonstrate the catalytic activity of the Au/TV2 catalyst. The TV2 lattice exhibits a quantum jump in benzene to phenol oxidation compared to that of TiO2, highlighting the importance of V for oxidation. Introduction of Au onto TV2 further increases the benzene to phenol oxidation and phenol yield by a factor of 2 under UV light compared to those of bare TV2. No significant phenol production was observed in visible light with or without gold, indicating the role of gold is indirect toward charge separation and electron storage. Nano gold clusters on TV2 selectively store photoexcited electrons and in turn maximize holes utilization on TiO2. The high photocatalytic activity of Au/TV2 is mainly attributed to the presence of Schottky junctions, disordered mesoporosity, and short diffusion lengths for charge carriers.

10anano gold10aphenol10aPhotocatalysis10aSchottky junction10atitania10aVanadium1 aDevaraji, Perumal1 aSathu, Naveen, K.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/ambient-oxidation-benzene-phenol-photocatalysis-auti098v002o2-role-holes-002673nas a2200265 4500008004100000022001400041245011200055210006900167260007700236300001200313490000600325520169700331653002802028653001302056653002502069653001902094653002002113100003302133700002502166700001602191700001502207700002702222700003002249856012802279 2014 eng d a1867-388000aDisordered mesoporous TiO2-xNx+Nano-Au: an electronically integrated nanocomposite for solar H-2 generation0 aDisordered mesoporous TiO2xNxNanoAu an electronically integrated aBOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcFEB a522-5300 v63 a

We report on H-2 generation by photocatalysis driven by simulated white light by electronically integrated Au nanoparticles with multifunctional, disordered mesoporous TiO2-xNx (Au-NT) nanocomposites. Solar H-2 generation (1.5 mmolh(-1)g(-1)) from aqueous methanol has been demonstrated with Au-NT nanocomposites. The water splitting activity of Au-NT is attributed to the 21.1 ps lifetime of charge carriers observed from fluorescence lifetime measurements, which indicates a high electron-injection efficiency from nano-Au to the conduction band of TiO2, and hence charge separation as well as utilization. This is directly supported by the observation of a high photoluminescence emission intensity with Au-NT that highlights the energy transfer from nano-Au to TiO2. The p-n heterojunction observed between the Au (001) and TiO2 (101) facets helps to-wards the higher charge separation and their utilization. A low mesochannel depth (< 10 nm) associated with disordered mesoporous TiO2-xNx helps the charge carriers to move towards the surface for redox reactions and hence charge utilization. Visible-light absorption, as a result of the surface plasmon resonance of nano-Au, is observed in a broad range between 500 and 750 nm, which helps in harvesting visible-light photons. Finally, electronically integrated nano-Au with TiO2-xNx in Au-NT is evident from Raman and X-ray photoelectron spectroscopy measurements. All of these factors help to achieve a high rate of H-2 production. It is likely that a higher rate of H-2 production than that reported here is feasible by strategically locating Au clusters in porous TiO2 to generate hot spots through electronic integration.

10aheterogeneous catalysis10aHydrogen10amesoporous materials10aphotochemistry10awater splitting1 aSivaranjani, Kumarsrinivasan1 aRajaambal, Sivaraman1 aDas, Tanmay1 aRoy, Kanak1 aBhattacharyya, Somnath1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/disordered-mesoporous-tio2-xnxnano-au-electronically-integrated-nanocomposite-solar-h-2-001851nas a2200289 4500008004100000022001400041245011400055210006900169260010100238300001200339490000800351520084700359653000801206653000901214653001601223653002401239653001101263100001601274700001601290700002501306700001701331700002201348700001801370700001701388700003001405856012601435 2014 eng d a0974-362600aEffect of method of preparation on hydrodesulphurization activity of Co- or Ni-promoted MoS2/SBA-15 catalysts0 aEffect of method of preparation on hydrodesulphurization activit aC V RAMAN AVENUE, SADASHIVANAGAR, P B \#8005, BANGALORE 560 080, INDIAbCatalysis Soc IndiacMAR a437-4440 v1263 a

Ordered mesoporous material SBA-15 was synthesized and used as a support for the preparation of molybdenum sulphide catalysts through precipitation from homogeneous solution (PFHS) technique with the Mo content varying from 2-12 wt%. The prepared catalysts were evaluated for thiophene hydrodesulphurizadon catalytic activities at 400 degrees C. Catalysts prepared through PFHS method resulted in highly dispersed MoS2 catalysts, which were inferred from powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), low temperature oxygen chemisorptions (LTOC) and BET surface area analysis. The relationship between XPS intensity ratio, oxygen chemisorption and catalytic activities is discussed in terms of highly dispersed nano particles of MoS2 and its consequence in accommodating more promoted atoms at the edge sites.

10aHDS10aMoS210aPFHS method10apromotional effects10aSBA-151 aGarg, Shelu1 aSoni, Kapil1 aPrasad, V., V. D. N.1 aKumar, Manoj1 aBhaskar, Thallada1 aGupta, J., K.1 aDhar, Murali1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/effect-method-preparation-hydrodesulphurization-activity-co-or-ni-promoted-mos2sba-15-002510nas a2200193 4500008004100000022001400041245010000055210006900155260011000224300001600334490000700350520170600357100002502063700001802088700002302106700002802129700003002157856012902187 2014 eng d a1463-907600aElectronic structure-sunlight driven water splitting activity correlation of (Zn1-yGay)(O1-zNz)0 aElectronic structuresunlight driven water splitting activity cor aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcSEP a23654-236620 v163 a

(Zn1-yGay)(O1-zNz) (y <= 0.10; z <= 0.15) solid solutions have been investigated for their electronic structure and visible light photocatalytic activity, and a correlation was found between them. (Zn1-yGay)(O1-zNz) with ZnO as the major component have been synthesized by a solution combustion method in 10 minutes using simple raw materials. The local structures of Zn K edge and Ga K edge, and changes in the chemical environment with the incorporation of Ga and N in ZnO were determined by EXAFS study. EXAFS and XRD results suggested the dissolution of GaN in the ZnO lattice. The homogeneity of the solid solution was demonstrated from HRTEM studies. Photoluminescence studies revealed the creation of a new band at the top of the ZnO valence band (VB), and thus the broadening of the VB of (Zn1-yGay)(O1-zNz) or a decrease in the band gap was attributed to the origin of visible light absorption. UV-Vis spectral studies showed light absorption up to 550 nm, which directly supports the VB broadening. Predominant oxygen vacancies and high photocorrosion observed for ZnO were fully suppressed for (Zn1-yGay)(O1-zNz) , indicating the minimization of defects, and thus more sustainability under irradiation conditions. The bare solid solution exhibited reasonable and promising activity for solar hydrogen evolution and photoelectrochemical current generation at 0 V. The present work explained factors such as the preparation method, single phase structure with the stabilization of integral parts, homogeneity in the structure, compensation of oxygen vacancies, and suppression of the density of recombination centres that play a pivotal role in realizing solar energy harvesting.

1 aRajaambal, Sivaraman1 aYadav, A., K.1 aJha, Shambhu, Nath1 aBhattacharyya, Dibyendu1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/electronic-structure-sunlight-driven-water-splitting-activity-correlation-zn1-ygayo1-znz-001589nas a2200217 4500008004100000022001400041245006700055210006500122260011000187300001400297490000700311520080700318100002201125700001801147700002601165700002201191700001601213700003001229700002001259856009201279 2014 eng d a1144-054600aFacile method for the synthesis of Co-core Au-shell nanohybrid0 aFacile method for the synthesis of Cocore Aushell nanohybrid aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcSEP a4107-41140 v383 a

Heterostructured Co-Au core-shell nanoparticles have been synthesized by reducing AuCl4- ions on cobalt nanoparticles after a minor but effective modification of cobalt surface by an amine. The core shell morphology is emphatically confirmed by thorough investigation through UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopic analysis (TEM). The chemical composition and topography were determined using STEM-HAADF analysis and EFTEM imaging. Fourier transform infrared (FTIR) spectroscopy confirms the surface modification of Co nanoparticles and the interactions involved between the ligands and the core and shell metals at various steps of the synthetic process. The magnetic properties confirm the material to be superparamagnetic in nature.

1 aSardar, Debasmita1 aNeogi, S., K.1 aBandyopadhyay, Sanjoy1 aSatpati, Biswarup1 aJain, Ruchi1 aGopinath, Chinnakonda, S.1 aBala, Tanushree uhttp://library.ncl.res.in/content/facile-method-synthesis-co-core-au-shell-nanohybrid-002798nas a2200253 4500008004100000022001400041245015200055210006900207260007100276300001400347490000600361520184700367653002102214653002002235653001002255653002802265653002102293653002302314100001602337700001502353700003002368700001502398856013102413 2014 eng d a1944-824400aFacile single-step synthesis of nitrogen-doped reduced graphene oxide-Mn3O4 hybrid functional material for the electrocatalytic reduction of oxygen0 aFacile singlestep synthesis of nitrogendoped reduced graphene ox a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcFEB a2692-26990 v63 a

Development of efficient electrocatalyst based on non-precious metal that favors the four-electron pathway for the reduction of oxygen in alkaline fuel cell is a challenging task. Herein, we demonstrate a new facile route for the synthesis of hybrid functional electrocatalyst based on nitrogen-doped reduced graphene oxide (N-rGO) and Mn3O4 with pronounced electrocatalytic activity towards oxygen reduction reaction (ORR) in alkaline solution. The synthesis involves one-step in situ reduction of both graphene oxide (GO) and Mn(VII), growth of Mn3O4 nanocrystals and nitrogen doping onto the carbon framework using a single reducing agent, hydrazine. The X-ray photoelectron (XPS), Raman and FTIR spectral, and X-ray diffraction measurements confirm the reduction of GO and growth of nanosized Mn3O4. The XPS profile reveals that N-rGO has pyridinic (40%), pyrrolic (53%), and pyridine N oxide (7%) types of nitrogen. The Mn3O4 nanoparticles are single crystalline and randomly distributed over the wrinkled N-rGO sheets. The hybrid material has excellent ORR activity and it favors the 4-electron pathway for the reduction of oxygen. The electrocatalytic performance of the hybrid catalyst is superior to the N-rGO, free Mn3O4 and their physical mixture. The hybrid material shows an onset potential of -0.075 V, which is 60-225 mV less negative than that of the other catalyst tested. It has excellent methanol tolerance and high durability. The catalytic current density achieved with the hybrid material at 0.1 mg cm(-2) is almost equivalent to that of the commercial Pt/C (10%). The synergistic effect of N-rGO and Mn3O4 enhances the overall performance of the hybrid catalyst. The nitrogen in N-rGO is considered to be at the interface to bridge the rGO framework and Mn3O4 nanoparticles and facilitates the electron transfer.

10aelectrocatalysis10ahybrid material10aMn3O410anitrogen-doped graphene10aoxygen reduction10asynergistic effect1 aBag, Sourav1 aRoy, Kanak1 aGopinath, Chinnakonda, S.1 aRaj, Retna uhttp://library.ncl.res.in/content/facile-single-step-synthesis-nitrogen-doped-reduced-graphene-oxide-mn3o4-hybrid-functional-002177nas a2200193 4500008004100000022001400041245008900055210006900144260011000213300001600323490000600339520138500345100002401730700003701754700002601791700002201817700003001839856011401869 2014 eng d a2046-206900aGreen chemistry approach to styrene from ethylbenzene and air on MnxTi1-xO2 catalyst0 aGreen chemistry approach to styrene from ethylbenzene and air on aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcOCT a57087-570970 v43 a

Styrene (ST) is an industrially important commodity chemical, and design of a suitable catalyst, which provides high ethyl benzene (EB) conversion and styrene selectivity at Lower temperature with sustainable activity, is one of the major challenges in the field of heterogeneous catalysis. Manganese incorporated in titania (MnxT1-xO2) anatase Lattice, prepared via the solution combustion method, was evaluated for oxidative dehydrogenation (ODH) of EB with O-2 or air. MnxTi1-xO2 catalysts were characterized by different physiochemical methods. Up to 15% Mn could be introduced into the TiO2 Lattice. TEM and XRD indicate disordered mesoporosity, further confirmed by adsorption isotherm analysis. MnxTi1-xO2 catalysts were evaluated for ST synthesis from EB using air or oxygen as oxidant between 440 and 570 degrees C. Reaction conditions have been varied systematically, such as catalyst composition, and EB/air/O-2 flow. MnxTi1-xO2 shows sustainable 55% styrene yield for 45 h without deactivation under optimum conditions. A thorough analysis of spent catalysts demonstrates the conversion of initial anatase phase MnxTi1-xO2 to Mn3O4 supported on the rutile (R) phase of TiO2. The above change occurs in the first few hours of reaction and the Mn3O4 on R-TiO2 phase is the active phase of the catalyst and responsible for sustainable activity for Longer duration.

1 aNegi, Sanjay, Singh1 aVenugopalan, Aswathy, Thareparam1 aRaja, Thirumalaiswamy1 aSingh, Anand, Pal1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/green-chemistry-approach-styrene-ethylbenzene-and-air-mnxti1-xo2-catalyst-001999nas a2200169 4500008004100000022001400041245013100055210006900186260011000255300001600365490000700381520124000388100002501628700001701653700003001670856012901700 2014 eng d a1477-922600aIn1-XGaXN@ZnO: a rationally designed and quantum dot integrated material for water splitting and solar harvesting applications0 aIn1XGaXNZnO a rationally designed and quantum dot integrated mat aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcSEP a12546-125540 v433 a

The highly desirable combination of the visible light absorption properties of In1-xGaxN Quantum dots (QD) along with the multifunctionality of ZnO into a single integrated material was prepared for solar harvesting. This is the first report on InGaN QD integrated with ZnO (InGaN@ZnO), synthesized by a highly reproducible, simple combustion method in 15 min. Structural, microstructural and electronic integration of the nitride and oxide components of InGaN@ZnO was demonstrated by appropriate characterization methods. Self-assembly of InGaN QD is induced in growing nascent zinc oxo nanoclusters taking advantage of the common wurtzite structure and nitrogen incorporation at the expense of oxygen vacancies. Direct integration brings about a single phase structure exhibiting extensive visible tight absorption and high photostability. InGaN@ZnO suggests synergistic operation of tight harvesting and charge conducting components for solar H-2 generation without using any co-catalyst or sacrificial agent, and a promising photocurrent generation at 0 V under visible light illumination. The present study suggests a direct integration of QD with the host matrix and is a potential method to realize the advantages of QDs.

1 aRajaambal, Sivaraman1 aMapa, Maitri1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/in1-xgaxnzno-rationally-designed-and-quantum-dot-integrated-material-water-splitting-and-001095nas a2200157 4500008004100000022001400041245009100055210006900146260008800215300001400303490000800317520044100325100001700766700003000783856012400813 2014 eng d a0587-424600aMapping of copper oxidation state using high pressure x-ray photoelectron spectroscopy0 aMapping of copper oxidation state using high pressure xray photo aAL LOTNIKOW 32-46, PL-02-668 WARSAW, POLANDbPOLISH ACAD SCIENCES INST PHYSICScAPR a1065-10660 v1253 a

The interaction of O-2 with polycrystalline foil of Cu, from ultra high vacuum to 1 mbar and up to 773 K has been investigated. The study were performed by using the high pressure X-ray photoelectron spectroscopy (electron spectroscopy for chemical analysis) ultraviolet photoelectron spectroscopy system. In this work the results of mapping copper oxidation states as a function of temperature at 1 mbar O-2 have been presented.

1 aKowalska, J.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/mapping-copper-oxidation-state-using-high-pressure-x-ray-photoelectron-spectroscopy-002028nas a2200181 4500008004100000022001400041245013600055210006900191260011000260300001600370490000600386520122300392100002201615700003001637700003001667700002501697856012401722 2014 eng d a2046-206900aNanocomposite of silver and thermo-associating polymer by a green route: a potential soft-hard material for controlled drug release0 aNanocomposite of silver and thermoassociating polymer by a green aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJAN a10261-102680 v43 a

Major research efforts are continuously being made to look for alternative, environment friendly green chemicals for the synthesis of nanoparticles in place of conventional and hazardous reducing agents such as sodium borohydride and hydrazine. We report here on the synthesis and characterization of AgNPs using a thermo-associating polymer namely, carboxymethyl guar grafted poly(ethylene oxide-co-propylene oxide) [CMG-g-PEPO]. The polymer acts as both reducing agent as well as stabilizing/capping agent. The formation of AgNPs with polymer was confirmed by UV/Vis spectroscopy and the TEM images indicated the size of nanoparticles to be in the range of 10-20 nm. We also demonstrated the use of these nanoparticles in the controlled release of doxorubicin hydrochloride (Dox), an anticancer drug. The binding of Dox onto the polymer and AgNPs was investigated by XPS and Raman spectroscopy which indicates that a charge-transfer mechanism is operative between the Dox and polymer holding both the entities together. The first synthesis of AgNPs using non-toxic thermo-associating polymer and subsequent release of Dox with body temperature (37 degrees C) as a trigger is the highlight of the present work.

1 aGupta, Nivika, R.1 aPrasad, Bhagavatula L. V.1 aGopinath, Chinnakonda, S.1 aBadiger, Manohar, V. uhttp://library.ncl.res.in/content/nanocomposite-silver-and-thermo-associating-polymer-green-route-potential-soft-hard-001607nas a2200217 4500008004100000022001400041245010200055210006900157260007700226300001200303490000600315520081200321653002801133653001301161653001101174653001401185653002201199100001501221700003001236856012301266 2014 eng d a1867-388000aNOx reduction at near ambient temperatures and under lean-burn conditions on modified pd surfaces0 aNOx reduction at near ambient temperatures and under leanburn co aBOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcFEB a531-5370 v63 a

Palladium surfaces that are modified with O atoms in the subsurface broaden the NO reduction temperature regime up to 325 K with O-2-rich NO+H-2+O-2 compositions. Compared to virgin Pd surfaces, up to 150% higher deNO(x) catalytic activity was observed with modified Pd surfaces at the reaction maximum. Molecular beam instrument and ambient-pressure photoelectron spectroscopy were employed to follow the kinetic and surface changes. These results open up a possibility to realize the cold-start reduction of NOx (deNO(x)). DeNO(x) activity reported in the literature with supported Pd catalysts after a simple calcination in air compares well with our present observations. Surface modification is likely to demonstrate a high potential for other catalytic reactions at relatively low temperatures.

10aheterogeneous catalysis10anitrogen10aoxygen10aPalladium10asurface chemistry1 aRoy, Kanak1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/nox-reduction-near-ambient-temperatures-and-under-lean-burn-conditions-modified-pd-001678nas a2200205 4500008004100000022001400041245008500055210006900140260011000209300001600319490000600335520088800341100001801229700002201247700002001269700001801289700003001307700002001337856011501357 2014 eng d a2046-206900aPreferential growth of Au on CdSe quantum dots using langmuir-blodgett technique0 aPreferential growth of Au on CdSe quantum dots using langmuirblo aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcNOV a64535-645410 v43 a

Oleyl amine capped CdSe quantum dots (QD) were synthesised by hot injection technique. These QDs formed a self-assembled monolayer on an aqueous subphase of a Langmuir-Blodgett (LB) trough. Here, in this report we introduced a simple but very efficient route to form a metal (Au)-QD hybrid nanostructure via the LB technique. In this method, the metal counterpart of the hybrid nanostructure could be deposited exclusively on one side of the QDs. The formation of stable monolayer of QDs was evidenced from a surface pressure-area (P-A) isotherm. The development of gold tip was confirmed and monitored by detailed TEM study on the monolayer deposited on TEM grids from the LB trough. Other characterizations like UV-Vis spectroscopy, FTIR, XPS and EDX also suggested the same. Oleyl amine was shown to act both as a reducing agent as well as a capping agent in this strategy.

1 aDas, Subhasis1 aSatpati, Biswarup1 aChauhan, Himani1 aDeka, Sasanka1 aGopinath, Chinnakonda, S.1 aBala, Tanushree uhttp://library.ncl.res.in/content/preferential-growth-au-cdse-quantum-dots-using-langmuir-blodgett-technique-001984nas a2200253 4500008004100000022001400041245010300055210006900158260007700227300001400304490000600318520106600324653002001390653000901410653002801419653001401447653001001461100002601471700002901497700002601526700002601552700003001578856012201608 2014 eng d a1867-388000aRole of nanointerfaces in Cu- and Cu plus Au-based near-ambient-temperature CO oxidation catalysts0 aRole of nanointerfaces in Cu and Cu plus Aubased nearambienttemp aBOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcNOV a3116-31240 v63 a

Disordered mesoporous Cu-doped ceria-zirconia (Cu0.1Ce0.85Zr0.05O2), and gold deposited (Au/Cu0.1Ce0.85Zr0.05O2) catalysts were synthesized and evaluated for CO oxidation. Onset of CO oxidation activity, and 50% (100%) CO2 formation occurs at room temperature (RT), and 77 (120)degrees C, respectively, with Cu0.1Ce0.85Zr0.05O2. A small amount of gold on Cu0.1Ce0.85Zr0.05O2 induces the sustainable oxidation catalysis around RT. Onset of copper reduction temperature decreases from 110 degrees C on Cu0.1Ce0.85Zr0.05O2 to 48 degrees C with Au/Cu0.1Ce0.85Zr0.05O2, highlighting the direct interaction between Cu and Au through a Cu-Au interface. Au particles with a (00 1) facet deposit on an oxygen-deficient site of (111) facet of CeO2-ZrO2. Any decrease in surface Cu-content with increasing Au-content further supports the Au-Cu-Ce/Zr interface interactions. Nanointerfaces of Au clusters on Cu next to oxygen-deficient sites of CeO2-ZrO2 facilitate all the elementary steps of the CO + O-2 reaction to occur in close proximity at ambient conditions.

