01846nas a2200229 4500008004100000022001400041245015600055210006900211260011000280300001600390490000700406520088500413100002601298700002101324700002001345700001801365700003201383700002401415700001901439700003001458856012801488 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. uhttps://library.ncl.res.in/content/mgcl2-center-dot-6phch2oh-new-molecular-adduct-support-material-ziegler-natta-catalyst-002024nas a2200253 4500008004100000022001400041245014100055210006900196260007100265300001400336490000800350520104100358100002101399700002601420700001801446700002401464700003201488700002401520700001901544700002601563700001901589700003001608856013201638 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. uhttps://library.ncl.res.in/content/toward-understanding-molecular-level-properties-ziegler-natta-catalyst-support-and-without-003050nas a2200205 4500008004100000022001400041245013800055210006900193260011000262300001600372490000700388520217100395100001902566700003302585700002602618700001902644700002502663700003002688856012602718 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. uhttps://library.ncl.res.in/content/gamma-al2-xmxo3-y-m-ti4-through-ga3-potential-pseudo-3d-mesoporous-materials-tunable-001978nas a2200217 4500008004100000022001400041245013400055210006900189260011000258300001600368490000700384520106800391100002101459700002601480700001801506700003201524700002401556700001901580700003001599856013101629 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. uhttps://library.ncl.res.in/content/mgcl2-center-dot-4ch32chch2oh-new-molecular-adduct-preparation-ticlxmgcl2-catalyst-olefin-002012nas a2200229 4500008004100000022001400041245009200055210006900147260007100216300001600287490000800303520114700311100002601458700002101484700002501505700002201530700003201552700002401584700002601608700003001634856011801664 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. uhttps://library.ncl.res.in/content/mgcl2-center-dot-6c6h11oh-high-mileage-porous-support-ziegler-natta-catalyst-001896nas a2200253 4500008004100000022001400041245008800055210006900143260009200212300001400304490000700318520097300325653001201298653001701310653002801327653003001355653001801385653002201403100002601425700001901451700002601470700003001496856011601526 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. uhttps://library.ncl.res.in/content/functional-and-disordered-meso-macroporous-gamma-al2-xmxo3-y-m-cu-andor-ce-002539nas a2200277 4500008004100000022001400041245012100055210006900176260007100245300001200316490000600328520150200334653002801836653001001864653002101874653002601895653002701921100002601948700002501974700002101999700003202020700002402052700002602076700003002102856012902132 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. uhttps://library.ncl.res.in/content/mgcl2-center-dot-6ch3oh-simple-molecular-adduct-and-its-influence-porous-support-olefin-001298nas a2200205 4500008004100000022001400041245013100055210006900186260011000255300001600365490000700381520043700388100002800825700002600853700002000879700001600899700003000915700001900945856012800964 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 uhttps://library.ncl.res.in/content/rationally-designed-cufe2o4-mesoporous-al2o3-composite-towards-stable-performance-high-002320nas a2200217 4500008004100000022001400041245009500055210006900150260011000219300001400329490000700343520144200350100002601792700002601818700002101844700003201865700002401897700002601921700003001947856012501977 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. uhttps://library.ncl.res.in/content/9-fluorenemethanol-internal-electron-donor-fine-tune-olefin-polymerization-activity-001985nas a2200253 4500008004100000022001400041245010300055210006900158260007700227300001400304490000600318520106600324653002001390653000901410653002801419653001401447653001001461100002601471700002901497700002601526700002601552700003001578856012301608 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. uhttps://library.ncl.res.in/content/role-nanointerfaces-cu-and-cu-plus-au-based-near-ambient-temperature-co-oxidation-002106nas a2200193 4500008004100000245008300041210006900124260000800193300000900201490000600210520145500216100001801671700002301689700002601712700001501738700001801753700003001771856011101801 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. uhttps://library.ncl.res.in/content/porous-thin-films-towards-bridging-material-gap-heterogeneous-catalysis01667nas a2200217 4500008004100000245009500041210006900136260000800205300001200213490000600225520093600231653001301167653002001180653002801200653001201228653001601240100001601256700002601272700003001298856012101328 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. uhttps://library.ncl.res.in/content/mechanistic-aspects-wet-and-dry-co-oxidation-co3o4-nanorod-surfaces-nap-ups-study