01328nas a2200157 4500008004100000245011800041210006900159260000800228300001200236490000600248520072700254100001800981700002000999700002301019856012801042 2016 eng d00aFine tuning the composition and nanostructure of Fe-based core-shell nanocatalyst for efficient CO2 hydrogenation0 aFine tuning the composition and nanostructure of Febased coreshe cOCT a989-9960 v23 a

Hydrogenation of CO2 to hydrocarbons is one of the crucial technologies to address the energy deficit and increasing environmental pollution. In this work, we have synthesized and systematically studied the influence of composition and nanostructure of a Fe-based, carbon-coated core shell nanocatalyst. The synthesis method offered good control over the thickness of the carbon coating in the core shell catalyst, which in turn controlled the chemical composition of the core. The results emphasized an optimal amount of Fe3O4, Fe5C2 in the core and partially graphitized carbon in the shell for a high catalytic activity in the conversion of CO2 at atmospheric pressure with higher selectivity to C-2-C-4 olefins.

1 aGupta, Sharad1 aJain, Vivek, K.1 aJagadeesan, Dinesh uhttps://library.ncl.res.in/content/fine-tuning-composition-and-nanostructure-fe-based-core-shell-nanocatalyst-efficient-co201971nas a2200253 4500008004100000022001400041245017400055210006900229260000800298300001100306490000700317520104800324653002201372653002101394653002001415653002001435653002501455100001801480700002101498700002101519700002701540700001801567856013201585 2020 eng d a2352-940700aEngineering pore morphology using silica template route over mesoporous cobalt oxide and its implications in atmospheric pressure carbon dioxide hydrogenation to olefins0 aEngineering pore morphology using silica template route over mes cJUN a1005860 v193 a

Highly ordered mesoporous cobalt oxides (denoted as m-Co-KIT-6 and m-Co-SBA-15) with three dimensional and two dimensional pore morphology respectively have been synthesized using 3D KIT-6, and 2D SBA-15 as silica template via nanocasting route. CO2 hydrogenation activity was evaluated for these mesoporous materials under atmospheric pressure conditions. In comparison to nanoparticles of cobalt oxide (Co3O4-nano), mesoporous catalysts showed excellent activity for CO2 hydrogenation due to their higher number of exposed active sites and lower mass diffusion limitations. The ordered mesoporous structure of Co3O4 catalysts favored the chain growth of carbon atoms for the production of C2+ hydrocarbons while Co3O4 nanoparticles showed strong selectivity toward CH4. High selectivity for C2+ (similar to 25%) was obtained for both m-Co-KIT-6 and m-Co-SBA-15 catalysts at 320 degrees C. In addition, the 3D pore structure of m-Co-KIT-6 catalyst exclusively formed more olefins (54.9%) fraction. (C) 2020 Published by Elsevier Ltd.

10aCO2 hydrogenation10aMesoporous CO3O410aOlefin fraction10aPore morphology10aSilica hard template1 aGupta, Sharad1 aCiotonea, Carmen1 aRoyer, Sebastien1 aDacquin, Jean-Philippe1 aVinod, C., P. uhttps://library.ncl.res.in/content/engineering-pore-morphology-using-silica-template-route-over-mesoporous-cobalt-oxide-and-its01257nas a2200145 4500008004100000245008900041210006900130260000800199490000700207520073300214100001700947700001800964700001800982856011101000 2020 eng d00aRole of exposed crystal facets in the atmospheric pressure CO hydrogenation on Co3O40 aRole of exposed crystal facets in the atmospheric pressure CO hy cJUL0 v233 a

Co3O4 nanostructures with different exposed planes are studied for atmospheric pressure CO hydrogenation. Existence of different facets is characterized by HR-TEM and found Co3O4 - NSP (nanospheres) expose (112) facet, NB (nanobelts) exhibit (110) plane and (100) is the dominant surface facet in NC (nanocubes). Different catalytic activity is demonstrated by the specific facet of Co3O4 catalysts. CO hydrogenation is facet dependent and the catalytic activity follows the order of Co3O4-NB > Co3O4-NC > Co3O4-NSP.