10acarbon monoxide10aGold10aheterogeneous catalysis10aOxidation10aredox1 aGnanakumar, Edwin, S.1 aNaik, Jarpla, Madhusudha1 aManikandan, Marimuthu1 aRaja, Thirumalaiswamy1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/role-nanointerfaces-cu-and-cu-plus-au-based-near-ambient-temperature-co-oxidation-001925nas a2200181 4500008004100000022001400041245015300055210006900208260007100277300001400348490000800362520113900370100002101509700003201530700002401562700003001586856012701616 2014 eng d a1089-563900aSolid-state NMR investigations of a MgCl2 center dot 4(CH3)(2)CHCH2OH molecular adduct: a peculiar case of reversible equilibrium between two phases0 aSolidstate NMR investigations of a MgCl2 center dot 4CH32CHCH2OH a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcFEB a1213-12190 v1183 a

MgCl2 center dot xROH molecular adducts are extensively employed as a support material for Ziegler-Natta polyolefin catalysis. However, their structural properties are not well understood. Recently, we reported on the preparation of an isobutanol adduct, MgCl2 center dot 4(CH3)(2)CHCH2OH (MgiBuOH) (Dalton Trans. 2012, 41, 11311), which is very sensitive to the preparation conditions, such as the temperature and refluxing time. For the present study, the structural properties of MgiBuOH adducts prepared under different conditions have been investigated thoroughly by solid-state NMR and nonambient XRD. Formation of two phases has been confirmed, and in situ variable temperature solid-state NMR measurements confirm the coexistence of two phases as well as the oscillation from one to another phase. It is expected that such molecular adducts could have a significant role in organic transformation reactions due to an oscillating structural component. An understanding of phase oscillation with the Mg2+ ion as the central metal ion might shed some light toward understanding various biological and structural functions.

1 aThushara, K., S.1 aAjithkumar, Thalasseril, G.1 aRajamohanan, P., R.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/solid-state-nmr-investigations-mgcl2-center-dot-4ch32chch2oh-molecular-adduct-peculiar-001692nas a2200253 4500008004100000022001400041245011000055210006900165260007300234300001200307490000800319520077400327653002801101653001001129653002101139653000801160653001501168653002701183100002101210700003201231700002401263700003001287856012101317 2014 eng d a0926-860X00aStructural investigations of porous MgCl2-2-butanol molecular adduct as support for olefin polymerization0 aStructural investigations of porous MgCl22butanol molecular addu aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJAN a267-2740 v4693 a

A new heterogeneous Ziegler-Natta (Z-N) catalyst support material, MgCl2 center dot 4(CH3CH(OH)CH2CH3) (Mg2BuOH) has been synthesized. 2-Butanol, a linear, secondary alcohol was chosen for the generation of an active MgCl2 support which results in a Z-N catalyst with TiCl4. Significant feature of this work is the formation of rod shaped molecular adduct with highly porous character. Adduct material is characterized by XRD, TG-DTA, Raman spectroscopy, solid-state NMR and SEM. Activity of the Z-N catalyst supported on Mg2BuOH for ethylene polymerization is comparable with that of commercially available heterogeneous Z-N catalyst. However, there is scope to improve the activity by optimizing textural properties. (C) 2013 Elsevier B.V. All rights reserved.

10aheterogeneous catalysis10aMgCl210aMolecular adduct10aNMR10aPolyolefin10aZiegler-Natta catalyst1 aThushara, K., S.1 aAjithkumar, Thalasseril, G.1 aRajamohanan, P., R.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/structural-investigations-porous-mgcl2-2-butanol-molecular-adduct-support-olefin-002869nas a2200265 4500008004100000022001400041245014500055210006900200260007100269300001400340490000600354520191100360653001202271653002802283653001302311653001402324653001902338653001702357653001402374653002502388100001502413700001602428700003002444856012902474 2014 eng d a2155-543500aTowards a sustainable and near ambient DeNO(x) under lean burn conditions: a revisit to no reduction on virgin and modified pd(111) surfaces0 aTowards a sustainable and near ambient DeNOx under lean burn con a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUN a1801-18110 v43 a

Catalytic conversion of NO in the presence of H-2 and O-2 has been studied on Pd(111) surfaces, by using a molecular beam instrument with mass spectrometry detection, as a function of temperature and reactants composition. N-2 and H2O are the major products observed, along with NH3 and N2O minor products under all conditions studied. Particular attention has been paid to the influence of O-2 addition toward NO dissociation. Although O-2-rich compositions were found to inhibit the deNO(x) activity of the Pd catalyst, some enhancement in NO reduction to N-2 was also observed up to a certain O-2 content. The reason for this behavior was determined to be the effective consumption of the H-2 in the mixture by the added O-2 and O atoms from NO dissociation. NO was proven to compete favorably against O-2 for the consumption of H-2, especially <= 550 K, to produce N-2 and H2O. Compared with other elementary reaction steps, a slow decay observed with the 2H + 0 -> H2O step under SS beam oscillation conditions demonstrates its contribution to the rate-limiting nature of the overall reaction. Pd(111) surfaces modified with O atoms in the subsurface (Md-Pd(111)) induces steady-state NO reduction at near-ambient temperatures (325 K) and opens up a possibility to achieve room temperature emission control. A 50% increase in the reaction rates was observed at the reaction maximum on Md-Pd(111), as compared with virgin surfaces. Oxygen adsorption is severely limited below 400 K, and effective NO + H-2 reaction occurs on Md-Pd(111) surfaces. Valence band photoemission with a UV light source (He I) under different oxygen pressures with APPES clearly identified the characteristics of the Md-Pd(111) surfaces and PdO. The electron-deficient or cationic nature of Md-Pd(111) surfaces enhances the NO dissociation and inhibits oxygen chemisorption <= 400 K under lean-burn conditions.

10adeNO(x)10aheterogeneous catalysis10aHydrogen10alean burn10amolecular beam10anitric oxide10aPalladium10asurface modification1 aRoy, Kanak1 aJain, Ruchi1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/towards-sustainable-and-near-ambient-denox-under-lean-burn-conditions-revisit-no-reduction01624nas a2200157 4500008004100000022001400041245012600055210006900181260007100250300001400321490000700335520095400342100001501296700003001311856012501341 2014 eng d a0003-270000aUV photoelectron spectroscopy at near ambient pressures: mapping valence band electronic structure changes from Cu to CuO0 aUV photoelectron spectroscopy at near ambient pressures mapping  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcAPR a3683-36870 v863 a

Valence band (VB) changes and hence electronic structure evolution was directly observed with low kinetic energy (KE) electrons at near ambient pressure (NAP) conditions with He I photon source in a custom built laboratory ambient pressure photoelectron spectrometer (Lab-APPES). Polycrystalline Cu surfaces were gradually oxidized in O-2 to Cu2O, to a mixture of Cu2O + CuO, and finally to CuO between 300 and 625 K and at NAP. Typical VB features for Cu, Cu2O, and CuO were observed, and the results corroborate well with core level and Auger spectral changes. High mean free path associated with low KE electrons, very low or no inelastic scattering, and effective pumping and the design of electrostatic lens regime help to minimize the electron attenuation at NAP conditions. The present results extend the capabilities of the APPES tool to explore the in situ evolution of electronic structure of materials at NAP and high temperatures.

1 aRoy, Kanak1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/uv-photoelectron-spectroscopy-near-ambient-pressures-mapping-valence-band-electronic-001865nas a2200229 4500008004100000022001400041245008200055210006900137260007700206300001200283490000600295520102500301653002801326653001401354653003101368653002201399653002501421100003001446700001501476700003201491856011201523 2015 eng d a1867-388000aCan we shift and/or broaden the catalysis regime towards ambient temperature?0 aCan we shift andor broaden the catalysis regime towards ambient  aBOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcFEB a588-5940 v73 a

An attempt was made to shift the temperature regime of oxidation catalysis towards ambient temperatures by employing surface modification (SM) as a handle. Systematic SM of Pd(111) was performed by O-atom diffusion into the subsurfaces. Virgin and modified Pd(111) catalysts were evaluated for CO oxidation. Typical CO poisoning observed on virgin surfaces was partially lifted, and ambient CO oxidation was observed on the modified surfaces. CO oxidation was followed by the molecular beam method and near-ambient pressure (NAP) photoelectron spectroscopy under different pressure regimes. UV valence band spectral analysis of the SM and the CO+O-2 reaction on modified Pd(111) surfaces under NAP conditions demonstrated changes in the electronic structures of the surfaces with a change in surface potential by 0.35eV and directly probed CO2 formation under the reaction conditions. Supported metal catalysts may be subjected to SM and evaluated for a shift in the catalysis regime for many different reactions.

10aheterogeneous catalysis10aOxidation10aphotoelectron spectroscopy10asurface chemistry10asurface modification1 aGopinath, Chinnakonda, S.1 aRoy, Kanak1 aNagarajan, Sankaranarayanan uhttp://library.ncl.res.in/content/can-we-shift-andor-broaden-catalysis-regime-towards-ambient-temperature-001504nas a2200169 4500008004100000022001400041245008400055210006900139260011000208300001400318490000600332520079700338100002801135700003001163700002501193856011601218 2015 eng d a2046-206900aEfficient Ag-nanoparticle embedded semi-IPN hydrogel for catalytic applications0 aEfficient Agnanoparticle embedded semiIPN hydrogel for catalytic aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcDEC a7567-75740 v53 a

Silver nanoparticle embedded semi-IPN hydrogels based on a combination of poly(acrylamide) and poly(aspartic acid) were synthesized. These semi-IPN hydrogel networks can potentially serve as micro or nano reactors for entrapment of metal nanoparticles. Current methodology allows us to entrap metal nanoparticles throughout hydrogel networks via poly(aspartic acid) chains which are dispersed homogeneously in the gel matrix. The Ag-NPs were characterized by UV-vis absorption spectroscopy, transmission electronic microscopy (TEM), X-ray diffraction (XRD) and energy dispersive X-ray analysis (EDAX). The Ag embedded hydrogels catalyze the reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4 very efficiently at room temperature with good recyclability upto 3 cycles.

1 aPatwadkar, Manjusha, V.1 aGopinath, Chinnakonda, S.1 aBadiger, Manohar, V. uhttp://library.ncl.res.in/content/efficient-ag-nanoparticle-embedded-semi-ipn-hydrogel-catalytic-applications-002604nas a2200205 4500008004100000022001400041245010700055210006900162260011000231300001600341490000600357520176600363100002402129700001802153700001602171700002602187700002702213700003002240856012802270 2015 eng d a2040-336400aM-Au/TiO2 (M = Ag, Pd, and Pt) nanophotocatalyst for overall solar water splitting: role of interfaces0 aMAuTiO2 M Ag Pd and Pt nanophotocatalyst for overall solar water aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJUL a13477-134880 v73 a

M-Au/TiO2 (M = Ag, Pd, Pt) composites were prepared through a facile one-pot photodeposition synthesis and evaluated for solar water splitting (SWS) with and without a sacrificial agent. The M-Au combination exhibits a dominant role in augmenting the H2 generation activity by forming a bi-metallic system. Degussa P25 was used as a TiO2 substrate to photodeposit Au followed by Au + M (M = Ag/Pd/Pt). The SWS activity of the M-Au/TiO2 was determined through photocatalytic H-2 production in the presence of methanol as a sacrificial agent under one sun conditions with an AM1.5 filter. The highest H-2 yield was observed for Pt-0.5-Au-1/TiO2 and was around 1.3 +/- 0.07 mmol h(-1) g(-1), with an apparent quantum yield (AQY) of 6.4%. Pt-0.5-Au-1/TiO2 also demonstrated the same activity for 25 cycles of five hours each for 125 h. Critically, the same Pt-0.5-Au-1/TiO2 catalyst was active in overall SWS (OSWS) without any sacrificial agent, with an AQY = 0.8%. The amount of Au and/or Pt was varied to obtain the optimum composition and it was found that the Pt0.5-Au1/TiO2 composition exhibits the best activity. Detailed characterization by physico-chemical, spectral and microscopy measurements was carried out to obtain an in-depth understanding of the origin of the photocatalytic activity of Pt-0.5-Au-1/TiO2. These in-depth studies show that gold interacts predominantly with oxygen vacancies present on titania surfaces, and Pt preferentially interacts with gold for an effective electron-hole pair separation at Pt-Au interfaces and electron storage in metal particles. The Pt in Pt-0.5-Au-1/TiO2 is electronically and catalytically different from the Pt in Pt/TiO2 and it is predicted that the former suppresses the oxygen reduction reaction.

1 aMelvin, Ambrose, A.1 aIllath, Kavya1 aDas, Tanmay1 aRaja, Thirumalaiswamy1 aBhattacharyya, Somnath1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/m-autio2-m-ag-pd-and-pt-nanophotocatalyst-overall-solar-water-splitting-role-interfaces-002031nas a2200241 4500008004100000022001400041245008300055210006900138260011000207300001400317490000700331520114000338100002201478700001801500700002601518700002201544700001801566700002101584700001601605700003001621700002001651856011801671 2015 eng d a1144-054600aMultifaceted core-shell nanoparticles: superparamagnetism and biocompatibility0 aMultifaceted coreshell nanoparticles superparamagnetism and bioc aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcAUG a8513-85210 v393 a

NicoreAgshell nanoparticles were synthesized by redox transmetallation reaction. Reduction potential match was encouraging to attempt the synthesis of the NicoreAushell system too. However, it could be achieved only after an effective surface modification on the Ni-core. Thorough characterization (UV-Vis spectroscopy, fluorescence spectroscopy, XRD, XPS, FTIR, TEM, and EDX) proved the necessity of surface modification and the success of synthesis of both types of core-shell structures. The chemical composition and topography were determined using STEM-HAADF analysis and EFTEM imaging. Fourier transform infrared (FTIR) spectroscopy confirmed the surface modification of Ni nanoparticles and the interactions involved between the ligands and metals (in the core and/or the shell) at various steps of the synthetic process. Even after the formation of the noble metal shell, the magnetic core was found to retain its superparamagnetic nature. In addition, the Au-shell protected the core from aerial oxidation and decreased toxicity as compared to pristine Ni nanoparticles as observed by MTT assay on normal cells (PBMCs).

1 aSardar, Debasmita1 aNeogi, S., K.1 aBandyopadhyay, Sanjoy1 aSatpati, Biswarup1 aAhir, Manisha1 aAdhikary, Arghya1 aJain, Ruchi1 aGopinath, Chinnakonda, S.1 aBala, Tanushree uhttp://library.ncl.res.in/content/multifaceted-core-shell-nanoparticles-superparamagnetism-and-biocompatibility-002146nas a2200169 4500008004100000022001400041245009700055210006900152260011000221300001600331490000600347520141000353100002401763700003301787700003001820856012601850 2015 eng d a2040-336400aRational approach towards enhancing solar water splitting: a case study of Au-RGO/N-RGO-TiO20 aRational approach towards enhancing solar water splitting a case aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcMAY a11206-112150 v73 a

A rational approach was employed to enhance the solar water splitting (SWS) efficiency by systematically combining various important factors that helps to increase the photocatalytic activity. The rational approach includes four important parameters, namely, charge generation through simulated sunlight absorption, charge separation and diffusion, charge utilization through redox reaction, and the electronic integration of all of the above three factors. The complexity of the TiO2 based catalyst and its SWS activity was increased systematically by adding reduced graphene oxide (RGO) or N-doped RGO and/or nanogold. Au-N-RGO-TiO2 shows the maximum apparent quantum yield (AQY) of 2.46% with a H-2 yield (525 mu mol g(-1) h(-1)) from aqueous methanol, and overall water splitting activity (22 mu mol g(-1) h(-1); AQY = 0.1%) without any sacrificial agent under one sun conditions. This exercise helps to understand the factors which help to enhance the SWS activity. Activity enhancement was observed when there is synergy among the components, especially the simulated sunlight absorption (or one sun conditions), charge separation/conduction and charge utilization. Electronic integration among the components provides the synergy for efficient solar light harvesting. In our opinion, the above synergy helps to increase the overall utilization of charge carriers towards the higher activity.

1 aBharad, Pradnya, A.1 aSivaranjani, Kumarsrinivasan1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/rational-approach-towards-enhancing-solar-water-splitting-case-study-au-rgon-rgo-tio2-002505nas a2200253 4500008004100000022001400041245006900055210006800124260010200192300001000294490000800304520163300312653001301945653001701958653001901975653001601994653001802010653001802028653002002046100002502066700003302091700003002124856009702154 2015 eng d a0974-362600aRecent developments in solar H-2 generation from water splitting0 aRecent developments in solar H2 generation from water splitting aC V RAMAN AVENUE, SADASHIVANAGAR, P B \#8005, BANGALORE 560 080, INDIAbINDIAN ACAD SCIENCEScJAN a33-470 v1273 a

Hydrogen production from water and sunlight through photocatalysis could become one of the channels, in the not-so-distant future, to meet a part of ever growing energy demands. However, accomplishing solar water splitting through semiconductor particulate photocatalysis seems to be the `Holy Grail' problem of science. In the present mini-review, some of the critical strategies of semiconductor photocatalysis are focused with the aim of enumerating underlying critical factors such as visible light harvesting, charge carrier separation, conduction and their utilization that determine the quantum efficiency. We attempted to bring out the essential requirements expected in a material for facile water splitting by explaining important and new designs contributed in the last decade. The newly emerged designs in semiconductor architecture employing nanoscience towards meeting the critical factors of facile photocatalysis are elucidated. The importance of band gap engineering is emphasized to utilize potential wide band gap semiconductors. Assistance of metal nanostructures and quantum dots to semiconductors attains vital importance as they are exuberant visible light harvesters and charge carrier amplifiers. Benevolent use of quantum dots in solar water splitting and photoelectrochemical water splitting provides scope to revolutionize the quantum efficiency by its multiple exciton generation features. A list of drawbacks and issues that hamper the much needed breakthrough in photocatalysis of water splitting is provided to invite attention to address them and move towards sustainable water splitting.

10aHydrogen10ananomaterial10aPhotocatalysis10aquantum dot10aSemiconductor10avisible light10awater splitting1 aRajaambal, Sivaraman1 aSivaranjani, Kumarsrinivasan1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/recent-developments-solar-h-2-generation-water-splitting-001373nas a2200253 4500008004100000022001400041245010500055210006900160260007700229300001400306490000700320520041200327653002800739653001900767653002100786653003100807653002700838100001900865700002300884700003000907700002900937700002400966856012900990 2015 eng d a1433-785100aSBA-15-oxynitrides as a solid-base catalyst: effect of nitridation temperature on catalytic activity0 aSBA15oxynitrides as a solidbase catalyst effect of nitridation t aBOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcMAY a5985-59890 v543 a

Solid bases, such as SBA-15-oxynitrides, have attracted considerable interest for potential applications as catalysts in important industrial processes. Reported herein is that by simply tuning the temperature of nitridation (ammonolysis), the catalytic activity of these solid bases can be enhanced. Solid-state NMR spectroscopy and XPS studies provided the reasoning behind this change in activity.

10aheterogeneous catalysis10aNanostructures10aNMR spectroscopy10aphotoelectron spectroscopy10asolid-state structures1 aSingh, Baljeet1 aMote, Kaustubh, R.1 aGopinath, Chinnakonda, S.1 aMadhu, Perunthiruthy, K.1 aPolshettiwar, Vivek uhttp://library.ncl.res.in/content/sba-15-oxynitrides-solid-base-catalyst-effect-nitridation-temperature-catalytic-activity-002361nas a2200193 4500008004100000022001400041245014400055210006900199260000800268300001600276490000700292520162800299100002301927700001801950700002201968700001901990700003002009856012802039 2016 eng d a1463-907600aAttempt to correlate surface physics and chemical properties : molecular beam and Kelvin probe investigations of Ce 1-x Zr x O 2 thin films0 aAttempt to correlate surface physics and chemical properties mol cSEP a27594-276020 v183 a

What is the correlation between physical properties of the surfaces (such as surface potential, electronic nature of the surface), and chemical and catalysis properties (such as chemisorption, sticking probability of surface)? An attempt has been made to explore any correlation that might exist between the physical and chemical properties of thin film surfaces. Kelvin probe microscopy (KPM) and the molecular beam (MB) methods were employed to carry out the surface potential, and oxygen adsorption and oxygen storage capacity (OSC) measurements on Ce1−xZrxO2 thin films. A sol–gel synthesis procedure and spin-coating deposition method have been applied to make continuous nanocrystalline Ce1−xZrxO2 (x = 0–1) (CZ) thin films with uniform thickness (35–50 nm); however, surface roughness and porosity inherently changes with CZ composition. MB studies of O2 adsorption on CZ reveal high OSC for Ce0.9Zr0.1O2, which also exhibits highly porous and significantly rough surface characteristics. The surface potential observed from KPM studies varied between 30 and 80 mV, with Ce-rich compositions exhibiting the highest surface potential. Surface potential shows large changes after reduction or oxidation of the CZ film demonstrating the influence of Ce3+/Ce4+ on surface potential, which is also a key to catalytic activity for ceria-based catalysts. The surface potential measured from KPM and the OSC measured from MB vary linearly and they depend on the Ce3+/Ce4+ ratio. More and detailed studies are suggested to arrive at a correlation between the physical and chemical properties of the surfaces.

1 aKolekar, Sadhu, K.1 aDubey, Anjani1 aDate, Kalyani, S.1 aDatar, Suwarna1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/attempt-correlate-surface-physics-and-chemical-properties-molecular-beam-and-kelvin-probe01907nas a2200145 4500008004100000245013800041210006900179260000800248300001400256490000600270520130600276100002501582700003001607856012401637 2016 eng d00aBimetallic and plasmonic Ag-Au on TiO2 for solar water splitting : an active nanocomposite for entire visible light region absorption0 aBimetallic and plasmonic AgAu on TiO2 for solar water splitting  cOCT a3294-33010 v83 a

The current study demonstrates a potential method for maximum utilization of the entire visible light region of the solar spectrum by designing a plasmonic-metals semiconductor composite. A combination of Ag+Au nanoclusters would broaden the visible-light absorption at least between 400 and 650nm. This hypothesis was evaluated through solar water splitting (SWS) activity of Au-TiO2, Ag-TiO2, and Ag on Au-TiO2 (AgAuT) composites. AgAuT bimetallic nanocomposite shows the maximum apparent quantum yield of 3.3% with hydrogen generation (718molh.g(-1)) from aqueous methanol, and overall water splitting activity (7molg.h(-1), AQY=0.04%) under one sun conditions. Enhanced photocatalytic activity of AgAuT is partly attributed to the formation of hot electrons. A thin layer of Ag coating on Au particles leads to a core-shell morphology with Au in the core. Fermi level equilibration between metal and titania, and Schottky junction formation are directly demonstrated. The strong electronic interaction between Ag and Au, and with TiO2 is evident from its electron rich character and confirmed by Raman spectroscopy, X-ray photoelectron spectroscopy, photoluminescence, and high-resolution TEM measurements. Electronic factors seem to be responsible for the high rate of hydrogen production.

1 aPatra, Kshirodra, K.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/bimetallic-and-plasmonic-ag-au-tio2-solar-water-splitting-active-nanocomposite-entire01853nas a2200157 4500008004100000245010600041210006900147260000800216300001600224490000600240520125700246100001801503700002301521700003001544856012101574 2016 eng d00aC-H activation of methane to formaldehyde on Ce1-xZrxO2 thin films: a step to bridge the material gap0 aCH activation of methane to formaldehyde on Ce1xZrxO2 thin films cDEC a3650–36560 v83 a

Ce1−xZrxO2 (CZ) thin films were prepared by a combination of sol–gel and spin-coating methods and were evaluated for the C−H activation of methane by using a molecular beam set-up with the aim to bridge the material gap. The C−H activation of methane begins at 950 K, and a Ce-rich CZ composition displays a high selectivity (4–12 %) to the partially oxidised product, formaldehyde. A 10–12 % selectivity towards HCHO with 1.6 % methane conversion was observed with methane-rich CH4/O2 reactant compositions at 1050 K. Short contact times, prevalent under molecular beam conditions, could be a possible reason for HCHO formation. Although combustion products were observed instantly upon shining the mixture of reactants on CZ surfaces, up to 20 s delay was observed before formaldehyde generation, which indicates that the oxygen vacancy migration contributes to the rate-determining step and the diffusion-controlled nature of the reaction. A burst in HCHO generation at the point of molecular beam opening, after beam-closed conditions, suggests that the diffusion of oxygen vacancies to the surface is the reason for HCHO formation. Kinetics results also indicate the necessity of reduction sites for HCHO generation.

1 aDubey, Anjani1 aKolekar, Sadhu, K.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/c-h-activation-methane-formaldehyde-ce1-xzrxo2-thin-films-step-bridge-material-gap01544nas a2200157 4500008004100000245008400041210006900125260000800194300001400202490000600216520098800222100001801210700002301228700003001251856010501281 2016 eng d00aC-H activation of methane to syngas on MnxCe1-x-yZryO2 - a molecular beam study0 aCH activation of methane to syngas on MnxCe1xyZryO2 a molecular  cJUL a2296-23060 v83 a

Mn-doped ceria zirconia thin films (MnxCe1-x-yZryO2, MCZ) were employed as flat model catalyst surfaces for CH4 activation. MCZ films exhibit characteristics of single crystal and powder materials, such as smooth surfaces and porosity. From molecular-beam studies, it has been identified that the oxygen storage capacity increases with Mn content. Mutually exclusive observation of H2O or a mixture of products (CO2+ CO + H-2) occurs, when the reactants was allowed to react directly on MCZ, underscoring their formation or prevention (and consumption), respectively. The results suggest that there is competition and cooperation among different elementary reactions under complementary conditions. From a significant partial oxidation of CH4 through C-H activation, it is found that formation of syngas begins at 700 K and the reaction rate increases with increasing temperature. Kinetic evidences indicate that the reaction proceeds through a combustion-reformation pathway.

1 aDubey, Anjani1 aKolekar, Sadhu, K.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/c-h-activation-methane-syngas-mnxce1-x-yzryo2-molecular-beam-study02075nas a2200205 4500008004100000245008600041210006900127260000800196300001200204490000800216520133700224100002101561700002101582700002801603700003701631700002801668700003001696700002601726856011701752 2016 eng d00aEffective and selective oxidation of 2-butanol over Mn supported catalyst systems0 aEffective and selective oxidation of 2butanol over Mn supported  cSEP a237-2460 v5253 a

Oxidation of alcohols to their corresponding aldehydes/ketones is an important reaction in industries as well as in academic perspective. Selective oxidation (Selox) of alcohols like methanol, ethanol and propanol are well studied in literature; however, alcohols like butanol, pentanol, octanol is a challenging task. Selective oxidation of 2-butanol to methyl ethyl ketone (MEK) is an important reaction due to its wide range of applications. Herein, we demonstrated the selective oxidation of 2-butanol to MEK over Mn supported on different oxide supports. A series of MnxOy-Al2O3 (MA), MnxOy-CeO2 (MC), MnxOy-ZrO2 (MZ) and MnxOy-SiO2 (MS) catalysts were prepared by co-precipitation followed by hydrothermal method. As synthesised catalysts were characterised by various physico-chemical characterisation techniques. It was found that the presence of Mn3O4 species in MA and MZ catalysts is responsible for maximum catalytic activity towards 2-butanol oxidation. MA catalyst conferred a maximum 2-butanol conversion of 51% and 88% selectivity towards MEK. XPS analysis revealed that Mn in MA catalyst exists in +2 and +3 oxidation states and responsible for 2-butanol oxidation. Moreover it was found that the acidity of the catalyst also plays an important role in catalytic activity. (C) 2016 Published by Elsevier B.V.

1 aPrabu, Kandasamy1 aPrabu, Marimuthu1 aVenugopal, Ashok, Kumar1 aVenugopalan, Aswathy, Thareparam1 aSandilya, W., V. Y. Sai1 aGopinath, Chinnakonda, S.1 aRaja, Thirumalaiswamy uhttp://library.ncl.res.in/content/effective-and-selective-oxidation-2-butanol-over-mn-supported-catalyst-systems01716nas a2200193 4500008004100000245006600041210006600107260000800173300002600181490000600207520106500213100002301278700002101301700002501322700002901347700003001376700002201406856009401428 2016 eng d00aEnhancement in rate of photocatalysis upon catalyst recycling0 aEnhancement in rate of photocatalysis upon catalyst recycling cOCT aArticle Number: 350750 v63 a

Recyclability is an important aspect for heterogeneous photo-catalysts. Ease of recovery and stability of the photo-catalyst in terms of efficiency over the number of cycles are highly desired and in fact it is ideal if the efficiency is constant and it should not decrease marginally with each cycle. Presented here is a seminal observation in which the photocatalytic activity is shown to improve with increasing number of catalytic cycles (it is 1.7 times better after the 1st cycle and 3.1 times better after the 2nd cycle). Specifically, nanorods of pure TiO2 and TiO2 doped with controlled amount of tungsten have been used to degrade two model pollutants: Phenol and Rhodamine B under exclusive visible light illumination. It was found that, in case of 1 mol.% W incorporation, rate of photocatalysis and also the range of visible light absorption of the photocatalyst increased after the photocatalysis as compared to before photocatalysis. This aspect is unique for doped TiO2 and hence provides an intriguing way to mitigate low photoactivity.

1 aSorathiya, Kalpesh1 aMishra, Biswajit1 aKalarikkal, Abhishek1 aReddy, Kasala, Prabhakar1 aGopinath, Chinnakonda, S.1 aKhushalani, Deepa uhttp://library.ncl.res.in/content/enhancement-rate-photocatalysis-upon-catalyst-recycling01153nas a2200193 4500008004100000022001400041245009100055210006900146260011000215300001400325490000700339520038900346100001800735700001600753700002200769700003000791700001800821856012000839 2016 eng d a1359-734500aExploration of magnetically separable Ag@AgxNiy core/graded-alloy-shell nanostructures0 aExploration of magnetically separable AgAgxNiy coregradedalloysh aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJUN a8737-87400 v523 a

We report novel bimetallic Ag@AgxNiy core@graded-alloy-shell nanoparticles (CGAS NPs), i.e. single Ag core NPs shelled by an AgxNiy graded alloy and stabilized by the CTAB surfactant employing a novel synthesis method. These Ag@AgxNiy CGAS NPs demonstrated superior catalytic performance in the synthesis of biologically active 3-amino alkylated indoles under green conditions.

1 aKumar, Mukesh1 aSoni, Kiran1 aSatpati, Biswarup1 aGopinath, Chinnakonda, S.1 aDeka, Sasanka uhttp://library.ncl.res.in/content/exploration-magnetically-separable-agagxniy-coregraded-alloy-shell-nanostructures02571nas a2200181 4500008004100000022001400041245011600055210006900171260011000240300001400350490000600364520180000370100001602170700001802186700002702204700003002231856012802261 2016 eng d a2044-475300aGas-solid interaction of H-2-Ce0.95Zr0.05O2: new insights into surface participation in heterogeneous catalysis0 aGassolid interaction of H2Ce095Zr005O2 new insights into surface aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcOCT a1746-17560 v63 a

A direct interaction between a reduction medium (H-2) and a Ce0.95Zr0.05O2 (CZ) solid surface was explored through ambient pressure photoelectron spectroscopy (APPES), with conventional X-ray and He-I photon sources, in H-2 atmosphere up to 0.1 mbar pressure and 773 K. A porous CZ thin film was prepared by a combination of sol-gel and spin-coating methods, and was employed to understand the redox nature of ceria under reduction conditions. The maximum of 45% Ce3+ along with the corresponding oxygen vacancy was observed due to reduction. An unprecedented decrease in the valence band (VB) energy up to 1.4 eV was observed on reduction along with a narrowing of VB. The highest occupied energy band derived from Ce 4f also shifts closer to E-F. H-2 molecular vibration observed in VB-APPES was employed as a probe to explore the surface potential changes along with the dynamic change in the nature of the surface under reduction conditions. The surface potential decreases by 0.27 eV up to 673 K, and then it reverts by 0.24 eV on further reduction at 773 K for different reasons. Further, an enhancement in the Ce 5d-O 2p interaction occurs at the expense of the Ce 4f-O 2p interaction under the above reduction conditions. Vacuum annealing and H-2 reduction after that show significantly more VB shift and enhanced reduction than H-2 reduction alone. Although Ce reduction occurs on high temperature vacuum annealing of CZ, a significantly lower amount of oxygen vacancies appears. This study shows the dynamic changes in the nature of the surface due to a gas (H-2)-solid (CZ) interaction and ensuing electronic structure changes that influence heterogeneous catalysis. It also underscores the necessity to study the catalytic materials under in situ conditions or closer to that.

1 aJain, Ruchi1 aDubey, Anjani1 aGhosalya, Manoj, Kumar1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/gas-solid-interaction-h-2-ce095zr005o2-new-insights-surface-participation-heterogeneous-001435nas a2200157 4500008004100000245005400041210005300095260000800148300001400156490000700170520094700177100002201124700002201146700003001168856007901198 2016 eng d00aGreen leaf to inorganic leaf: a case study of ZnO0 aGreen leaf to inorganic leaf a case study of ZnO cSEP a9203-92080 v163 a

Can we use green leaves, available freely in our gardens, as a template for making inorganic leaf, while retaining the nanospace available within the leaf architecture. The answer is 'yes', and it is demonstrated with inorganic leaf made up of ZnO, by intercalating Zn2+ ions into the porous channels of the champa (Plumeria, Magnolia champaca) tree leaves. TEM studies reveal a variety of macro-micro-nanospace available in the inorganic leaf ZnO (IL-ZnO), and suggest the possibility of exploiting the same to produce natural nano-architecture for various applications. A speciality of the present work is the maximum suppression of defects in photoluminescence of IL-ZnO leaf, compared to the commercial ZnO, which is exploited for light harvesting through chemical conversion. Benzene to phenol conversion was studied in UV light and IL-ZnO show significant conversion and yield demonstrating C-H activation at ambient temperature.

1 aSathu, Naveen, K.1 aDevaraji, Perumal1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/green-leaf-inorganic-leaf-case-study-zno01964nas a2200169 4500008004100000245012400041210007000165260000800235300001600243490000600259520129900265100002301564700001901587700002401606700003001630856013401660 2016 eng d00aPalladium supported on fluorite structured redox CeZrO4-δ for heterogeneous suzuki coupling in water: a green protocol0 aPalladium supported on fluorite structured redox CeZrO4δ for het cJUL a2673–26810 v13 a

Pd on redox CeZrO4-δ catalysts was prepared, characterized and their activity was evaluated for Suzuki coupling reaction in water under reflux condition. Fresh and reduced form of 5 % Pd (R−Pd5) on CeZrO4-δ catalyst exhibited 100 % conversion in 2.5 and 1 h, respectively. R−Pd5 shows significant activity for wide range of substrate compatibility and for less reactive aryl bromides too. The mechanistic investigations proved the important role of redox CeZrO4-δ support on the catalytic activity. It was observed that the presence of oxygen vacancy along with Ce3+ enhances the activity. 1 wt % Pd photodeposited on pre-reduced CeZrO4-δ support requires a mere 20 min. for 100 % conversion of Suzuki coupling. Effect of metal dispersion and particle size on catalytic activity is also discussed. High Pd dispersion with small particle size (4±1 nm), particle size preservation after reaction, strong metal-support interaction and no leaching fully suggest the heterogeneous mechanism is operative for Suzuki coupling on 1 wt % Pd photodeposited on reduced CeZrO4-δ support. Present work hints the possibility of achieving high conversion for Suzuki reaction with very small amount of Pd through better dispersion by taking advantage of redox support and in water.

1 aBurange, Anand, S.1 aShukla, Rakesh1 aTyagi, Avesh, Kumar1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/palladium-supported-fluorite-structured-redox-cezro4-%CE%B4-heterogeneous-suzuki-coupling-water02105nas a2200193 4500008004100000245008300041210006900124260000800193300000900201490000600210520145500216100001801671700002301689700002601712700001501738700001801753700003001771856011001801 2016 eng d00aPorous thin films towards bridging the material gap in heterogeneous catalysis0 aPorous thin films towards bridging the material gap in heterogen cMAR a1-120 v23 a

An attempt has been made to bridge the material gap, existing between ideal single crystals and real-world powder nanocatalyst employed in surface science and heterogeneous catalysis, respectively. Simple wet chemical method (sol–gel and spin-coating deposition) has been applied to make continuous Ce1 − xZrxO2 (x = 0–1) (CZ) thin films with uniform thickness (~40 nm) and smooth surface characteristics. Uniform thickness and surface smoothness of the films over a large area was supported by a variety of measurements. Molecular beam (MB) studies of O2 adsorption on CZ surfaces reveals the oxygen storage capacity (OSC), and sticking coefficient increases from 400 to 800 K. Porous nature of Ce-rich CZ compositions enhances O2 adsorption and OSC, predominantly due to O-diffusion and redox nature, even at 400 K. A good correlation exists between MB measurements made on CZ films for oxygen adsorption, and OSC, and ambient pressure CO oxidation on powder form of CZ; this demonstrates the large potential to bridge the material gap. CZ was particularly chosen as a model system for the present studies, since it has been well-studied and a correlation between surface science properties made on thin films and catalysis on powder CZ materials could be a litmus test. Ambient catalysis on ceria-zirconia nanocatalyst correlates well with surface properties measured through molecular beam on thinfilm and close the material gap.

1 aDubey, Anjani1 aKolekar, Sadhu, K.1 aGnanakumar, Edwin, S.1 aRoy, Kanak1 aVinod, C., P.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/porous-thin-films-towards-bridging-material-gap-heterogeneous-catalysis01618nas a2200217 4500008004100000022001400041245007500055210006900130260011000199300001600309490000600325520081000331100001801141700002201159700002001181700001801201700002701219700003001246700002001276856010401296 2016 eng d a2046-206900aSeeding of Au on CdSe/CdS nanoplates using Langmuir-Blodgett technique0 aSeeding of Au on CdSeCdS nanoplates using LangmuirBlodgett techn aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJAN a14658-146650 v63 a

Oleyl amine capped CdSe/CdS nanoplates were synthesized by hot injection technique which formed a stable monolayer over both a water subphase and an aqueous HAuCl4 subphase using a Langmuir-Blodgett trough. Au islands were generated at the edge as well as on one specific surface of the flat nanoplates by exploiting the reducing capacity of oleyl amine to form Au nanoseeds from AuCl4- ions. The initial Au nanoseeds changed to a shell surrounding these nanoplates on prolonged exposure to the subphase containing the Au precursor. Monolayer of the hybrid structures was deposited onto suitable substrates for characterization by a number of different techniques and to study the photocatalytic activity. The same substrate with the monolayers could be re-used in several cycles of photocatalysis.

1 aDas, Subhasis1 aSatpati, Biswarup1 aChauhan, Himani1 aDeka, Sasanka1 aGhosalya, Manoj, Kumar1 aGopinath, Chinnakonda, S.1 aBala, Tanushree uhttp://library.ncl.res.in/content/seeding-au-cdsecds-nanoplates-using-langmuir-blodgett-technique-001917nas a2200181 4500008004100000245013000041210006900171260000800240300001400248490000600262520121900268100002401487700002401511700001801535700002401553700003001577856012801607 2016 eng d00aIs there any real effect of low dimensional morphologies towards light harvesting? a case study of Au-rGO-TiO2 nanocomposites0 athere any real effect of low dimensional morphologies towards li cAPR a917–9230 v13 a

Nanotube and nanosheet morphologies have been celebrated for their electron transport properties. Present work has been explored to exploit the same by combining 1D TiO2 nanotube (1D-TN) with 2D reduced graphene oxide (rGO) along with nano gold for visible light sensitization for photocatalytic H2 generation under one sun condition and visible light (λ≥ 400 nm). Vertical and horizontal electron transport in 1D-TN and rGO, respectively, is combined with the visible light absorption capability of Au nanoparticle. H2 yield (HY) varies between 100 and 655 µmol/g.h with an apparent quantum yield between 0.45 and 3.2 %, respectively, depending on Au/rGO/1D-TN preparation method and reaction conditions. It has been demonstrated that interfacial contact between rGO/1D-TN and Au is crucial for high photocatalytic HY. Preparation method influences charge utilization, and hence HY, to a large extent. Nonetheless, the maximum HY reported in the present work is just comparable to HY reported in literature with the most commonly found spherical morphology, and this leads to a question of, is there any real influence of 1D and/or 2D materials, particularly, towards light harvesting applications?

1 aMelvin, Ambrose, A.1 aBharad, Pradnya, A.1 aIllath, Kavya1 aLawrence, Meenu, P.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/there-any-real-effect-low-dimensional-morphologies-towards-light-harvesting-case-study-au01571nas a2200181 4500008004100000245010500041210006900146260000800215300001400223490000700237520090200244100001501146700001601161700002701177700002901204700003001233856012601263 2016 eng d00aThree way catalytic converter reactions aspects at near ambient temperatures on modified pd-surfaces0 aThree way catalytic converter reactions aspects at near ambient  cOCT a1363-13690 v193 a

The dissolution of oxygen in palladium plays an important role in palladium catalysis. The present study shows that the surface modification (SM) due to the dissolution of atomic oxygen into the subsurfaces of palladium can be used as a control to tune its catalytic activity. CO oxidation and NO + H-2 + O-2 reaction was separately carried out on metallic Pd and on surface modified Pd using a molecular beam instrument and the results were compared. The metallic Pd does not show activity below 400 K for both reactions, whereas the SM-Pd shows activity at near-ambient temperatures. The electronic change due to SM was investigated using ambient pressure photoelectron spectroscopy, and the investigation clearly shows the effect of subsurface oxygen in the ambient temperature activity of palladium. (C) 2016 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

1 aRoy, Kanak1 aJain, Ruchi1 aGhosalya, Manoj, Kumar1 aReddy, Kasala, Prabhakar1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/three-way-catalytic-converter-reactions-aspects-near-ambient-temperatures-modified-pd-001364nas a2200145 4500008004100000245009100041210006900132260000800201300001400209520080400223100001801027700002901045700003001074856011401104 2017 eng d00aAmbient CO oxidation on in-situ generated Co3O4 spinel surfaces with random morphology0 aAmbient CO oxidation on insitu generated Co3O4 spinel surfaces w cJAN a431–4323 a

The influence of the Co3O4 morphology on its redox behavior and catalytic performance in the CO oxidation reaction is studied. Three different Co3O4 morphologies were synthesized by precipitation and hydrothermal methods. TEM and SEM observations clearly show the different obtained morphologies: rods, wires and a mixture of plates and cubes. The textural properties depend on the morphology and the redox ones on the particle size. XRD analysis reveals a spinel structure in all solids but a preferential exposition of the [110] plane is presented in the Co3O4 rods. This preferential exposition, along with its higher specific surface area provides the rods with more efficient oxygen storage capacity resulting in an excellent catalytic performance compared to the other two morphologies.

1 aDubey, Anjani1 aReddy, Kasala, Prabhakar1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/ambient-co-oxidation-situ-generated-co3o4-spinel-surfaces-random-morphology02926nas a2200325 4500008004100000245010200041210006900143260000800212490000600220520185800226653003302084653001302117653001202130653003002142653002002172653002502192653001802217653001402235653001002249653002102259653001602280653002002296653002002316653003902336100002302375700002902398700003002427700001802457856012502475 2017 eng d00aCopper Cobalt Sulfide Nanosheets Realizing a Promising Electrocatalytic Oxygen Evolution Reaction0 aCopper Cobalt Sulfide Nanosheets Realizing a Promising Electroca cSEP0 v73 a

Nanostructured CuCo2S4, a mixed metal thiospinel, is found to be a benchmark electrocatalyst for oxygen evolution reaction (OER) in this study with a low overpotential, a low Tafel slope, a high durability, and a high turnover frequency (TOF) at lower mass loadings. Nanosheets of CuCo2S4 are realized from a hydrothermal synthesis method in which the average thickness of the sheets is found to be in the range of 815 nm. Aggregated nanosheets form a highly open hierarchical structure. When used as an electrocatalyst, CuCo2S4 nanosheets offer an overpotential value of 310 mV at a 10 mA cm(2) current density, which remains consistent for 10000 measured cycles in a 1 M KOH electrolyte. A chronoamperometric study reveals constant oxygen evolution for 12 h at a 10 mV s(-1) scan rate without any degradation of the activity. Furthermore, the calculated mass activity of the CuCo2S4 electrocatalyst is found to be 14.29 A/g and to afford a TOF value of 0.1431 s(-1) at 310 mV at a mass loading of 0.7 mg cm(-2). For comparison, nanostructures of Co3S4 and Cu0.5Co2.5S4 have been synthesized using a similar method followed for CuCo2S4. When compared to the OER activities among these three thiospinels and standard IrO2, CuCo2S4 nanosheets offered the highest OER activities at the same mass loading (0.7 mg/cm(-2)). Extensive X-ray photoelectron spectroscopy and electron paramagnetic resonance analyses for a mechanistic study reveal that introduction of Cu into the Co3S4 lattice enhances the oxygen evolution and kinetics by offering Cu2+ sites for utilitarian adsorption of OH, O, and OOH reactive species and also by offering a highly active high-spin state of octahedral Co3+ for OER catalysis.

10aBifunctional Electrocatalyst10aCatalyst10aCuco2s410aEfficient Electrocatalyst10aelectrocatalyst10aElectronic-structure10aNanoparticles10aNanosheet10aoxide10aoxygen evolution10aperformance10aRecent Progress10aWater oxidation10aWater Splitting Hydrogen Evolution1 aChauhan, Meenakshi1 aReddy, Kasala, Prabhakar1 aGopinath, Chinnakonda, S.1 aDeka, Sasanka uhttp://library.ncl.res.in/content/copper-cobalt-sulfide-nanosheets-realizing-promising-electrocatalytic-oxygen-evolution01798nas a2200181 4500008004100000022001400041245012100055210006900176260000900245300001400254490000600268520112600274100002601400700001601426700003001442700001801472856012601490 2017 eng d a2044-475300aDiverse reactivity trends of Ni surfaces in Au@Ni core-shell nanoparticles probed by near ambient pressure (NAP) XPS0 aDiverse reactivity trends of Ni surfaces in AuNi coreshell nanop cOCT  a4489-44980 v73 aA mild temperature sequential reduction method in aqueous medium is reported for the synthesis of Au@Ni nanoparticles with a core-shell morphology. The nickel shell thickness with a gold core in the nanostructure can be tuned from 2 nm up to about 10 nm. Near ambient pressure XPS (NAPXPS) studies under oxygen atmosphere show that Au-80@Ni-20 with an extremely thin nickel shell (similar to 2 nm) follows a distinctly different decomposition pathway of metastable Ni(OOH) species compared to those with larger shell thickness which behave more like individual nickel surfaces. Thus, Ni(OOH) on Au-80@Ni-20 decomposes to metallic Ni at 100 degrees C and is found to resist oxidation at 0.1 mbar oxygen at this temperature. Those with a larger nickel shell thickness behave more like monometallic Ni in terms of their decomposition and oxidation properties. The Au@Ni system with an ultra thin metallic nickel overlayer (2 nm) shows high catalytic activity and selectivity for phenylacetylene hydrogenation under mild conditions which outweighs their monometallic counterparts and those with higher nickel shell thickness.1 aBharathan, Vysakh, A.1 aJain, Ruchi1 aGopinath, Chinnakonda, S.1 aVinod, C., P. uhttp://library.ncl.res.in/content/diverse-reactivity-trends-ni-surfaces-auni-core-shell-nanoparticles-probed-near-ambient01849nas a2200241 4500008004100000022001400041245009900055210006900154260000900223300001400232490000800246520101600254100001601270700001801286700002201304700002901326700002001355700002201375700003001397700002201427700003001449856012801479 2017 eng d a1932-744700aEfficient organic photovoltaics with improved charge extraction and high short-circuit current0 aEfficient organic photovoltaics with improved charge extraction  cMAR  a5523-55300 v1213 a

Exciton generation, dissociation, free carrier transport, and charge extraction play an important role in the short-circuit current (J(sc)) and power conversion efficiency of an organic bulk heterojunction (BHJ) solar cell (SC). Here we study the impact of band offset at the interfacial layer and the morphology of active layer on the extraction of free carriers. The effects are evaluated on an inverted BHJ SC using zinc oxide (ZnO) as a buffer layer, prepared via two different methods: ZnO nanoparticle dispersed in mixed solvents (ZnO A) and sol-gel method (ZnO B). The device with ZnO A buffer layer improves the charge extraction and J(sc),. The improvement is due to the better band offset and morphology of the blend near the ZnO A/active layer interface. Further, the numerical analysis of current-voltage characteristics illustrates that the morphology at the ZnO A/active layer interface has a more dominant role in improving the performance of the organic photovoltaic than the band offset.

1 aMohan, Minu1 aNandal, Vikas1 aParamadam, Sanish1 aReddy, Kasala, Prabhakar1 aRamkumar, Sekar1 aAgarwal, Sumanshu1 aGopinath, Chinnakonda, S.1 aNair, Pradeep, R.1 aNamboothiry, Manoj, A. G. uhttp://library.ncl.res.in/content/efficient-organic-photovoltaics-improved-charge-extraction-and-high-short-circuit-current01273nas a2200181 4500008004100000245007400041210006900115260000800184300002700192490000600219520064600225100001800871700002000889700002700909700003000936700002000966856010500986 2017 eng d00aFacile synthesis of Al2O3-Pt nanocomposite and its catalytic activity0 aFacile synthesis of Al2O3Pt nanocomposite and its catalytic acti cNOV aArticle Number: 1150020 v43 aPt nanoparticles were synthesized on gamma-alumina support in presence of oleic acid which was found to prevent clustering of Pt nanoparticles on the support. Various percentage of Pt loading on the alumina changed the catalytic activity for preferential oxidation of CO at relatively low temperature in H-2 rich stream. Pt nanoparticles when synthesized in absence of oleic acid, were all clustered and did not have any catalytic activity. The presence of oleic acid promoted stability preventing agglomeration of Pt nanoparticles. The catalyst thus prepared was characterized thoroughly and their catalytic activity was studied in details.1 aDas, Subhasis1 aBordoloi, Ankur1 aGhosalya, Manoj, Kumar1 aGopinath, Chinnakonda, S.1 aBala, Tanushree uhttp://library.ncl.res.in/content/facile-synthesis-al2o3-pt-nanocomposite-and-its-catalytic-activity01447nas a2200181 4500008004100000245007700041210006900118260000800187300002700195490000600222520081200228100002201040700001801062700002701080700003001107700002001137856010801157 2017 eng d00aFacile synthesis of ZnO-Ag nanocomposite and its photocatalytic activity0 aFacile synthesis of ZnOAg nanocomposite and its photocatalytic a cMAY aArticle Number: 0550110 v43 a

The evolution of photoactive hybrid materials (e.g. noble metal-semiconductor) has resulted in heterogeneous photocatalysis. We report a facile route for the synthesis of ZnO-Ag nanocomposites with varying percentage of loading of the noble metal, expecting a great boost in the photocatalytic behavior of ZnO. The as prepared material was thoroughly characterized by UV-Vis, FTIR, TEM, FESEM, XRD, XPS analyses. The photocatalytic activities of the nanocomposites have been assessed from the ability to degrade methylene blue dye in aqueous solution. The results suggest that incorporation of Ag nanoparticles on the surface of ZnO particles can enhance catalytic activity in comparison to pure ZnO particles under visible light by minimizing the recombination of photogenerated electron-hole pairs.

1 aSardar, Debasmita1 aMaity, Jayeta1 aGhosalya, Manoj, Kumar1 aGopinath, Chinnakonda, S.1 aBala, Tanushree uhttp://library.ncl.res.in/content/facile-synthesis-zno-ag-nanocomposite-and-its-photocatalytic-activity01666nas a2200217 4500008004100000245009500041210006900136260000800205300001200213490000600225520093600231653001301167653002001180653002801200653001201228653001601240100001601256700002601272700003001298856012001328 2017 eng d00aMechanistic aspects of wet and dry CO oxidation on Co3O4 nanorod surfaces: a NAP-UPS study0 aMechanistic aspects of wet and dry CO oxidation on Co3O4 nanorod cMAR a828-8340 v23 a

Catalytic activity, electronic structure, and the mechanistic aspects of Co3O4 nanorod (NR) surfaces have been explored for CO oxidation in dry and wet atmosphere using near-ambient pressure ultraviolet photoelectron spectroscopy. Presence of water with CO + O2 plummets the catalytic activity because of the change in the electronic nature from predominantly oxide (without water in feed) to a Co3O4 surface covered by a few intermediates. However, at ≥375 K, the Co3O4 surface recovers and regains the oxidation activity, at least partially, even in the presence of water. This is fully supported by the changes observed in the work function of Co3O4 under wet (H2O + CO + O2) conditions compared with dry (CO + O2) conditions. This study focuses on the comparative CO oxidation rate on Co3O4 NR surfaces and highlights the changes in the electronic structure that occur in the catalyst during the CO oxidation reaction.

10aCatalyst10aNano Structures10aPower X-Ray Diffraction10aspectra10aWater Vapor1 aJain, Ruchi1 aGnanakumar, Edwin, S.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/mechanistic-aspects-wet-and-dry-co-oxidation-co3o4-nanorod-surfaces-nap-ups-study02356nas a2200181 4500008004100000022001400041245011900055210006900174260000800243300001600251490000800267520167700275100002901952700001601981700002701997700003002024856012002054 2017 eng d a1932-744700aMetallic cobalt to spinel Co3O4-electronic structure evolution by near-ambient pressure photoelectron spectroscopy0 aMetallic cobalt to spinel Co3O4electronic structure evolution by cOCT a21472-214810 v1213 a

In the present study, valence band (VB) and core level photoelectron spectroscopy was carried out to investigate the electronic structural changes from polycrystalline Co to spinel Co3O4, via CoO at near ambient pressures (NAP; similar to 0.1). O-2 Co and H-2-CoOx gas solid oxidative and reductive interactions, respectively, have been explored with UV photons (He I) or low kinetic energy electrons (<= 16 eV) under NAP conditions. Typical VB features of Co metal, CoOx Co3O4, and a mixed phase between any two adjacent features were observed and well corroborated with core level changes. Very significant and characteristic changes were observed with Co 3d features in the VB for each stage from Co oxidation to Co3O4 as well as Co3O4 reduction to CoOx Co(3O)4 and CoO can be reversibly obtained by alternating the conditions between 0.1 mbar of H-2 at 650 K and 0.1 mbar of O 2 at 400 K, respectively. A meaningful correlation is observed between the changes in work function with cation oxidation state; small changes in the stoichiometry can strongly influence the shift in Fermi level and changes in work function under NAP conditions. Reversible work function changes are observed at a constant BE (similar to 5 ev) between oxidation and reduction conditions. While the O 2 p derived feature for CoOx was observed at throughout the redox conditions, the Co 3d band and molecular oxygen or hydrogen vibration feature shifts significantly underscoring the physicochemical changes, such as charge transfer energy and hence changes in satellite intensity. The peak close to E-F originated from the 3d(6)L final state of the octahedral Co3+ 3d band of Co3O4.

1 aReddy, Kasala, Prabhakar1 aJain, Ruchi1 aGhosalya, Manoj, Kumar1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/metallic-cobalt-spinel-co3o4-electronic-structure-evolution-near-ambient-pressure01719nas a2200205 4500008004100000245013500041210006900176260000800245520093500253100002201188700002401210700002001234700001901254700001801273700002601291700001601317700003001333700002001363856013001383 2017 eng d00aMultiple functionalities of Ni nanoparticles embedded in carboxymethyl guar gum polymer: catalytic activity and superparamagnetism0 aMultiple functionalities of Ni nanoparticles embedded in carboxy cJAN3 aComposites comprising of metallic nanoparticles in polymer matrices have allured significant importance due to multifunctionalities. Here a simple protocol has been described to embed Ni nanoparticles in carboxymethyl guar gum (CMGG) polymer. The composite formation helps in the stabilization of Ni nanoparticles which are otherwise prone towards aerial oxidation. Further the nanoparticles retain their superparamagnetic nature and catalytic capacity. Ni-Polymer composite catalyses the reduction of 4-Nitrophenol to 4-Aminophenol very efficiently in presence of NaBH4, attaining a complete conversion under some experimental conditions. Ni-Polymer composite is well characterized using UV–vis spectroscopy, FTIR, XPS, powder XRD, TGA, SEM and TEM. A detailed magnetic measurement using superconducting quantum interference device-vibrating sample magnetometer (SQUID-VSM) reveals superparamagnetic behaviour of the composite.1 aSardar, Debasmita1 aSengupta, Manideepa1 aBordoloi, Ankur1 aAhmed, Md., A.1 aNeogi, S., K.1 aBandyopadhyay, Sanjoy1 aJain, Ruchi1 aGopinath, Chinnakonda, S.1 aBala, Tanushree uhttp://library.ncl.res.in/content/multiple-functionalities-ni-nanoparticles-embedded-carboxymethyl-guar-gum-polymer-catalytic01874nas a2200157 4500008004100000245008400041210006900125260000800194300002500202490000600227520128900233100002801522700002301550700003001573856011301603 2017 eng d00aPossibly scalable solar hydrogen generation with quasi-artificial leaf approach0 aPossibly scalable solar hydrogen generation with quasiartificial cJUL aArticle Number: 65150 v73 aAny solar energy harvesting technology must provide a net positive energy balance, and artificial leaf concept provided a platform for solar water splitting (SWS) towards that. However, device stability, high photocurrent generation, and scalability are the major challenges. A wireless device based on quasi-artificial leaf concept (QuAL), comprising Au on porous TiO2 electrode sensitized by PbS and CdS quantum dots (QD), was demonstrated to show sustainable solar hydrogen (490 +/- 25 mu mol/h (corresponds to 12 ml H-2 h(-1)) from similar to 2mg of photoanode material coated over 1 cm(2) area with aqueous hole (S2-/SO32-) scavenger. A linear extrapolation of the above results could lead to hydrogen production of 6 L/h.g over an area of similar to 23 x 23 cm(2). Under one sun conditions, 4.3 mA/cm(2) photocurrent generation, 5.6% power conversion efficiency, and spontaneous H-2 generation were observed at no applied potential (see S1). A direct coupling of all components within themselves enhances the light absorption in the entire visible and NIR region and charge utilization. Thin film approach, as in DSSC, combined with porous titania enables networking of all the components of the device, and efficiently converts solar to chemical energy in a sustainable manner.1 aPatra, Kshirodra, Kumar1 aBhuskute, Bela, D.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/possibly-scalable-solar-hydrogen-generation-quasi-artificial-leaf-approach02123nas a2200181 4500008004100000245010700041210006900148260000800217300002600225490000600251520144700257100002001704700002301724700001701747700002001764700003001784856012701814 2017 eng d00aStudy on doped heterojunctions in TiO2 nanotubes: an efficient photocatalyst for solar water splitting0 aStudy on doped heterojunctions in TiO2 nanotubes an efficient ph cOCT aArticle Number: 143140 v73 aThe two important factors that affect sunlight assisted water splitting ability of TiO2 are its charge recombination and large band gap. We report the first demonstration of nitrogen doped triphase (anatase-rutile-brookite) TiO2 nanotubes as sun light active photocatalyst for water splitting with high quantum efficiency. Nitrogen doped triphase TiO2 nanotubes, corresponding to different nitrogen concentrations, are synthesized electrochemically. Increase in nitrogen concentration in triphase TiO2 nanotubes is found to induce brookite to anatase phase transformation. The variation in density of intra-band states (Ti3+ and N 2p states) with increase in nitrogen doping are found to be critical in tuning the photocatalytic activity of TiO2 nanotubes. The presence of bulk heterojunctions in single nanotube of different nitrogen doped TiO2 samples is confirmed from HRTEM analysis. The most active nitrogen doped triphase TiO2 nanotubes are found to be 12 times efficient compared to pristine triphase TiO2, for solar hydrogen generation. The band alignment and charge transfer pathways in nitrogen doped TiO2 with triphase heterojunctions are delineated. Bulk heterojunctions among the three phases present in the nanotubes with intra-band defect states is shown to enhance the photocatalytic activity tremendously. Our study also confirms the theory that three phase system is efficient in photocatalysis compared to two phase system.1 aPreethi, L., K.1 aAntony, Rajini, P.1 aMathews, Tom1 aWalczak, Lukasz1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/study-doped-heterojunctions-tio2-nanotubes-efficient-photocatalyst-solar-water-splitting02883nas a2200301 4500008004100000022001400041245016300055210006900218260000800287300001800295490000800313520181300321653002402134653002002158653001402178653001702192653001202209653002902221653001902250653002802269653003602297653001502333100001602348700002902364700002702393700003002420856013102450 2017 eng d a1932-744700aWater mediated deactivation of Co3O4 naonrods catalyst for CO oxidation and resumption of activity at and above 373 K: electronic structural aspects by NAPPES0 aWater mediated deactivation of Co3O4 naonrods catalyst for CO ox cSEP a20296–203050 v1213 a

The catalytic activity of the Co3O4 nanorods (NRs) for the CO oxidation reaction and the effect of water on the catalytic reaction have been explored with near-ambient pressure photoelectron spectroscopy (NAPPES) and mass spectral analysis. Comparative NAPPES studies have been employed to understand the elucidation of the catalytic reaction pathway and the evolution of various surface species. The results confirm the suppression of the CO oxidation activity on the Co3O4 NRs in the presence of water vapor. Various type of surface species, such as CO(ads), hydroxyl, carbonate, formate, are found to be present on the catalyst surface depending on the reaction conditions. Vibrational features of CO, O-2, and CO, were observed and shift in binding energy of these features under the reaction conditions directly suggests a change in work function of the catalyst surface. Under dry conditions, CO couples with labile 0 atoms to form CO2; however, under wet conditions, CO predominantly interacts with surface OH groups resulting in the formation of carbonate and formate intermediates. In situ studies of oxidation of CO on Co3O4 shows that CO oxidation depends not only on surface Co3+ concentration but also influenced by Co-3/Co' ratio on the catalyst surface. The carbonate was found to be a reaction inhibitor at room temperature; however, it acts as an active intermediate at 375 K and above. Above the boiling point of water, Co3O4 NR surfaces begin to show the oxidation activity even in the presence of water vapor. The intrinsic role of intermediate species was used to derive a possible reaction mechanism under different reaction conditions.

10aAmbinent-temprature10acarbon monoxide10aGas Shift10aH Activation10aIn-situ10aLow-temprature oxidation10aMolecular-beam10aPerformance enhancement10aRay Photoelectron-Spectroscopyu10aThin-films1 aJain, Ruchi1 aReddy, Kasala, Prabhakar1 aGhosalya, Manoj, Kumar1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/water-mediated-deactivation-co3o4-naonrods-catalyst-co-oxidation-and-resumption-activity-and01636nas a2200181 4500008004100000022001500041245009700056210006900153260000800222300001600230490000600246520100000252100002401252700000501276700001701281700003001298856012601328 2018 eng d a 2365-654900aCuOx-TiO2 composites: electronically integrated nanocomposites for solar hydrogen generation0 aCuOxTiO2 composites electronically integrated nanocomposites for cNOV a12022-120300 v33 a

CuOx-TiO2 (CT) composites were prepared by different methods (impregnation, microwave and photodeposition methods) and evaluated for solar water splitting (SWS) with aqueous methanol. CT composites prepared by three different methods were characterized by relevant methods to understand the correlation between synthesis method and activity, and the mechanism of water splitting. A comparison of photocatalytic activity of CT composite materials indicates that the photocatalyst prepared by photodeposition method shows significantly improved activity for hydrogen production from aqueous methanol as well as with water (overall water splitting) under one sun conditions. Cu is present in Cu/Cu+1 form in photodeposition method prepared CT, which is more effective and helpful for solar light absorption as well as charge carrier separation due to the formation of bulk p-n (Cu2O-TiO2) heterojunctions. However, CuO formation seems to decrease the activity with other preparation methods.

1 aBharad, Pradnya, A.1 a1 aThomas, Femi1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/cuox-tio2-composites-electronically-integrated-nanocomposites-solar-hydrogen-generation01645nas a2200229 4500008004100000022001400041245009800055210006900153260000900222300001400231490000700245520085500252100001801107700002601125700002201151700001801173700001801191700002701209700003001236700002001266856012901286 2018 eng d a1144-054600aDeposition of Au nanoparticles inside porous CeO2 nanocubes using Langmuir-Blodgett technique0 aDeposition of Au nanoparticles inside porous CeO2 nanocubes usin cJAN  a1379-13860 v423 a

Porous 3D CeO2 nanocubes were synthesized using hot injection technique. These nanocubes were able to form a stable monolayer over water and HAuCl4 subphase in Langmuir-Blodgett (LB) trough due to the presence of surface capped oleic acid and oleylamine. CeO2-Au nanocomposites were synthesized exploiting the ability of oleylamine to reduce AuCl4 ions to Au-0, via LB method. CeO2 nanocubes gave rise to excellent long-range assembly at air/water interface and gold nanoparticles were formed inside these porous nanocubes without disturbing this arrangement. The formation of a stable monolayer was evidenced from the surface pressure-area (P-A) isotherm. The development of Au nanoparticles was confirmed with great effort from a comprehensive study using UV-Vis spectroscopy, XRD, XPS, FTIR, TEM, STEM, EDX, tomography and chemical mapping.

1 aDas, Subhasis1 aBhattacharjee, Gourab1 aSatpati, Biswarup1 aKumar, Mukesh1 aDeka, Sasanka1 aGhosalya, Manoj, Kumar1 aGopinath, Chinnakonda, S.1 aBala, Tanushree uhttp://library.ncl.res.in/content/deposition-au-nanoparticles-inside-porous-ceo2-nanocubes-using-langmuir-blodgett-technique02178nas a2200181 4500008004100000022001500041245013700056210006900193260000800262300001000270490000700280520148400287100002501771700003001796700002501826700001901851856012601870 2018 eng d a 0925-963500a Enhanced microwave absorption property of reduced graphene oxide (RGO)-strontium hexaferrite (SF)/poly (vinylidene) fluoride (PVDF)0 aEnhanced microwave absorption property of reduced graphene oxide cOCT a28-340 v893 aEnormous growth in the use of electronic gadgets presents a challenge to develop efficient electromagnetic interference (EMI) shielding materials specifically using composites with properties such as light weight and high shielding due to absorption. In the present work we have synthesized a composite material with three components; Reduced Graphene Oxide (RGO) and Strontium Hexaferrite (SrFe12O19) (SF) bound together by polymer Poly (Vinylidene) Fluoride (PVDF). Composite RGO/SF (RGOSF) was prepared by facile one port chemical reduction method. Surface anchoring of similar to 500 nm of magnetic particles over the graphene sheet was confirmed by Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM). Crystal structure of SF particles was analyzed before and after composite formation with RGO. Effective crystallite size was estimated from both XRD and Raman Spectroscopy which showed similar trend moving from SF to RGOSF to RGOSFPVDF. Polymer composite films of RGOSFPVDF were prepared by hot pressing. Both real and imaginary part of magnetic and dielectric parameters were studied. It was observed that enhancement of interfacial polarization and anisotropic heat loss in PVDF matrix was generated by RGOSF which ultimately created more scattering center and helped in absorption of electromagnetic radiation. Critical film thickness of 3 mm was capable to shield up to 33 dB EM energy of which > 99.9% was due to absorption.1 aAcharya, Sanghamitra1 aGopinath, Chinnakonda, S.1 aAlegaonkar, Prashant1 aDatar, Suwarna uhttp://library.ncl.res.in/content/enhanced-microwave-absorption-property-reduced-graphene-oxide-rgo-strontium-hexaferrite01970nas a2200157 4500008004100000022001400041245010800055210006900163260000900232300001400241490000800255520136400263100002801627700003001655856012701685 2018 eng d a1932-744700aHarnessing visible-light and limited near-IR photons through plasmon effect of gold nanorod with AgTiO20 aHarnessing visiblelight and limited nearIR photons through plasm cJAN  a1206-12140 v1223 a

The utilization of the red-green-blue (RGB) and limited near-IR photons for solar hydrogen evolution (SHE) has been reported in a single plasmonic nanocomposite. Present study describes the use of AgTiO2 (AgT) decorated with Au nanorods (AgT-AuNR) to enhance the absorption of entire visible-light and limited near-IR wavelength range in the sunlight for SHE from photocatalytic water splitting reaction. It is demonstrated that the longitudinal plasmon resonance of AuNR in AgT-AuNR induces SHE between 550 and 800 nm, whereas TiO2-AuNR or AgT shows no activity in this wavelength range. The key aspect of achieving the high photocatalytic activity of AgT-AuNR in the solar spectrum is the electronic integration among metal NPs as well as with TiO2, and the heterojunctions among them. Presence of such heterojunctions has been supported by different characterization studies. However, gold nanorod exhibits field effect and further enhances light harvesting. Although the absolute amount of energy harvested only from near-IR photons is low, when combined with high-energy visible-light photons within one sun conditions, it shows a multiplier effect rather than a simple additive effect. Likely, this is the first report, where SHE has been achieved with significant amount of light absorption at lambda >= 550 nm with a plasmonic nanocomposite.

1 aPatra, Kshirodra, Kumar1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/harnessing-visible-light-and-limited-near-ir-photons-through-plasmon-effect-gold-nanorod02683nas a2200181 4500008004100000022001400041245015500055210006900210260000800279300001600287490000800303520195400311100002902265700002302294700002702317700003002344856012702374 2018 eng d a1932-744700aMapping valence band and interface electronic structure changes during the oxidation of Mo to MoO3 via MoO2 and MoO3 reduction to MoO2: A NAPPES study0 aMapping valence band and interface electronic structure changes  cOCT a23034-230440 v1223 a

Tuning the surface energetics, especially work function (phi) of the materials, is of a great deal of interest for a wide range of surface- and interface-based devices and applications. How the phi of a solid surface changes under the reaction conditions is of paramount interest to the chemists, particularly in the areas of surface dependent phenomena such as, catalysis and electrochemistry. In the present study, by using the valence band and core-level photoelectron spectroscopy, surface-electronic changes from Mo to MoO3 via MoO2 was studied under relevant near-ambient pressure (NAP) and high temperature conditions. A very significant change in phi from Mo to MoO3 was observed and it is well corroborated with the changes in gas-phase vibrational features of O-2 in both near-ambient pressure ultraviolet photoelectron spectra (NAPUPS) as well in NAP X-ray photoelectron spectroscopy. Reversible changes in the electronic structure is observed when MoO3 was reduced in H-2 to MoO2. On the basis of the extent of oxidation/reduction of MoOx NAPUPS has shown, one or two additional peaks in the band gap at 0.6 and 1.6 eV below the Fermi level. Mo5+ features are identified in the VB and in the Mo 3d core levels with distinct features. Mo5+ features are also stable and essential to bridge MoO2 and MoO3 layers, and their co-existence. In addition, characteristic changes in Mo 4d and O 2p features observed from Mo to MoO3 and well corelated to the band gap of MoO3. Oxidation and reduction propagate from the surface to bulk; indeed, this has significant implications in surface-dependent phenomena. The present study demonstrates (a) the uniqueness of NAPUPS in identifying the subtle to large changes in the electronic structure on solid surfaces under common oxidation and reduction (in general, under reaction) conditions, and (b) relevance of NAPUPS to all surface dependent phenomena, such as catalysis and electrochemistry.

1 aReddy, Kasala, Prabhakar1 aMhamane, Nitin, B.1 aGhosalya, Manoj, Kumar1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/mapping-valence-band-and-interface-electronic-structure-changes-during-oxidation-mo-moo302084nas a2200241 4500008004100000022001400041245011900055210006900174260000800243300001200251490000600263520126900269653002001538653001201558653001801570653001201588653002001600100002601620700001701646700002001663700003001683856012901713 2018 eng d a2194-428800aMarginally hydrogenated triphasic titania nanotubes for effective visible-light photocatalytic hydrogen generation0 aMarginally hydrogenated triphasic titania nanotubes for effectiv cFEB a280-2880 v63 a

We report the first demonstration of hydrogen-annealed triphase TiO nanotubes (anatase-rutile-brookite) (T-ARB) as a visible-light-active photocatalyst for water splitting with high quantum efficiency. As-synthesized T-ARB was annealed under hydrogen atmosphere at 250 and 4508 degrees C for 2 h. We found that the tubular structures were retained in the hydrogenated TiO2 samples. It was observed that the concentrations of Ti3+ and the oxygen vacancies and their distribution significantly increased with respect to the hydrogen annealing temperature. Such changes in defects were found to be critical in enhancing the photocatalytic activity of the hydrogen-annealed triphase TiO2 nanotubes. The triphase TiO2 nanotubes hydrogen annealed at 450 degrees C were 16 times more efficient than pristine TiO2. Such an increase in the photocatalytic activity was explained by a triphase band diagram with defect states below the conduction band of each phase, which facilitated visible-light activity and easy transfer of charge carriers from one phase to another. Our study showed that the well-designed multiphase construction with oxygen vacancies enhanced the photocatalytic activity tremendously owing to the presence of a higher number of phase junctions.

10acharge transfer10aDefects10aHydrogenation10atitania10awater splitting1 aPreethi, Laguduva, K.1 aMathews, Tom1 aWalczak, Lukasz1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/marginally-hydrogenated-triphasic-titania-nanotubes-effective-visible-light-photocatalytic02570nas a2200157 4500008004100000022001400041245017100055210006900226260000900295300001600304490000700320520191700327100001602244700003002260856012202290 2018 eng d a1944-824400aNew strategy toward a dual functional nanocatalyst at ambient conditions: influence of the Pd-Co interface in the catalytic activity of Pd@Co core-shell nanoparticles0 aNew strategy toward a dual functional nanocatalyst at ambient co cDEC  a41268-412780 v103 a

Bimetallic nanostructures with a combination of noble and nonnoble metals hold promise for improving catalyst activity and selectivity. Here, we report the synthesis of Pd@Co (PC) core shell morphology nanoparticles with three different ratios of palladium (Pd) and cobalt (Co), and a possibility to fine tune the ratio of core and shell thickness. PC exhibits superior and selective hydrogenation as well as oxidation catalytic activity at ambient or near-ambient conditions. Various characterization techniques have been employed to confirm the core shell morphology. Without any pre-treatment or activation, fresh catalysts with different Pd to Co ratios, that is, 2:1, 1:1, and 1:2, were subjected to olefin (phenylacetylene) hydrogenation and oxidation (styrene to styrene oxide) reaction. The catalytic activity results demonstrate that the 1:1 ratio of Pd/Co is the most active composition for controlled and stepwise reduction of phenyl acetylene to styrene and then to ethyl benzene; 1:1 Pd/Co shows 100% styrene conversion in 30 min. with an order of magnitude higher turnover frequency than other catalysts. The 1:1 PC ratio is also the most active composition for selective oxidation of styrene to styrene oxide. NAPXPS (near-ambient pressure XPS) results show that the active sites for catalytic hydrogenation and oxidation reaction are Co and Co3+, respectively. However, the superior catalytic performance can be attributed to Co (for reduction) or Co3+ (for oxidation), and the Pd Co interface plays a critical role in stabilizing the required functional character. NAPXPS results confirm that the superior catalytic performance can be attributed not only to Co or Co3+, but also to the Pd Co interface. The electronic effect and synergism between Co and Pd helps Co to stabilize in different oxidation states depending on the reaction conditions, and making it a dual functional catalyst.

1 aJain, Ruchi1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/new-strategy-toward-dual-functional-nanocatalyst-ambient-conditions-influence-pd-co02415nas a2200217 4500008004100000022001400041245009900055210006900154260000800223300001200231490000700243520166800250653002701918653001901945653002101964653001901985653002002004100002202024700003002046856012102076 2018 eng d a0360-319900aPt - g-C3N4 - (Au/TiO2): electronically integrated nanocomposite for solar hydrogen generation0 aPt gC3N4 AuTiO2 electronically integrated nanocomposite for sola cJAN a601-6130 v433 a

A potential nanocomposite photocatalyst was designed by integrating Pt nanoclusters (co catalyst and electron sink) with graphitic carbon nitride (g-C3N4 (gcn)) (charge diffusion) and 0.5 wt % Au containing Au-TiO2 (AuT) (plasmonic on semiconductor) for solar water splitting (SWS). Variety of Pt-gcn-AuTiO2 compositions has been evaluated for SWS under one sun conditions. Complexity of the photocatalyst was increased systematically from Au-TiO2, gcn-TiO2 to Pt-gcn-Au-TiO2 to explore the influence of different combinations. Electronic integration of charge separation/diffusion component (gcn) with light absorbing sensitizer components (Au and gcn), and co-catalyst (Pt) seems to be the critical factor to improve hydrogen yield (HY) or overall efficiency. Although addition of gcn increase the HY of composites, there is no SWS activity observed on bare TiO2 or gcn. Au or Pt on gcn enhances the charge separation effectively and interface between Au and/or Pt with gcn works as the Schottky barrier. A monodispersion of Au over TiO2 and Pt nanoclusters over gcn/AuTiO2 composite lead to the maximum solar hydrogen yield (1.52 mmol/h g) with an apparent quantum yield (AQY) of 7.5%. Photoelectron and photoluminescence spectral studies confirm the electron transfer from Au to gcn, and Au and/or gcn to titania. A thorough physico-chemical investigation of various composites underscores the electronic integration aspects of the nanocomposite towards storage of electrons in the Pt co-catalyst and hence an effective charge separation and an increase in AQY. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

10aElectronic integration10aPhotocatalysis10aSchottky barrier10aSolar hydrogen10awater splitting1 aDevaraji, Perumal1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/pt-g-c3n4-autio2-electronically-integrated-nanocomposite-solar-hydrogen-generation02625nas a2200181 4500008004100000022001400041245012400055210006900179260000900248300001400257490000800271520193900279100002702218700001602245700002902261700003002290856012302320 2018 eng d a1932-744700aSilicon oxidation by NAPPES: From dangling bonds to oxygen islands to 2D SiOx layer to the onset of bulk SiO2 formation0 aSilicon oxidation by NAPPES From dangling bonds to oxygen island cMAR  a4331-43380 v1223 a

Valence band and core level photoelectron spectral measurements at near-ambient pressures (NAP; up to 0.5 mbar) were made in the presence of molecular oxygen to explore the various oxidation stages of silicon surfaces. Dangling bonds feature observed on clean Si-surfaces in the valence band at ultrahigh vacuum decreases dramatically due to oxygen adsorption between ambient temperature and up to 400 K at 0.1 mbar of O-2 pressure. The adsorption of oxygen on dangling bonds appears to be localized as islands; this reflects in the surface heterogeneous character and also responsible for the broadening in the oxygen gas phase vibrational features. This is further supported by an increase in the work function and can be correlated to the presence of Hofer (molecular) precursor. When the temperature was increased to 500 K, molecular precursor species dissociates to form Si-=-0 species. This is fully supported by the change in the Si work function as well as from the observation of oxidized Si species from Si 2p core level spectra. At >= 600 K, the Si-=-0 species dissociates to form a uniform 2D oxide layer on the silicon surface, which is characterized by the reappearance of sharp vibration features for gas-phase O-2 molecules. This layer is also quite stable up to 800 K and without any further oxidation in the bulk. On increasing the temperature to 850 K at 0.2 mbar oxygen pressure, bulk Si oxidation begins and the work function increases drastically by 1 eV. An angle-dependent Si 2p spectra recorded map out the presence of elemental Si to Si4+ from bulk to the surface, respectively. A simple model is proposed to show the various stage of silicon oxidation. A continuous change in the work function and electronic states observed due to gas-lattice (O-2-Si) interaction indicates the implications for surface-dependent phenomena, such as heterogeneous catalysis, electrochemistry, 2D layered materials.

1 aGhosalya, Manoj, Kumar1 aJain, Ruchi1 aReddy, Kasala, Prabhakar1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/silicon-oxidation-nappes-dangling-bonds-oxygen-islands-2d-siox-layer-onset-bulk-sio202197nas a2200241 4500008004100000022001200041245012300053210006900176260000800245300000700253490000800260520135300268653002501621653001601646653002801662653002001690100002701710700002901737700001601766700001501782700003001797856012801827 2018 eng d a974362600aSubtle interaction between Ag and O 2 : a near ambient pressure UV photoelectron spectroscopy (NAP-UPS) investigations0 aSubtle interaction between Ag and O 2 a near ambient pressure UV cMAR a300 v1303 aThe Ag-O2 interaction, which is at the center-stage of Ag-catalyzed partial oxidation reactions, is studied with NAP-UPS up to 0.2 mbar O2 pressure between 295 and 550 K. Three temperature regimes were identified for distinct Ag-O2 interaction, which are (a) 295–390 K, where mainly dissociative chemisorption of O2 happens, (b) 390–450 K, where diffusion of O-atoms into the sub-surfaces of Ag is prominent, and (c) >450 K, where metastable oxide forms on polycrystalline Ag surfaces. The work function (WF) of Ag changed from 4.95 (≤390 K) to 5.30 eV (390–450 K), and then to 5.7 eV (≥450 K) at 0.1 mbar O2 pressure. Oxygen population in the sub-surfaces imparts crucial modifications to Ag at 390–450 K; it makes the surface to be electron-deficient that relates to the change in the WF of Ag and facilitates the formation of space charge layer on Ag surface. Oxygen adsorbed on such modified Ag-surfaces is electrophilic in nature, and this appears at a higher binding energy in core level XPS than the chemisorbed oxygen on metallic Ag. This is supported by angle-dependent NAP-XPS studies. The subsurface population of oxygen in Ag no longer persists at >410 K when the O2 supply is removed. A high ratio of antibonding/bonding O 2p bands suggests the unique silver-oxygen interaction under the measurement conditions.10aElectronic Structure10aepoxidation10aheterogeneous catalysis10aSurface Science1 aGhosalya, Manoj, Kumar1 aReddy, Kasala, Prabhakar1 aJain, Ruchi1 aRoy, Kanak1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/subtle-interaction-between-ag-and-o-2-near-ambient-pressure-uv-photoelectron-spectroscopy02295nas a2200253 4500008004100000022001400041245013400055210006900189260000800258300001200266490000800278520141400286653002001700653001701720653002301737653001901760653001901779100002301798700001801821700001901839700003001858700002301888856013001911 2019 eng d a0169-433200aCadmium sulfide nanostructures: influence of morphology on the photocatalytic degradation of erioglaucine and hydrogen generation0 aCadmium sulfide nanostructures influence of morphology on the ph cJUL a696-7050 v4833 a

Size and shape of inorganic materials are known to have great effects on their physical and chemical properties. Here, for the first time we report the visible light driven photocatalytic degradation of erioglaucine - a stable organic dye molecule in the presence of chemically synthesized nanoscale CdS with 1D (nanorods), 2D (nanosheets) and 3D (hierarchical) morphology. Visible light driven photocatalytic degradation efficiency of both 1D and 3D CdS in the removal of erioglaucine are identical. Surprisingly, with 5 min of sonication, the highly crystalline 3D CdS stacked with many thin nanowires containing numerous active surface sites exhibited fourfold enhanced photodegradation efficiency in comparison to 1D and 2D CdS. Scavenger studies revealed that electrons and superoxide radicals are primary reactive species involved in the photodegradation of erioglaucine, while cyclic photodegradation studies revealed the good stability of 3D CdS against photocorrosion. Further, the photocatalytic hydrogen evolution studies also revealed the excellent activity of 3D CdS in comparison to 1D and 2D CdS. Thus, we find that the morphology indeed influences the photocatalytic activity. These results reveal that 3D CdS nanostructures investigated in the present work are efficient photocatalysts that could be fine-tuned for both environmental remediation and hydrogen generation applications.

10aCadmium sulfide10aErioglaucine10aHydrogen evolution10aNanostructures10aPhotocatalysis1 aShenoy, Sulakshana1 aJang, Eunyong1 aPark, Tae, Joo1 aGopinath, Chinnakonda, S.1 aSridharan, Kishore uhttp://library.ncl.res.in/content/cadmium-sulfide-nanostructures-influence-morphology-photocatalytic-degradation-erioglaucine02228nas a2200181 4500008004100000022001400041245011500055210006900170260000800239300001400247490000600261520154900267100002801816700002901844700001901873700003001892856012401922 2019 eng d a2050-748800aDirect solar-to-hydrogen generation by quasi-artificial leaf approach: possibly scalable and economical device0 aDirect solartohydrogen generation by quasiartificial leaf approa cFEB a3179-31890 v73 a

Often, a disadvantage in one area of science may become an advantage in another area. In contrast, a successful concept in one area could work for a complementary area of research too. These two philosophies have been successfully used for solar hydrogen generation and they underscore the necessity to connect relevant concepts. We, herein, report a quasi-artificial leaf (QuAL) device in a wireless configuration with a TiO2/Mn-CdS composite and NiCu as a co-catalyst for possibly scalable as well as commercially viable solar hydrogen production under one sun conditions. The device works at no applied potential and generates 10.5 mL h(-1) (16 mL h(-1)) H-2 with Ni5Cu2.5 alloy (Pt) as a co-catalyst, which corresponds to a power conversion efficiency (PCE) of 4.8% (7.3%). The significant resemblance of NiCu alloy to Pt in terms of its electrochemical activity and electronic structure makes the device more economical. While the millisecond lifetime of electrons in Mn-CdS is known to help for white light emission, the same factor helps to greatly improve charge utilization for H-2 production in the QuAL device. In contrast, the reabsorption of emitted light is a vexing problem in emission applications; however in the present work, reabsorption is successfully utilized to enhance hydrogen yield. Spectroscopy techniques combined with electrocatalytic studies were employed and the results correlated with solar hydrogen generation, demonstrating this as a new pathway to design better solar-light-harvesting architectures.

1 aPatra, Kshirodra, Kumar1 aBharad, Pradnya, Arunrao1 aJain, Vanshika1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/direct-solar-hydrogen-generation-quasi-artificial-leaf-approach-possibly-scalable-and02820nas a2200253 4500008004100000022001400041245010600055210006900161260000800230300001600238490000700254520197500261653001202236653001902248653003002267653000902297653002002306100001602326700002102342700002202363700002002385700003002405856013102435 2019 eng d a1944-824400aElectronic integration and thin film aspects of Au-Pd/rGO/TiO2 for improved solar hydrogen generation0 aElectronic integration and thin film aspects of AuPdrGOTiO2 for  cSEP a32869-328780 v113 a

In the present work, we have synthesized noble bimetallic nanoparticles (Au-Pd NPs) on a carbon-based support and integrated with titania to obtain Au-Pd/C/TiO2 and Au-Pd/rGO/TiO2 nanocomposites using an ecofriendly hydrothermal method. Here, a 1:1 (w/w) Au-Pd bimetallic composition was dispersed on (a) high-surface-area (3000 m(2) g(-1)) activated carbon (Au-Pd/C), prepared from a locally available plant source (in Assam, India), and (b) reduced graphene oxide (rGO) (Au-Pd/rGO); subsequently, they were integrated with TiO2. The shift observed in Raman spectroscopy demonstrates the electronic integration of the bimetal with titania. The photocatalytic activity of the above materials for the hydrogen evolution reaction was studied under 1 sun conditions using methanol as a sacrificial agent in a powder form. The photocatalysts were also employed to prepare a thin film by the drop-casting method. Au-Pd/rGO/TiO2 exhibits 43 times higher hydrogen (H-2) yield in the thin film form (21.50 mmol h(-1) g(-1)) compared to the powder form (0.50 mmol h(-1) g(-1)). On the other hand, Au-Pd/C/TiO2 shows 13 times higher hydrogen (H-2) yield in the thin film form (6.42 mmol h(-1) g(-1)) compared to the powder form (0.48 mmol h(-1) g(-1)). While powder forms of both catalysts show comparable activity, the Au-Pd/rGO/TiO2 thin film shows 3.4 times higher activity than that of Au-Pd/C/TiO2. This can be ascribed to (a) an effective separation of photogenerated electron-hole pairs at the interface of Au-Pd/rGO/TiO2 and (b) the better field effect due to plasmon resonance of the bimetal in the thin film form. The catalytic influence of the carbon-based support is highly pronounced due to synergistic binding interaction of bimetallic nanoparticles. Further, a large amount of hydrogen evolution in the film form with both catalysts (Au-Pd/C/TiO2 and Au-Pd/rGO/TiO2) reiterates that charge utilization should be better compared to that in powder catalysts.

10abimetal10aPhotocatalysis10asurface plasmon resonance10aTiO210awater splitting1 aTudu, Bijoy1 aNalajala, Naresh1 aReddy, Kasala, P.1 aSaikia, Pranjal1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/electronic-integration-and-thin-film-aspects-au-pdrgotio2-improved-solar-hydrogen-generation04102nas a2200205 4500008004100000245012200041210006900163260000800232300001600240490000700256520332100263100002903584700001903613700002303632700002403655700002603679700003303705700003003738856012803768 2019 eng d00a Molybdenum carbide catalyst for the reduction of CO2 to CO: surface science aspects by NAPPES and catalysis studies 0 aMolybdenum carbide catalyst for the reduction of CO2 to CO surfa cAUG a12199-122090 v483 a

Carbon dioxide is a greenhouse gas, and needs to be converted into one of the useful feedstocks, such as carbon monoxide and methanol. We demonstrate the reduction of CO2 with H-2 as a reducing agent, via a reverse water gas shift (RWGS) reaction, by using a potential and low cost Mo2C catalyst. Mo2C was evaluated for CO2 hydrogenation at ambient pressure as a function of temperature, and CO2 : H-2 ratio at a gas hourly space velocity (GHSV) of 20 000 h(-1). It is demonstrated that the Mo2C catalyst with 1 : 3 ratio of CO2 : H-2 is highly active (58% CO2 conversion) and selective (62%) towards CO at 723 K at ambient pressure. Both properties (basicity and redox properties) and high catalytic activity observed with Mo2C around 700 K correlate well and indicate a strong synergy among them towards CO2 activation. X-ray diffraction and Raman analysis show that the Mo2C catalyst remains in the beta-Mo2C form before and after the reaction. The mechanistic aspects of the RWGS reaction were determined by near-ambient pressure X-ray photoelectron spectroscopy (NAPXPS) with in situ generated Mo2C from carburization of Mo-metal foil. NAPXPS measurements were carried out at near ambient pressure (0.1 mbar) and various temperatures. Throughout the reaction, no significant changes in the Mo2+ oxidation state (of Mo2C) were observed indicating that the catalyst is highly stable; C and O 1s spectral results indicate the oxycarbide species as an active intermediate for RWGS. A good correlation is observed between catalytic activity from atmospheric pressure reactors and the electronic structure details derived from NAPXPS results, which establishes the structure-activity correlation.

1 aReddy, Kasala, Prabhakar1 aDama, Srikanth1 aMhamane, Nitin, B.1 aGhosalya, Manoj, K.1 aRaja, Thirumalaiswamy1 aSatyanarayana, Chilukuri, V.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/molybdenum-carbide-catalyst-reduction-co2-co-surface-science-aspects-nappes-and-catalysis02248nas a2200157 4500008004100000022001400041245008400055210006900139260000900208300001400217490000700231520169300238100001601931700003001947856011301977 2019 eng d a1477-922600aMorphology-dependent, green, and selective catalytic styrene oxidation on Co3O40 aMorphologydependent green and selective catalytic styrene oxidat cAPR  a4574-45810 v483 a

Despite the great successes in the controlled fabrication of nanomaterials with specific composition and morphology, it is still challenging to have the desired control on the defect sites of catalyst materials. For unfolding the mystery of this aspect, catalytic styrene epoxidation was attempted on spinel Co3O4 with two different morphologies, namely, SNR (nanorods prepared by the solvothermal method with the (110) facet), HNR (nanorods prepared by the hydrothermal methodwith the (111) facet) and NC (nanocubes with the (110) facet) were synthesized and subjected to olefin oxidation with O-2. Even without any catalyst pretreatment, all three Co3O4 catalyst systems were found to be active for selective epoxidation of styrene with O-2 at ambient pressure in the liquid phase. The correlation between catalytic activity and selectivity trend suggests that the reaction is highly structure-sensitive and facile on the (110) facet. Temperature-dependent near ambient pressure X-ray photoelectron spectroscopy (NAPXPS) was carried out at 0.1 mbar O-2 pressure to understand the mechanistic aspects. The distinct catalytic activity of NC (110) and SNR (110) can be attributed to the population of defect sites on the catalyst surface. NC morphology with comparatively fewer defect sites shows high activity and selectivity, suggesting that styrene oxidation on Co3O4 is structure-sensitive; however, unlike metal surfaces, fewer defects are more favourable for catalytic styrene epoxidation due to facile adsorption and activation of the substrate and O-2 on Co3+ sites. The present investigations suggest that surface defects need not necessarily increase catalytic activity.

1 aJain, Ruchi1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/morphology-dependent-green-and-selective-catalytic-styrene-oxidation-co3o403435nas a2200181 4500008004100000245019300041210006900234260000800303300001700311490000800328520267900336100002803015700002703043700002103070700001603091700003003107856011603137 2019 eng d00aOxidative disproportionation of MoS2/GO to MoS2/MoO3-x/RGO : integrated and plasmonic 2D-multifunctional nanocomposites for solar hydrogen generation from near-infrared and visible regions0 aOxidative disproportionation of MoS2GO to MoS2MoO3xRGO integrate cSEP a 21685-216930 v1233 a

Two dimensional (2D) semiconductor materials have been recently demonstrated to be effective plasmonic materials and alternatives to costly noble metals. However, tuning the plasmon resonance of 2D semiconductors and integrating with another material or semiconductor for various applications, such as solar light harvesting, remains a challenge. Herein, we designed a simple and attractive method, which facilitates the diffusion of oxygen from the graphene oxide (GO) layers of the MoS2/GO (MG) composite to oxidize the MoS2 layers significantly due to thermal treatment under inert atmosphere. This is the key step in the formation of MoS2/MoO3-x/RGO (MMR) (x = 0, 0.5, and 1, and all stoichiometries co-exist), due to disproportionation of MoS2/GO, with bulk heterojunctions among the components. The observed behavior is attributed to the oxidation of Mo4+ cations (of MoS2) to higher oxidation states in MMR (Mo(5+ )and Mo6+ of MoO3-x), which also alters the valence-band electronic structure and work function of the resulting composite. The 2D MoO3-x layers with a large amount of Mo5+ oxidation states enables facile charge carrier generation due to plasmonic effect, whereas MoS2 provides active sites for catalysis. The solar H-2 generation was demonstrated in the visible and near-infrared region by combining both the plasmonic and catalytic effects in one composite. These results demonstrate the important role of RGO to provide energy-level alignment, charge carrier diffusion, and help to generate plasmonic effect in the composite.

1 aPatra, Kshirodra, Kumar1 aGhosalya, Manoj, Kumar1 aBajpai, Himanshu1 aRaj, Sreeya1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/oxidative-disproportionation-mos2go-mos2moo3-xrgo-integrated-and-plasmonic-2d01391nas a2200217 4500008004100000022001400041245007900055210006900134260000900203300001600212490000600228520065400234100002300888700002300911700002900934700002400963700002100987700003001008700002601038856010901064 2019 eng d a2470-134300aPhase transfer ceria-supported nanocatalyst for nitrile hydration reaction0 aPhase transfer ceriasupported nanocatalyst for nitrile hydration cOCT  a16037-160440 v43 a

The present study elaborates the catalytic effect of rare-earth metal oxides (Sm2O3 and La2O3) over ceria as a support phase transfer catalyst. The synthesized catalysts have been subjected to different characterization techniques, such as field-emission scanning electron microscopy, high-resolution transmission electron microscopy, powder X-ray diffraction, N-2 adsorption-desorption (BET surface analysis), temperature-programmed desorption study (NH3/CO2-TPD), Fourier transform infrared, Raman analysis, and X-ray photoelectron spectroscopy to get better insights into the catalytic activity of the catalysts for hydration of nitrile.

1 aGupta, Nikitra, N.1 aPunekar, Amrin, S.1 aRaj, Karthik, Raja E. K.1 aGhodekar, Medha, M.1 aPatil, Vipul, S.1 aGopinath, Chinnakonda, S.1 aRaja, Thirumalaiswamy uhttp://library.ncl.res.in/content/phase-transfer-ceria-supported-nanocatalyst-nitrile-hydration-reaction02392nas a2200205 4500008004100000022001400041245012000055210006900175260000900244300001400253490000600267520164700273100002301920700001601943700002001959700002901979700003002008700001802038856013002056 2019 eng d a2050-748800aPromising visible-light driven hydrogen production from water on a highly efficient CuCo2S4 nanosheet photocatalyst0 aPromising visiblelight driven hydrogen production from water on  cMAR  a6985-69940 v73 a

Here we report the development of CuCo2S4 nanosheets (NSs) as a promising semiconductor photocatalyst for the first time for water splitting reactions under visible light ( 420 nm) conditions, without the support of any noble metal co-catalyst. These NSs were produced via a simple hydrothermal route and have desirable properties with a band gap of 2.24 eV, and are photo-catalytically active under visible light with an apparent quantum yield (AQY) of 2.48%. Under visible light, CuCo2S4 NSs exhibit excellent weight-normalized photoactivity that generates approximate to 25900 mol h(-1) H-2 for 1 g of material with sulphide + sulphite as the sacrificial agent under 7.68 mW cm(-2) illumination, which is the best evolution reported for any chalcogenide semiconductor material without any co-catalyst to date with unprecedented long-term operational stability (up to 12 h study time). The rate and number of hydrogen gas molecules produced are 8.2855 x 10(15) s(-1) cm(-2) which remained constant for three catalytic cycles with a turnover frequency (TOF) value of 0.017 s(-1). The effect of Cu substitution on photoactivity was also investigated for comparative studies and it was found that CuCo2S4 NSs show superior activity to Cu0.5Co2.5S4 and Co3S4. These CuCo2S4 NSs absorb the entire visible range of the spectrum from 420 to 800 nm, and have a highly populated density of states at the Fermi level and a high donor concentration of 7.22 x 10(18) cm(-3) which have been evaluated by Mott-Schottky analysis and favourable adsorption of H+ on S-sites and conversion to H-2 corroborate their efficient photocatalytic activity.

1 aChauhan, Meenakshi1 aSoni, Kiran1 aKarthik, P., E.1 aReddy, Kasala, Prabhakar1 aGopinath, Chinnakonda, S.1 aDeka, Sasanka uhttp://library.ncl.res.in/content/promising-visible-light-driven-hydrogen-production-water-highly-efficient-cuco2s4-nanosheet01704nas a2200277 4500008004100000022001400041245012400055210006900179260000900248300001100257490000800268520078900276653002101065653001501086653001101101653002001112653002401132653002701156100001901183700001901202700001601221700001601237700003001253700001801283856012501301 2019 eng d a0926-860X00aSurfactant free synthesis of Au@Ni core-shell nanochains in aqueous medium as efficient transfer hydrogenation catalyst0 aSurfactant free synthesis of AuNi coreshell nanochains in aqueou cAPR  a93-1000 v5753 a

A surfactant free aqueous phase synthesis method is reported for the generation of highly lattice mismatched Au@Ni core-shell nanochains without using any expensive and hazardous organic ligands. As synthesised Au@Ni nanochain structures showed high thermal stability and bulk oxidation resistance up to 300 degrees C. In situ near ambient pressure XPS (NAPXPS) analysis has been done for the bare Au@Ni nanochain surfaces under oxygen atmosphere and at different temperatures which showed evidence for the surface oxidation resistance of naked Au@Ni nanochains up to 200 degrees C. Ligand or capping agent free Au@Ni nanochain surfaces are found to be highly active for transfer hydrogenation of acetophenone to 1-phenyl ethanol an important commodity in perfumery industry.

10aAu@Ni nanochains10acore-shell10aNAPXPS10aSurfactant free10asynergistic effects10atransfer hydrogenation1 aVysakh, A., B.1 aShebin, K., J.1 aJain, Ruchi1 aSumanta, P.1 aGopinath, Chinnakonda, S.1 aVinod, C., P. uhttp://library.ncl.res.in/content/surfactant-free-synthesis-auni-core-shell-nanochains-aqueous-medium-efficient-transfer01946nas a2200181 4500008004100000022001400041245014500055210006900200260000800269300001400277490000600291520123600297100002101533700002801554700002401582700003001606856012801636 2019 eng d a2046-206900aWhy the thin film form of a photocatalyst is better than the particulate form for direct solar-to-hydrogen conversion: a poor man's approach0 aWhy the thin film form of a photocatalyst is better than the par cFEB a6094-61000 v93 a

We demonstrated an easy method to improve the efficiency of photocatalysts by an order of magnitude by maximizing light absorption and charge carrier diffusion. Degussa titania (P25) and Pd/P25 composite photocatalyst thin films coated over regular glass plates were prepared and evaluated for solar hydrogen production in direct sunlight with aqueous methanol. It is worth noting that only UV light present in direct sunlight (similar to 4%) was absorbed by the catalysts. The hydrogen production activities of catalysts were compared for thin film and particulate forms at 1 and 25 mg levels. The hydrogen yield values suggested that 1 mg thin film form of Pd/P25 provided 11-12 times higher activity than 25 mg powder form. Comparable light absorption throughout the entire thickness of photocatalyst device and better contact of nanostructures that enabled the charge diffusion and charge utilization at redox sites are the reasons for high efficiency. While solar cells require charge carriers to diffuse through long distances of microns, they are utilized locally in an ensemble of particles (of nanometres) for hydrogen generation in photocatalyst thin films; this concept was used effectively in the present work.

1 aNalajala, Naresh1 aPatra, Kshirodra, Kumar1 aBharad, Pradnya, A.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/why-thin-film-form-photocatalyst-better-particulate-form-direct-solar-hydrogen-conversion01968nas a2200265 4500008004100000022001400041245014300055210006900198260000900267300001600276490000700292520103800299653002001337653001801357653001901375653001301394653001901407100002101426700002801447700001701475700002101492700002901513700003001542856013001572 2020 eng d a1944-824400aCan half-a-monolayer of pt simulate activity like that of bulk pt? solar hydrogen activity demonstration with quasi-artificial leaf device0 aCan halfamonolayer of pt simulate activity like that of bulk pt  cJUL  a30420-304300 v123 a

Pt is the best cocatalyst for hydrogen production. It is also well-known that the surface atomic layer is critical for catalysis. To minimize the Pt content as cocatalyst, herein we report on half-a-monolayer of Pt (0.5 theta(Pt)) decorated on earth-abundant Ni-Cu cocatalyst, which is integrated with a quasiartificial leaf (QuAL) device (TiO2/ZnS/CdS) and demonstrated for efficient solar hydrogen production. For the QuAL, TiO2 is sensitized with ZnS and CdS quantum dots by the SILAR method. The 0.5 theta(Pt)-decorated Ni-Cu shows an onset potential of 0.05 V vs reversible hydrogen electrode for the hydrogen evolution reaction, which is almost similar to that of commercial Pt/C. Photoactivity of the present QuAL device with either bulk Pt or 0.5 theta(Pt)-coated Ni-Cu cocatalyst is, surprisingly, equal. Our findings underscore that a fraction of a monolayer of Pt can enhance the activity of the cocatalyst, and it is worth exploring further for the high activity associated with atomic Pt and other noble metals.

10aartificial leaf10anickel-copper10aPhotocatalysis10aplatinum10aSolar hydrogen1 aBajpai, Himanshu1 aPatra, Kshirodra, Kumar1 aRanjan, Ravi1 aNalajala, Naresh1 aReddy, Kasala, Prabhakar1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/can-half-monolayer-pt-simulate-activity-bulk-pt-solar-hydrogen-activity-demonstration-quasi01739nas a2200241 4500008004100000022001400041245008300055210006900138260000800207300001200215490000600227520098000233653001301213653002201226653001301248653001901261653001701280100001601297700002101313700002001334700003001354856011301384 2020 eng d a2367-198X00aCu-Ni bimetal integrated TiO2 thin film for enhanced solar hydrogen generation0 aCuNi bimetal integrated TiO2 thin film for enhanced solar hydrog cMAY a19005570 v43 a

A series of non-noble Cu-Ni bimetallic catalysts is prepared with different molar proportions of metals. Of these bimetallic catalysts, 1 wt% is subsequently integrated with titania P25. The catalysts are evaluated for solar hydrogen generation under 1 sun condition in both the powder and thin film forms. All the photocatalysts in the thin film exhibit an 8-24 times higher hydrogen yield (HY) compared with the corresponding particulate counterpart. The highest HY (41.7 mmol h(-1) g(-1)) is demonstrated for the photocatalyst Cu-Ni/TiO2 (CNT; 1:1 = Cu:Ni) in the thin film form, which is 24 times higher than that with its powder counterpart (1.75 mmol h(-1) g(-1)) and exceeds the performance of other Cu-Ni/TiO2 compositions. This enhanced activity in the thin film can be ascribed to improved absorption of visible light and an effective separation of photogenerated charge carriers at the interface of Cu-Ni/TiO2 leading to better charge carrier utilization.

10abimetals10aenergy conversion10aHydrogen10aPhotocatalysis10asolar energy1 aTudu, Bijoy1 aNalajala, Naresh1 aSaikia, Pranjal1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/cu-ni-bimetal-integrated-tio2-thin-film-enhanced-solar-hydrogen-generation02343nas a2200181 4500008004100000022001400041245017700055210006900232260000800301300001600309490000600325520161800331100001701949700001701966700003001983700001802013856013002031 2020 eng d a2050-748800aDirected holey and ordered g-C(3)N(4.5)nanosheets by a hard template nanocasting approach for sustainable visible-light hydrogen evolution with prominent quantum efficiency0 aDirected holey and ordered gC3N45nanosheets by a hard template n cJUL a13328-133390 v83 a

It is desirable yet challenging to synthesize a highly ordered holey carbon nitride material with excess nitrogen atoms for a sustainable solar H(2)evolution. Herein, we report the development of directed highly ordered nitrogen-rich honeycomb-like mesoporous carbon nitride nanosheets by using a novel synthetic approach for this purpose. The unique formation route, surface structure and charge carrier dynamics of the two dimensional holey nanosheets are comprehensively monitored and confirmed by SAXS, HRTEM, AFM, BET, XPS and TRPL analyses. Non-stoichiometric high nitrogen content mesoporous nanosheets with the final stoichiometry of g-C(3)N(4.5)acquiring a high specific surface area (382 m(2)g(-1)), remarkable pore size (7.2 nm) and sheet thickness similar to 5-6 nm are realized in this first report. This elegant material possesses unique low band-gap energy (2.42 eV). Remarkably, the as-synthesized g-C(3)N(4.5)NSs exhibit a record high photocatalytic H(2)evolution rate of 8180 mu mol g(-1)h(-1)under the present light irradiation (420 <=lambda <= 510 nm) condition. The apparent quantum efficiency is found to be as high as 27.14% at 420 nm and retains its photocatalytic activity for longer consecutive catalytic cycles. Bigger pore size and pore volume, and thin walls leading to shortening of the path length of exciton pairs, efficient charge separation and the prolonged average life time of the charge carriers, and lone electron pairs associated with the excess nitrogen content are found to be the reasons behind the excellent visible light driven water splitting reaction.

1 aAntil, Bindu1 aRanjan, Ravi1 aGopinath, Chinnakonda, S.1 aDeka, Sasanka uhttp://library.ncl.res.in/content/directed-holey-and-ordered-g-c3n45nanosheets-hard-template-nanocasting-approach-sustainable02041nas a2200217 4500008004100000022001400041245012900055210006900184260000900253300001400262490000700276520126400283653002601547653002501573653002801598653001401626653000801640100001601648700003001664856012901694 2020 eng d a1867-388000aElectronic structure evolution of Pd@Co nanocatalysts under oxidation and reduction conditions and preferential CO oxidation0 aElectronic structure evolution of PdCo nanocatalysts under oxida cAUG  a4176-41840 v123 a

Herein, we present the surface electronic structure and morphological evolution under reduction and oxidation conditions for Pd@Co (PC) core-shell nanoparticles with different Pd : Co ratio (PC=2 : 1, 1 : 1 and 1 : 2). Extensive measurements have been made with NAPXPS (near ambient pressure x-ray photoelectron spectroscopy) under oxidising and reducing conditions, and ex-situ HRTEM. It has been demonstrated that PC catalysts are thermally stable towards morphological changes, at least up to 575 K. Nonetheless, it shows a significant surface electronic structure changes under reaction environments, which are highly relevant to heterogeneous catalysis. As expected, high (low) population of metallic (oxidised) Co was observed, while retaining core shell structure under reduction (H(2)and vacuum annealing) environment. Interestingly, the Pd-Co metallic interface helps to overcome the pyrophoric nature of cobalt and stabilised a significant amount of metallic Co at Pd-Co interface even in the presence of 0.1 mbar O(2)up to 575 K. The presence of Pd-Co and Pd-Co@Co(3)O(4)interfaces in reaction environment makes the catalyst dual functional. The proof of concept has been explored in terms of oxidation of CO in the presence of H(2)or O-2.

10aCore-Shell morphology10aElectronic Structure10aheterogeneous catalysis10ainterface10aXPS1 aJain, Ruchi1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/electronic-structure-evolution-pdco-nanocatalysts-under-oxidation-and-reduction-conditions02858nas a2200193 4500008004100000022001400041245014100055210006900196260000800265300001600273490000700289520211300296100002702409700002902436700002302465700001702488700003002505856012902535 2020 eng d a1463-907600aGas-solid interactions with reactive and inert gas molecules by NAPUPS: can work function be a better descriptor of chemical reactivity?0 aGassolid interactions with reactive and inert gas molecules by N cJUL a15528-155400 v223 a

The gas-phase vibrational spectra of reactive (H(2)and O-2) and inert gases (N(2)and Ar) have been studied by near-ambient pressure (NAP) ultraviolet photoelectron spectroscopy (NAPUPS) up to 0.3 mbar pressure. The results obtained are divided into two parts and discussed. In the first part, the photoelectron spectra of monoatomic Ar and some homonuclear diatomic molecules, such as H-2, O-2, and N-2, have been recorded by NAPUPS and the effect of pressure on their energy position has been studied. It has been demonstrated that NAPUPS could be an essential tool to determine the intermolecular or interatomic interactions. In the second part, we have evaluated the influence of different solid surfaces on the binding energy (BE) position, the pattern of the vibrational features of diatomic N(2)molecules, and the first atomic levels (3p(3/2)and 3p(1/2)) of monoatomic Ar. It has been observed that with a change in the (electronic/chemical) nature of the surface, the BE of the above features also changes and reflects the change in the work function (phi) of the material. It is to be noted that Ar is an inert/noble gas and N(2)is the most stable molecule, and the above changes observed underscore that they can be employed as probe atoms/molecules to explore even the minor changes that occur on a solid surface due to a variety of reasons. Further, if the solid surface undergoes any chemical/electronic changes due to gas-solid interaction, such as oxidation/reduction, the phi of the surface changes again; this highlights the precise identification of the changes that occur under the reaction/measurement conditions. Therefore, the change in the BE of the gas-phase features can be used to determine even the minor changes in the phi of solid surfaces during the reaction or due to the reaction. The present findings have implications in probing the surface changes that occur in any surface-dependent phenomena, such as heterogeneous catalysis, electrochemistry, and materials that are predominantly controlled by surface contribution, such as layered (2D) materials, nanomaterials.

1 aGhosalya, Manoj, Kumar1 aReddy, Kasala, Prabhakar1 aMhamane, Nitin, B.1 aRanjan, Ravi1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/gas-solid-interactions-reactive-and-inert-gas-molecules-napups-can-work-function-be-better02460nas a2200253 4500008004100000022001400041245017300055210006900228260000900297300001600306490000600322520151900328653002801847653001801875653001401893653001901907653002501926100002101951700002701972700002301999700002502022700003002047856012902077 2021 eng d a2574-096200aAqueous methanol to formaldehyde and hydrogen on Pd/TiO2 by photocatalysis in direct sunlight: structure dependent activity of nano-Pd and atomic Pt-coated counterparts0 aAqueous methanol to formaldehyde and hydrogen on PdTiO2 by photo cNOV  a13347-133600 v43 aIn the present investigation, facet-controlled Pd nanoparticles with nanocube (Pd-NC) and truncated octahedron (Pd-TO) morphologies, and their counterparts with half-a-monolayer of atomic Pt coated (0.5 theta(Pt)-Pd-NC and 0.5 theta(Pt)-Pd-TO) surfaces were prepared. All of them were characterized and evaluated as cocatalyst after supporting them on commercial titania (P25) (Pd-NC/P25, Pd-TO/P25, 0.5 theta(Pt)-Pd-NC/P25, and 0.5 theta(Pt)-Pd-TO/P25) under direct sunlight and/or one sun conditions for the oxidation of methanol to formaldehyde along with solar hydrogen production. Pd-NC/P25 shows higher activity for hydrogen generation compared to Pd-TO/P25; however, activity reversal occurs with the above cocatalysts, but, after Pt-coating with further enhanced activity. The highest conversion of methanol (0.2 mu mol/h.mg) to 100% selective formaldehyde was observed with 0.5 theta(Pt)-Pd-TO/P25, while other catalysts show significantly lower methanol conversion in the following order: 0.5 theta(Pt)-Pd-TO/P25 > 0.5 theta(Pt)-Pd-NC/P25 > Pd-NC/P25 > Pd-TO/P25. Pt-coated on (111) facets of Pd-TO simulates the activity associated as that of Pt(111) facets and demonstrating the highest and facet dependent activity. The present study is truly in resonance with exploiting the surface properties for heterogeneous catalysis, and highlights that less than a monolayer of Pt is sufficient to simulate the activity as that of bulk Pt. It is worth exploring this concept to other metals and substrates too.10aheterogeneous catalysis10aNanomaterials10aOxidation10aPhotocatalysis10asurface modification1 aNalajala, Naresh1 aSalgaonkar, Kranti, N.1 aChauhan, Inderjeet1 aMekala, Siva, Prasad1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/aqueous-methanol-formaldehyde-and-hydrogen-pdtio2-photocatalysis-direct-sunlight-structure01520nas a2200217 4500008004100000245013400041210006900175260000800244300001100252490000700263520073000270653002001000653002001020653001701040653002801057653001701085653001601102100002301118700003001141856013101171 2021 eng d00aCatalytic applications of hydrotalcite and related materials in multi -component reactions: concepts, challenges and future scope0 aCatalytic applications of hydrotalcite and related materials in  cSEP a1004580 v223 aHydrotalcites (HTs) are the potential substitute to conventional base catalysts. HTs are useful in efficient syntheses of various heterocycles, such as chromenes, pyrans, pyrazoles, triazoles, using multi-component reactions. This review focuses on the chemistry of HTs and particularly hydrotalcites and related materials in the synthesis of heterocycles. The effects of preparation method and, physico-chemical parameters, such as calcination, molar ratio of metals, role of intercalated ions, surface area, on the catalytic activities are discussed. Along with technical aspects, this review also unlocks various untouched areas in developing sustainable catalyst for syntheses of heterocycles, drugs, etc. for the future.10agreen chemistry10agreen synthesis10aheterocycles10aheterogeneous catalysis10ahydrotalcite10aMetal Oxide1 aBurange, Anand, S.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/catalytic-applications-hydrotalcite-and-related-materials-multi-component-reactions-concepts01935nas a2200265 4500008004100000022001400041245013300055210006900188260000800257300001200265490000700277520102200284653002801306653002001334653001901354653001101373653002801384653001901412100002101431700002301452700002101475700001901496700003001515856012401545 2021 eng d a2194-428800aElectronically integrated mesoporous Ag-TiO2 nanocomposite thin films for efficient solar hydrogen production in direct sunlight0 aElectronically integrated mesoporous AgTiO2 nanocomposite thin f cAUG a21003560 v103 a

The synthesis of mesoporous TiO2 by a solution-based assembly process and Ag/TiO2 nanocomposites is provided. The efficacy of Ag/TiO2 nanocomposite as photocatalyst in thin-film form is demonstrated for solar hydrogen generation in sunlight. Integration of Ag with TiO2 dramatically enhanced the H-2 production: with 1 wt% Ag on TiO2 (TiAg-1), the H-2 yield was observed to be 4.59 mmol h(-1) g(-1), which is 2.3 (30) times larger than 0.5 wt% Ag on TiO2. TiAg-1 shows 4.3 times higher activity in film form compared with its powder counterpart. High photocatalytic efficiency is attributed to the surface plasmon resonance effect of Ag, electronic integration of Ag with TiO2, and subsequent valence band broadening, large distribution of Ag nanoparticles and abundant Ag-TiO2 Schottky junctions, and the later minimizes electron-hole recombination. Interparticle mesoporous network increases necking and the high surface area offers easy accessibility of the reactants to a large number of active sites.

10aheterogeneous catalysis10aheterojunctions10aplasmon effect10aSilver10asolar energy conversion10aSolar hydrogen1 aMani, Sunesh, S.1 aRajendran, Sivaraj1 aNalajala, Naresh1 aMathew, Thomas1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/electronically-integrated-mesoporous-ag-tio2-nanocomposite-thin-films-efficient-solar12210nas a2200289 45000080041000000220014000412450146000552100069002012600008002703000011002784900008002895201119900297653001111496653000811507653005211515653002111567100002011588700002311608700003011631700002511661700001911686700002211705700001811727700002111745700002711766856012711793 2021 eng d a1385-894700aGreen route for carbonylation of amines by CO2 using Sn-Ni-O bifunctional catalyst and theoretical study for finding best suited active sites0 aGreen route for carbonylation of amines by CO2 using SnNiO bifun cSEP a1294390 v4193 a

Reaction between n-alkylamine and CO2 has gained interest due to the demand for the dialkylurea for various applications. For the first time, the tool Mathematica was used to analyze the experimental data with an idea to derive an equation which determines the best suited active sites for any given input set of dependent parameters. The equation can further be used to predict the product yield with the known values of active sites for a reaction. Among several Sn containing mixed oxides, Sn-Ni oxide (Sn-Ni-O) was found to be the better performing catalyst. The studies indicate that the formation of new defect sites when NiO and SnO2 are in the mixed state and possibly a solid solution enhances the catalytic efficiency. There are two main reasons for improved catalytic performance; one, mixing of SnO2 into NiO which reduces the number of holes (h+) localized on lattice oxygen (O2−+ h+→ O•−) and two, smaller SnO2 particles are dispersed on the bigger particle NiO which alters the acidic and basic active sites in the catalyst. FT-IR adsorption study with amine and CO2 helped in deriving a plausible mechanism for this reaction. Under optimized reaction condition, Sn1.1-Ni-O-600 gave 77.3% of n-butylamine conversion and 75.7% of yield for 1,3-dibutylurea. The versatility of the catalyst was tested for carbonylation of different aliphatic and aromatic amines, diamine and hydroxy amine with CO2.

10aamines10aCO210aMixed oxide catalyst and bi-functional catalyst10aSubstituted urea1 aKulal, Nagendra1 aVetrivel, Rajappan1 aGopinath, Chinnakonda, S.1 aRavindran, Rahul, K.1 aRao, Vinod, N.1 aShetty, Manjunath1 aShrikanth, R.1 aRangappa, Dinesh1 aShanbhag, Ganapati, V. uhttp://library.ncl.res.in/content/green-route-carbonylation-amines-co2-using-sn-ni-o-bifunctional-catalyst-and-theoretical01536nas a2200265 4500008004100000022001400041245010300055210006900158260000800227520062000235653002000855653001700875653002800892653001700920653001800937100002300955700002100978700002700999700002201026700002101048700002001069700002301089700003001112856012801142 2021 eng d a1610-365300aGreen synthesis of xanthene and acridine-based heterocycles of pharmaceutical importance: a review0 aGreen synthesis of xanthene and acridinebased heterocycles of ph cMAR3 a

Xanthene and acridine-based heterocyclic compounds find applications in cancer chemotherapy, biological staining and laser dyes and are known for their antibacterial and anti-tumor properties. Here we review green catalytic routes for the synthesis of 1,8-dioxo-octahydroxanthenes, 1,8-dioxo-decahydroacridines and related heterocyclic molecules with catalysts such as metal oxides, mixed metal oxides, resins, supported organocatalysts, heteropolyacids, carbon-based materials, zeolites, sulfides and ionic liquids. We compare protocols for their catalytic activities, and proposed mechanisms are discussed.

10agreen chemistry10aheterocycles10aheterogeneous catalysis10aMetal oxides10ananocatalysis1 aBurange, Anand, S.1 aGadam, Komal, G.1 aTugaonkar, Prajyot, S.1 aThakur, Seema, D.1 aSoni, Ravish, K.1 aKhan, Rubej, R.1 aTai, Mubashira, S.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/green-synthesis-xanthene-and-acridine-based-heterocycles-pharmaceutical-importance-review02044nas a2200337 4500008004100000022001400041245014400055210006900199260000900268300001100277490000800288520095100296653001401247653001401261653001901275653000901294653001601303100002101319700001801340700001701358700002301375700002601398700002401424700002101448700001701469700002001486700003001506700002301536700001701559856013001576 2021 eng d a0926-860X00aIn-situ experimental and computational approach to investigate the nature of active site in low-temperature CO-PROX over CuOx-CeO2 catalyst0 aInsitu experimental and computational approach to investigate th cAUG  a1183050 v6243 aPreferential oxidation (PROX) of carbon monoxide (CO) in presence of excess hydrogen is a necessity to prevent poisoning of the Pt-anode by CO in PEMFCs (Polymer Electrolyte Membrane Fuel Cell). A highly active catalyst, 5 wt% Cu-CeO2 showed 100 % CO conversion at 65 degrees C without any undesirable oxidation of H-2. The catalyst showed no deactivation even after 100 h on stream, making it viable for practical fuel cell application. Operando EPR in the PROX reaction condition revealed highly dispersed mixed valent cations with oxygen vacancies, responsible for the low-temperature PROX activity. At the active site, both Cu and Ce ions were shown to reversibly change their valence states to facilitate the abstraction of bridging lattice oxygen for CO oxidation to CO2. This surface oxygen mediated CO oxidation was found to be much faster than that of H-2 to H2O, which could explain the complete selectivity of oxygen for CO2 formation.10aCuOx-CeO210ainterface10aOxygen vacancy10aPROX10aSynergistic1 aAdak, Shubhadeep1 aRabeah, Jabor1 aRanjan, Ravi1 aKhan, Tuhin, Suvra1 aPoddar, Mukesh, Kumar1 aGupta, Rishi, Kumar1 aSasaki, Takehiko1 aKumar, Sagar1 aBordoloi, Ankur1 aGopinath, Chinnakonda, S.1 aBruckner, Angelika1 aBal, Rajaram uhttp://library.ncl.res.in/content/situ-experimental-and-computational-approach-investigate-nature-active-site-low-temperature02730nas a2200277 4500008004100000022001400041245015700055210006900212260000900281300001400290490000600304520175500310653001902065653003002084653003202114653001802146653001802164100001702182700001902199700001702218700002302235700002202258700003002280700001802310856012402328 2021 eng d a2574-096200aOne-dimensional multichannel g-C3N4.7 nanostructure realizing an efficient photocatalytic hydrogen evolution reaction and its theoretical investigations0 aOnedimensional multichannel gC3N47 nanostructure realizing an ef cAPR  a3118-31290 v43 a

The emerging metal-free carbon nitride (C3N4) offers prominent possibilities for realizing the highly effective hydrogen evolution reaction (HER). However, its poor surface conductivity and insufficient catalytic sites hinder the HER performance. Herein, a one-dimensional vermicular rope-like graphitic carbon nitride nanostructure is demonstrated that consists of multichannel tubular pores and high nitrogen content, which is fabricated through a cost-effective approach having the final stoichiometry g-C3N4.7 for HER application. The present g-C3N4.7 is unique owing to the presence of abundant channels for the diffusion process, modulated surface chemistry with rich- electroactive sites from N-electron lone pairs, greatly reduced recombination rate of photoexcited exciton pairs, and a high donor concentration (4.26 x 10(17) cm(3)). The catalyst offers a visible-light-driven photocatalytic H-2 evolution rate as high as 4910 mu mol h(-1)g(-1) with an apparent quantum yield of 14.07% at band gap absorption (2.59 eV, 479 nm) under 7.68 mW cm(-2) illumination. The number of hydrogen gas molecules produced is 1.307 x 10(15) s(-1) cm(-2), which remained constant for a minimum of 18 h of repeated cycling in the HER without any degradation of the catalyst. In density functional theory calculations, a significant change in the band offset is observed due to N doping into the system in favor of electron catalysis. The theoretical band gap of a monolayer of g-C3N4.7 was enormously reduced because of the presence of additional densities of states from the doped N atom inside the band gap. These impurity or donor bands are formed inside the band gap region, which ultimately enhance the hydrogen ion reduction reaction enormously.

10acarbon nitride10aDensity functional theory10ahydrogen evolution reaction10anitrogen-rich10aPhotocatalyst1 aAntil, Bindu1 aKumar, Lakshya1 aRanjan, Ravi1 aShenoy, Sulakshana1 aTarafder, Kartick1 aGopinath, Chinnakonda, S.1 aDeka, Sasanka uhttp://library.ncl.res.in/content/one-dimensional-multichannel-g-c3n47-nanostructure-realizing-efficient-photocatalytic02521nas a2200265 4500008004100000022001400041245010300055210006900158260000900227300001600236490000600252520166000258653001501918653001301933653001601946653001701962653000901979653002001988100001602008700002102024700002902045700002002074700003002094856013102124 2021 eng d a2168-048500aRationally designed, efficient, and earth-abundant Ni-Fe cocatalysts for solar hydrogen generation0 aRationally designed efficient and earthabundant NiFe cocatalysts cOCT  a13915-139250 v93 aDeveloping highly efficient and affordable catalysts for solar hydrogen (H-2) generation is crucial, and employing a cocatalyst from earth-abundant elements has a critical role to play. In this context, different compositions of earth-abundant Ni-Fe alloy (1:1, 1:3, and 3:1) have been prepared by hydrothermal method; subsequently, 1 wt % of these Ni-Fe cocatalysts were integrated with TiO2-P25 and thoroughly characterized. The resultant catalysts have been evaluated for solar H-2 production, in powder and thin film forms, under one sun condition and in direct sunlight. Interestingly, all the catalysts in the thin film form exhibit superior hydrogen yield (HY), up to 27 times higher activity than its powder counterpart. Among the photocatalysts, Ni-Fe/TiO2 (3:1 = Ni/Fe; NFT31) composition exhibits the best HY in thin film (8.27 mmol.h(-1).g(-1)) and exceeds all other compositions of catalyst. It is also to be reported that HY measured for the powder form with 1 mg shows 3-17 times higher activity than that measured with 25 mg. This is mainly attributed to effective solar light absorption with a smaller amount of photocatalyst either spread over large area in a thin film form or well-dispersed in suspension forms. Furthermore, the enhanced activity obtained with Ni-Fe/TiO2 photocatalysts is also ascribed to strong electronic integration of Ni-Fe cocatalyst with TiO2 and higher performance obtained with a thin film is attributed to increased charge carrier generation and subsequent charge separation and effective utilization. A decrease in work function of TiO2 by 0.6 eV was observed after its integration with cocatalyst in NFT31.10aCocatalyst10aHydrogen10aNi-Fe alloy10asolar energy10aTiO210awater splitting1 aTudu, Bijoy1 aNalajala, Naresh1 aReddy, Kasala, Prabhakar1 aSaikia, Pranjal1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/rationally-designed-efficient-and-earth-abundant-ni-fe-cocatalysts-solar-hydrogen-generation02473nas a2200157 4500008004100000022001400041245011900055210006900174260000800243300001400251490000600265520186600271100003002137700002102167856012702188 2021 eng d a2050-748800aScalable and thin film approach for solar hydrogen generation: a review on enhanced photocatalytic water splitting0 aScalable and thin film approach for solar hydrogen generation a  cJAN a1353-13710 v93 a

Although nearly five decades of efforts have gone into solar water splitting (SWS), still success eludes and there is no big breakthrough till date. While huge importance is given either individually or concurrently to the three fundamental steps, namely, light absorption, charge carrier separation and diffusion and charge utilization at redox sites, many aspects that are practically helpful to improve the efficiency are not widely discussed and practised. Nonetheless, by adopting a number of small, but significant changes, solar hydrogen production can be enhanced. The present review discusses such different approaches employed for photocatalytic water splitting reported in the literature. For example, an increase of up to two orders of magnitude in solar hydrogen generation was observed with a film form compared to the particulate form of the same catalyst. Discussion on various approaches of enhanced hydrogen production under sunlight and one sun conditions is the main focus of this review, in particular with thin-film forms. The merits and demerits of thin film and particulate methods, respectively, are addressed in detail. Potential methods and successful stories on scalability are also discussed in the present review. In contrast to charge collection over a long distance in solar cell-based methods, a film-based method discussed shows that the local charge utilisation at a zero applied potential is an attractive feature for SWS. A comparison is provided between the PEC-WS and SWS for solar hydrogen generation, and how far we are from the reality to produce solar hydrogen on an industrial scale. We believe the presently practised diverse evaluation efforts may be truncated to fewer methods such as film-based evaluation and in a focussed manner to tackle the SWS issue towards sustainable production of solar hydrogen.

1 aGopinath, Chinnakonda, S.1 aNalajala, Naresh uhttp://library.ncl.res.in/content/scalable-and-thin-film-approach-solar-hydrogen-generation-review-enhanced-photocatalytic01228nas a2200205 4500008004100000022001400041245011300055210006900168260000800237300001400245490000700259520049900266100001900765700001600784700002100800700001800821700003000839700002400869856012900893 2022 eng d a1359-734500aConcerted effect of Ni-in and S-out on ReS2 nanostructures towards high-efficiency oxygen evolution reaction0 aConcerted effect of Niin and Sout on ReS2 nanostructures towards cMAR a3689-36920 v583 a

Herein, a one-step hydrothermal reaction is developed to synthesize a Ni-doped ReS2 nanostructure with sulphur defects. The material exhibited excellent OER activity with a current density of 10 mA cm(-2) at an overpotential of 270 mV, a low Tafel slope of 31 mV dec(-1), and good long-term durability of 10 h in 1 M KOH. It shows high faradaic efficiency of 96%, benefiting from the rapid charge transfer caused by the concerted effect of Ni-in and S-out on the ReS2 nanostructure.

1 aDas, Tapas, K.1 aPing, Tapan1 aMohapatra, Manoj1 aAnwar, Shahid1 aGopinath, Chinnakonda, S.1 aJena, Bikash, Kumar uhttp://library.ncl.res.in/content/concerted-effect-ni-and-s-out-res2-nanostructures-towards-high-efficiency-oxygen-evolution02940nas a2200181 4500008004100000022001400041245012200055210006900177260000800246300001600254490000800270520225900278100001702537700002302554700002302577700003002600856012802630 2022 eng d a1932-744700aElectronic structure evolution from metallic vanadium to metallic VxOy: a nappes study for o2+v gas-solid interaction0 aElectronic structure evolution from metallic vanadium to metalli cNOV a19136-191460 v1263 a

Gas-solid interactions between molecular oxygen and metallic vanadium surfaces and the systematic evolution in the electronic structure of vanadium oxide (VOx) surfaces have been explored in the present work by near-ambient pressure photo-electron spectroscopy (NAPPES). The current article studies the evolution of various oxides of vanadium as a function of partial pressure of O2 (ultrahigh vacuum to 1 mbar), temperature (298- 875 K), and the exposure time to oxygen (up to 18 h). Valence -band (VB) and core-level spectral measurements recorded with UV (He-I = 21.2 eV) and Al K alpha (1486.6 eV) photons, respectively, show interesting changes. (1) Oxidation is limited to the top layers of vanadium at 298 K and up to a partial pressure of 1 mbar O2. About 50% of vanadium gets oxidized, and the remaining amount exists as metal within the top 10 nm. (2) Metallic vanadium disappears above 625 K, and it is predominantly oxidized to a mixture of V4+ and V5+ oxidation states at a 0.1 mbar partial pressure of O2. Points 1 and 2 suggest the predominantly thermodynamically controlled nature of vanadium oxidation through oxygen diffusion into the subsurface and bulk layers. (3) The Fermi-level (EF) feature observed first at >= 725 K at a 0.1 mbar O2 pressure demonstrates the formation of metallic VO2; however, its metallic nature is preserved even at ambient temperature due to interweaving nanodomains of VOx with VO2. (4) Only partial conversion of surface layers to V5+ (V2O5) along with VO2 and V2O3 (within the probing depth of 8-10 nm by near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS)) was observed even after prolonged heating (18 h) in 1 mbar O2 pressure. (5) The nature of the surface changes between metal and semiconducting/ insulator oxides is substantiated by the observation of changes in work function (phi) and EF features. Typical VB features and Fermi intensity of V-metal and vanadium oxides were observed, and the results were corroborated with core-level and VB spectra. The present results extend the capabilities of NAPPES to explore the electronic structure evolution as a function of reaction conditions and underscore its relevance to areas such as heterogeneous catalysis and sensing.

1 aRanjan, Ravi1 aMhamane, Nitin, B.1 aKolekar, Sadhu, K.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/electronic-structure-evolution-metallic-vanadium-metallic-vxoy-nappes-study-o2v-gas-solid02471nas a2200349 4500008004100000022001400041245015100055210006900206260000900275300001600284490000700300520122500307653002401532653001101556653002801567653001801595653002001613653002101633100002901654700003201683700002901715700002901744700002401773700003101797700003001828700002001858700003101878700002401909700003001933700003101963856012701994 2022 eng d a0360-319900aEnhanced hydrogen fuel production using synergistic combination of solar radiation and TiO2 photocatalyst coupled with Burkholderia cepacia lipase0 aEnhanced hydrogen fuel production using synergistic combination  cAPR  a14483-144920 v473 a

Promising and sustainable alternatives for hydrogen production have been investigated. Among these, the use of enzymes may represent an efficient alternative. In this work, an increase in hydrogen production under simulated sunlight by combining TiO2 and TiO2/MgCl2 with Burkholderia cepacia lipase (BCL) was reported. The samples (TiO2, TiO2/MgCl2, and TiO2 /MgCl2/BCL) were characterized by X-ray diffraction (XRD), thermo-gravimetric (TGA), N-2 adsorption-desorption isotherms (BET), scanning electron microscopy (SEM), and UV-Visible absorption spectra. Hydrogen production tests were performed in aqueous methanol solutions under simulated sunlight. The results demonstrated that 130-times greater increase in hydrogen production rate was observed by the addition of BCL than individual TiO2. This better hydrogen production rate can be attributed to the increase in the amount of reduction equivalent of the system due to the oxidation of protein peptides caused by TiO2. In conclusion, the results indicate that hydrogen production efficiency can be significantly improved when integrating TiO2/MgCl2 with BCL. (C) 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

10ahydrogen production10aLipase10aNano-conjugated enzymes10aPhotocatalyst10aSolar radiation10aTitanium dioxide1 aBrandao, Luma, Mirely de1 aBarbosa, Milson, dos Santos1 ade Jesus, Roberta, Anjos1 aBharad, Pradnya, Arunrao1 aLima, Alvaro, Silva1 aSoares, Cleide, Mara Faria1 aYerga, Rufino, Manuel Nav1 aBilal, Muhammad1 aFerreira, Luiz, Fernando R1 aIqbal, Hafiz, M. N.1 aGopinath, Chinnakonda, S.1 aFigueiredo, Renan, Tavares uhttp://library.ncl.res.in/content/enhanced-hydrogen-fuel-production-using-synergistic-combination-solar-radiation-and-tio202228nas a2200241 4500008004100000022001400041245010800055210006900163260000800232300000700240490000800247520142000255653001001675653002701685653001901712653001401731653002001745100001801765700002601783700002401809700003001833856012301863 2022 eng d a0974-362600aFacile, sustainable and unassisted plain water oxidation on Au/Ce0.9Ti0.1O2 nanorods in direct sunlight0 aFacile sustainable and unassisted plain water oxidation on AuCe0 cJUN a610 v1343 a

Impressive rate of solar water oxidation to molecular oxygen (O-2) has been demonstrated on nanorods (NRs) of Ce0.9Ti0.1O2 (CT-NR) and Au-deposited CT-NR (Au-CT-NR) photocatalysts with a sacrificial agent (Fe3+) and in plain water in one sun condition, direct sunlight and with lambda >= 455 nm. Probably the highest 0 2 yield of 11 mmol/h.g was observed with Au-CT-NR thin film in plain water in direct sunlight, with no sacrificial agent or applied potential. Photoelectrochemical measurements demonstrate a marked reduction in oxidation onset potential of Au-CT-NR by 150 mV with stable photocurrent (0.75 mA/cm(2)), compared to CT-NR (0.23 mA/cm(2)), indicating the operative of plasmon-induced resonant energy transfer (PIRET) process. Effective electron quenching by nanogold and hence low recombination in the depletion region is a critical step for the observation of a high rate of oxygen evolution. In addition to this, a predominant change in the nature of the valence band from O-2p dominated on CeO2 to Ce-4f dominated with CT-NR (due to Ti4+ introduction in CeO2), the efficient light absorption of photocatalysts in thin-film form, functional and effective PIRET process, and facile E-F alignment, enhances the oxygen evolution with Au-CT-NR in direct sunlight and make it highly sustainable. A possible mechanism of water oxidation is proposed from the observed experimental findings.

10aceria10aElectronic integration10aPhotocatalysis10athin film10awater splitting1 aDubey, Anjani1 aMishra, Abhaya, Kumar1 aNegi, Sanjay, Singh1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/facile-sustainable-and-unassisted-plain-water-oxidation-auce09ti01o2-nanorods-direct02672nas a2200205 4500008004100000022001400041245012200055210006900177260000900246300001600255490000700271520190500278100002802183700002602211700002302237700002602260700002002286700003002306856013002336 2022 eng d a0020-166900aPossible fine-tuning of methane activation toward C2 oxygenates by 3d-transition metal-ions doped nano-ceria-zirconia0 aPossible finetuning of methane activation toward C2 oxygenates b cDEC  a19577-195870 v613 a

In this work, we demonstrate a simple sol-gel technique to prepare metal-ion(s)-doped ceria-zirconia solid solution for efficient catalytic methane activation. The cation -depicting formula units are Ce0.80Zr0.20 (CZ), Ce0.79Zr0.20M0.01 (CZM), and Ce0.79Zr0.20M0.005M10.005 (CZMM1) (M and M1 = V, Mn, Fe, Co, and Cu), employed for undoped, mono-metal-ion -doped, and bi-metal-ion-doped solid solutions, respectively. Methane activation with Mn, Fe, Cu mono-metal-ion-doped CZ favors the C1 product, while CZCo assists C-C coupling with the formation of acetaldehyde. On the other hand, the Co-and Fe -doped bi-metal-ion combination catalyst (CZCoFe) shows significant ethanol but predominant formic acid formation. This is further promoted by the Co + V bi-metal-ion combination (CZCoV) catalyst, and it shows ethanol as the major product along with methyl hydrogen peroxide, methanol, and formic acid as minor products. An impressive ethanol yield of 93 mu mol/g h with 76% selectivity obtained with the CZCoV catalyst is at par with that obtained with noble-metal-based catalysts under comparable reaction conditions. When Co and V content was increased two and four times from 0.005 to 0.01 and 0.02, ethanol yield increased at the expense of formic acid. The 213 mu mol/g h ethanol yield (86% selectivity) observed with Ce0.76Zr0.20Co0.02V0.02 is probably the highest observed. The partial oxidation of CH4 in Co-based bi-metal combinations (Co + V or Co + Fe) suggests the synergistic effect of doped metal ions owing to the heterogeneous near -neighbor environment. The present results are attributed to the surface heterogeneity between the host and the dopants, which selectively promotes methane activation as well as C-C coupling. This indicates a large scope to tune the activity of partial oxidation of methane and product selectivity with different metal-ion(s) combinations.

1 aKanungo, Subhashree, S.1 aMishra, Abhaya, Kumar1 aMhamane, Nitin, B.1 aMarelli, Udaya, Kiran1 aKumar, Dharmesh1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/possible-fine-tuning-methane-activation-toward-c2-oxygenates-3d-transition-metal-ions-doped01609nas a2200181 4500008004100000022001400041245013500055210006900190260000800259300001200267490000700279520091500286100001901201700002101220700003001241700002701271856012901298 2022 eng d a0020-166900aSulfur functionalization via epoxide ring opening on a reduced graphene oxide surface to form metal (II) Organo-bis-[1,2]-oxathiin0 aSulfur functionalization via epoxide ring opening on a reduced g cJAN a279-2860 v613 a

The epoxide ring-opening reaction in graphene oxide (GO) by nucleophiles is a very fascinating and advanced methodology to develop novel functional material. Herewith, we report an advanced strategy for opening the epoxide ring on the rGO surface via easily an available nucleophile (Na2S), which is further functionalized with O atom to obtain four-membered rings (FMRs). The Cd coordination with the S atom puts extra stress on the FMR leading to the C-C bond cleavage of the four-membered heteroatomic rings on the rGO surface. This strategic approach leads to the fabrication of an innovative metal organo-bis-[1,2]-oxathiin (MOBOT) chemical moiety (M = Cd, Zn). The MOBOT compound further shows enhanced H-2 generation activity and hence is promising as a potential photocatalyst for solar hydrogen generation. This compound might also be a potential candidate for optoelectronic applications.

1 aKumar, Praveen1 aBajpai, Himanshu1 aGopinath, Chinnakonda, S.1 aLuwang, Meitram, Niraj uhttp://library.ncl.res.in/content/sulfur-functionalization-epoxide-ring-opening-reduced-graphene-oxide-surface-form-metal-ii02753nas a2200253 4500008004100000022001400041245014800055210006900203260000800272300001400280490000700294520185500301653002802156653001902184653003102203653000902234653001802243100002302261700001702284700001702301700002602318700003002344856012502374 2022 eng d a2168-048500aSustainable CO2 reduction on in (2)O(3 )with exclusive CO selectivity: catalysis and in situ valence band photoelectron spectral investigations0 aSustainable CO2 reduction on in 2O3 with exclusive CO selectivit cMAR a3521-35310 v103 a

This study demonstrates a sustainable catalytic CO2 conversion to near 100% CO selectivity at ambient pressure on In2O3. Critically, high CO yield could be observed at the cost of undesired methanation, using a lower than stoichiometric amount of hydrogen in the feed; 1:1 and 1:0.67 CO2:H-2 ratios exhibit 98-99.6% CO selectivity with 25-38% CO2 conversion between 773 and 873 K. CO2 and H-2 conversion under steady-state conditions at 773-873 K suggests a 1:1 ratio of adsorbed reactants (with 1:0.67 CO2:H-2 feed) on the catalyst surface, underscoring the presence of an ideal reactant composition for the reverse water-gas shift reaction, while H-2-rich feed compositions show the H-2-dominated surface. Surface electronic structure changes, under near-operating conditions, were explored with near ambient pressure photoelectron spectroscopy (NAPPES), and the interesting findings are as follows: (a) A shift in the valence band to lower binding energy, up to 0.6 eV, was observed because of electron filling at high temperatures. (b) An observation of heterogeneous nature of the catalyst surface under NAPPES measurement conditions is attributed to the generation of active oxygen vacancy (O-v) sites, which in turn changes the work function of In2O3. (c) The above changes are found to be reversible, when the reaction was stopped. Vibrational features of the reactant molecules were observed to be broadened in the active temperature window of the catalyst supporting the heterogeneous character of the catalyst surface because of dynamic O-v generation. By optimizing gas hourly space velocity, CO2:H-2 ratio, and reaction temperature, exclusive CO selectivity is possible with a H-2:CO2 ratio of similar to 0.67, which will avoid the product separation stage altogether, while minimizing the expensive H-2 in the reactant feed.

10aheterogeneous catalysis10aOxygen vacancy10aphotoelectron spectroscopy10aRWGS10aWork function1 aMhamane, Nitin, B.1 aChetry, Sibo1 aRanjan, Ravi1 aRaja, Thirumalaiswamy1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/sustainable-co2-reduction-2o3-exclusive-co-selectivity-catalysis-and-situ-valence-band02916nas a2200229 4500008004100000022001400041245015400055210006900209260000900278300001600287490000700303520206700310100002702377700002102404700002302425700002102448700002302469700002002492700001802512700003002530856012602560 2023 eng d a2050-748800aBaby step in assembling and integrating the components of an artificial photosynthesis device with forced heterojunctions towards improved efficiency0 aBaby step in assembling and integrating the components of an art cJUL  a15168-151820 v113 a

How to achieve unassisted, economical, scalable, and sustainable artificial photosynthesis for liquid fuels/products with improved solar-to-fuel efficiency (STFE) to address a carbon-neutral economy remains a big question. To a large degree, the extent of charge separation at heterojunction interfaces and charge utilization determine the STFE. Towards this, BiVO3 is assembled from ionic-precursors into TiO2 pores, and integrated structurally and electronically with TiO2 on calcination as BiVO4 quantum dots (BVQDs). BVQDs in TiO2 (BVT) pores lead to an all-inorganic system with a sub-quadrillion number of heterojunctions in a 1 cm(2) device (contains similar to 25 mu g of BiVO4 (similar to 2.5 wt%) in the nanopores of similar to 975 mu g of TiO2 (similar to 97.5 wt%)) and facilitate artificial photosynthesis. We demonstrate 31-38% STFE with a photon to chemical conversion turn over frequency (ToF(P2C)) of 2.73 s(-1) with a 1 cm(2) wireless BiVO4-TiO2 artificial leaf (BVT-AL) device for HCHO and CH3OH. The sequential nature of CO2 reduction to HCHO and then to CH3OH is evident from the reaction results. (CO2)-C-13 isotopic labeling experiments confirm that the input CO2 is the source for product formation. A large increase in the photocurrent density and incident photon-to-current efficiency (IPCE) of BVT, over 100% for the BiVO4 photoanode in visible light, demonstrates and supports efficient visible light absorption, charge separation and migration to the redox sites. A device has been demonstrated to show sustainable activity in direct sunlight, and addresses scalability from 1 to 9 cm(2). Assuming no change (50% decrease) in the STFE, a 6.74 m(2) device is expected to convert 1 (0.5) kg h(-1) CO2 into C1-oxygenates in sunlight. DFT calculations carried out with anatase TiO2 (101) and BiVO4 (121) interfaces support many of the experimental findings, including electron flow from the latter to the former, and interaction of the oxygen of TiO2 with BiVO4 and vice versa at the interface towards forced heterojunctions.

1 aSalgaonkar, Kranti, N.1 aBajpai, Himanshu1 aMhamane, Nitin, B.1 aNalajala, Naresh1 aChauhan, Inderjeet1 aThakkar, Kavita1 aJoshi, Kavita1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/baby-step-assembling-and-integrating-components-artificial-photosynthesis-device-forced01641nas a2200157 4500008004100000022001400041245011700055210006900172260000800241300001400249490000700263520102900270100002801299700003001327856012601357 2023 eng d a1359-734500aCO2 electrolysis towards large scale operation: rational catalyst and electrolyte design for efficient flow-cell0 aCO2 electrolysis towards large scale operation rational catalyst cJUN a6774-67950 v593 a

The electrochemical CO2 reduction reaction (CO2RR) to renewable fuels/chemicals is a potential approach towards addressing the carbon neutral economy. To date, a comprehensive analysis of key performance indicators, such as an intrinsic property of catalyst, reaction environment and technological advancement in the flow cell, is limited. In this study, we discuss how the design of catalyst material, electrolyte and engineering gas diffusion electrode (GDE) could affect the CO2RR in a gas-fed flow cell. Significant emphasis is given to scale-up requirements, such as promising catalysts with a partial current density of >= 100 mA cm(-2) and high faradaic efficiency. Additional experimental hurdles and their potential solutions, as well as the best available protocols for data acquisition for catalyst activity evaluation, are listed. We believe this manuscript provides some insights into the making of catalysts and electrolytes in a rational manner along with the engineering of GDEs towards CO2RR.

1 aPatra, Kshirodra, Kumar1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/co2-electrolysis-towards-large-scale-operation-rational-catalyst-and-electrolyte-design02552nas a2200265 4500008004100000022001400041245009700055210006900152260000800221300001100229490000800240520168600248653002701934653002801961653000901989653000801998653002002006100001702026700002102043700001602064700002302080700002602103700003002129856012702159 2023 eng d a1385-894700aCo3O4 for sustainable CO2 reduction and possible fine-tuning towards selective CO production0 aCo3O4 for sustainable CO2 reduction and possible finetuning towa cSEP a1444590 v4713 a

Two main challenges involved in heterogeneous catalytic CO2 reduction are: (a) decreasing the consumption of H2 to the minimum required level with possibly the maximum CO2 conversion, and (b) concurrently enhancing the selectivity of the desired CO, at the cost of methane. Towards meeting these two challenges, Co3O4 spinel has been identified as a potential catalyst and it exhibits predominant CO selectivity > 673 K at atmospheric pressure. CO2 conversion begins > 523 K, with 100% CO selectivity observed > 673 K with CO2:H2 = 3:2. Current work shows a sustainable catalytic CO2 conversion to 100% CO selectivity with Co3O4-Nanocube (NC). Critically, CO selectivity and yield is observed to increase at the cost of methane with smaller amount of H2. 1:1 and 3:2 CO2:H2 ratio exhibits 88-100% CO selectivity with 24-32.5% CO2 conversion between 623 and 823 K. Irrespective of the input CO2:H2, ratio of CO2:H2 uptake changes from around 1:3 at 523 K to 1:1-1.5 at 823 K with concurrent production of significant methane to predominant CO, respectively. Surface electronic state changes was explored by near ambient pressure photoelectron spectroscopy, and the results suggests that Co3O4 is the active phase that promotes CO2 reduction selectively to CO. Broadening observed with the vibrational feature of the CO2 molecules at high temperature underscores the heterogeneous character of the catalyst surface, under operating conditions, due to changing electron density. By optimizing the gas hourly space velocity (GHSV), H2-lean CO2:H2 ratio, and the reaction temperature/pressure, 100% CO selectivity could be broadened to a range of operating conditions.

10aCarbon neutral economy10aheterogeneous catalysis10aRWGS10aSDG10aSurface Science1 aRanjan, Ravi1 aTekawadia, Jyoti1 aJain, Ruchi1 aMhamane, Nitin, B.1 aRaja, Thirumalaiswamy1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/co3o4-sustainable-co2-reduction-and-possible-fine-tuning-towards-selective-co-production02216nas a2200205 4500008004100000022001400041245012900055210006900184260000800253300001400261490000700275520145200282100002301734700002801757700002101785700002301806700002701829700003001856856012401886 2023 eng d a1477-922600aNanostructured Co-doped BiVO4 for efficient and sustainable photoelectrochemical chlorine evolution from simulated sea-water0 aNanostructured Codoped BiVO4 for efficient and sustainable photo cFEB a2051-20610 v523 a

The co-production of hydrogen and chlorine from sea-water splitting could be a potential, sustainable and attractive route by any method. However, challenges to overcome are many, and critically, the sustainability and operating potential of the electrocatalyst are important. In this work, we report on Co-doping in the BiVO4 (Co-BV) crystal lattice and employed the same as the photoanode; Co-BV exhibits a photocurrent of 190 mu A cm(-2) at 1.1 V vs. RHE (the reversible hydrogen electrode) in the acidic sodium chloride solution (pH 2.3) under one sun illumination. The best-performing photoanode, with 0.05 mol% of Co doping (0.05 Co-BV), selectively produced active chlorine with 92% faradaic efficiency at 1.1 V vs. RHE by successfully suppressing the kinetically sluggish oxygen evolution reaction (OER) and the stability of the catalyst was demonstrated for up to 20 h. This is the lowest operating potential reported for the chlorine evolution reaction (CER), thus far. The overpotential required for CER with 0.05 Co-BV is lower than that of OER, which leads to selective CER at 1.1 V (vs. RHE). Co-doping into the BiVO4 lattice decreases the charge transfer resistance and enhances the CER kinetics due to its structural and electronic integration with the BV lattice. We demonstrate that Co-doping also improves the lifetime of the charge carrier and enhances the current density of CER and sustainability of the catalyst.

1 aChauhan, Inderjeet1 aPatra, Kshirodra, Kumar1 aBajpai, Himanshu1 aMhamane, Nitin, B.1 aSalgaonkar, Kranti, N.1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/nanostructured-co-doped-bivo4-efficient-and-sustainable-photoelectrochemical-chlorine01481nas a2200277 4500008004100000022001400041245012100055210006900176260000800245300001200253490000700265520056300272653001000835653001400845653001900859653002000878100002400898700002000922700001900942700001700961700002000978700002100998700003001019700002301049856013101072 2023 eng d a0909-049500aPhotocatalytic setup for in situ and operando ambient-pressure X-ray photoelectron spectroscopy at MAX IV Laboratory0 aPhotocatalytic setup for in situ and operando ambientpressure Xr cMAY a613-6190 v303 a

The Ambient-Pressure X-ray Photoelectron Spectroscopy (APXPS) endstation at the SPECIES beamline at MAX IV Laboratory has been improved. The latest upgrades help in performing photo-assisted experiments under operando conditions in the mbar pressure range using gas and vapour mixtures whilst also reducing beam damage to the sample caused by X-ray irradiation. This article reports on endstation upgrades for APXPS and examples of scientific cases of in situ photocatalysis, photoreduction and photo-assisted atomic layer deposition (photo-ALD).

10aAPXPS10aphoto-ALD10aPhotocatalysis10asolar simulator1 aKlyushin, Alexander1 aGhosalya, Manoj1 aKokkonen, Esko1 aEads, Calley1 aJones, Rosemary1 aNalajala, Naresh1 aGopinath, Chinnakonda, S.1 aUrpelainen, Samuli uhttp://library.ncl.res.in/content/photocatalytic-setup-situ-and-operando-ambient-pressure-x-ray-photoelectron-spectroscopy-max02212nas a2200241 4500008004100000022001400041245018400055210006900239260000800308490000700316520131500323653002201638653001801660653001401678653001901692653001901711100002701730700002101757700002101778700002001799700003001819856012101849 2023 eng d a1861-472800aSelective and generic photocatalytic oxidation of alcohol with Pd-TiO2 thin films: butanols to butanal/butanone with different morphologies of Pd and 0.5 theta(Pt)-Pd counterparts0 aSelective and generic photocatalytic oxidation of alcohol with P cMAR0 v183 a

The present study reports on the photocatalytic oxidation of butanols to butanal/butanone using thin film form of facet-dependent nano-Pd supported on commercial TiO2 under one-sun condition and demonstrates the generic nature. Pd-nanocube (Pd-NC(100)), Pd-truncated octahedron (Pd-TO (100) and (111)), polycrystalline (Pd-PC), and their counterparts with half-a-monolayer Pt-coated on Pd (0.5 theta(Pt)-Pd)) have been used as co-catalyst. A potentially scalable thin film form of Pd/TiO2 photocatalyst, prepared by drop-casting method, has been employed to study oxidation of n-butanol, 2-butanol, and iso-butanol to corresponding aldehyde/ketone. 100% selectivity is demonstrated to respective aldehyde/ketone with any catalyst used in the present study with varying degree of butanols conversion by NMR. 0.5 theta(Pt)-Pd-TO/TiO2 shows the highest conversion of 2-butanol to butanone (13.6% in 4 h). Continuous 10 h of reaction with the most active 0.5 theta(Pt)-Pd-TO/P25 catalyst demonstrates 31% conversion of 2-butanol to butanone, and catalyst recyclability has been demonstrated. The present protocol can be scalable to large scales to maximize the conversion in direct sunlight. Due to its generic nature, the current method can also be applied to many other alcohols and substrate molecules.

10aenergy conversion10aNanomaterials10aOxidation10aPhotocatalysis10aSustainability1 aSalgaonkar, Kranti, N.1 aKale, Sandip, R.1 aNalajala, Naresh1 aMansuri, Sayana1 aGopinath, Chinnakonda, S. uhttp://library.ncl.res.in/content/selective-and-generic-photocatalytic-oxidation-alcohol-pd-tio2-thin-films-butanols