1 aJain, Preeti1 aGupta, Sharad1 aVinod, C., P. uhttps://library.ncl.res.in/content/role-exposed-crystal-facets-atmospheric-pressure-co-hydrogenation-co3o403575nas a2200205 4500008004100000022001400041245006600055210006400121260000900185300001200194490000700206520292200213100001903135700002803154700001803182700002103200700002803221700002403249856009603273 2021 eng d a1528-748300aCan we identify the salt-cocrystal continuum state using XPS?0 aCan we identify the saltcocrystal continuum state using XPS cFEB  a735-7470 v213 a

X-ray photoelectron spectroscopy (XPS) is used to understand the nature of acid-base crystalline solids, to know whether the product is a salt (proton transfer, O-center dot center dot center dot H-N+) or a cocrystal (neutral adduct, O-H center dot center dot center dot N). The present study was carried out to explore if intermediate states of proton transfer from COOH to nitrogen (the proton resides between hydrogen bonded to O and N, O center dot center dot center dot H center dot center dot center dot N, quasi state) can be differentiated from a salt (complete proton transfer, N+-H center dot center dot center dot center dot O-) and cocrystal (no proton transfer, O-H center dot center dot center dot N) using N 1s XPS spectroscopy. The intermediate states of proton transfer arise when the pK(a) difference between the acid and the conjugate base is between -1 and 4, -1 < Delta pK(a) < 4, a situation common with COOH and pyridine functional groups present in drug molecules and pharmaceutically acceptable coformers. Complexes of pyridine N bases with aromatic COOH molecules in nine salts/cocrystals were cocrystallized, and their N 1s core binding energies in XPS spectra were measured. The proton state was analyzed by single-crystal X-ray diffraction for confirmation. Three new complexes were crystallized and analyzed by XPS spectra (without knowledge of their X-ray structures), to assess the predictive ability of XPS spectra in differentiating salt-cocrystal intermediate states against the extremities. The XPS results were subsequently confirmed by single-crystal X-ray data. Complexes of 3,5-dinitrobenzoic acid and isonicotinamide in 1:1 and 1:2 ratios exist as a salt and a salt-cocrystal continuum, respectively, as shown by the N 1s core binding energies. The proton states of the crystalline solids by XPS are in good agreement with the corresponding crystal structures. Other complexes, such as those of 3,5-dinitrobenzoic acid with 1,2-bis(4-pyridyl)ethylene, exhibit a salt-cocrystal continuum, maleic acids with 1,2-bis(4-pyridyl)ethylene and acridine are salts, 2-hydroxybenzoic acid and acridine is a salt, and the complex of 3,5-dinitrobenzoic acid and 3-hydroxypyridine is a salt and salt-cocrystal continuum, while fumaric acids with 1,2-bis(4-pyridyl)ethylene and acridine are cocrystals. Furthermore, three new acidbase complexes of 3,5-dinitrobenzoic acid with phenazine, 4-hydroxypyridine, and 4-cyanopyridine were studied initially by XPS and then confirmed by X-ray diffraction. In summary, since the N 1s binding energies cluster in a narrow range as cocrystals (398.7-398.9 eV) and salts (400.1-401.1 eV), it is clearly possible to differentiate between cocrystals and salts, but the saltcocrystal continuum values in XPS spectra are clustered in an intermediate range of cocrystals and salts but overlap with those of cocrystal or salt binding energies.

1 aTothadi, Srinu1 aShaikh, Tabrez, Rafique1 aGupta, Sharad1 aDandela, Rambabu1 aVinod, Chathakudath, P.1 aNangia, Ashwini, K. uhttps://library.ncl.res.in/content/can-we-identify-salt-cocrystal-continuum-state-using-xps01588nas a2200229 4500008004100000022001400041245016600055210006900221260000800290300001100298490000800309520073100317653002201048653003001070653003801100653002101138653002001159100001701179700001801196700001801214856012601232 2021 eng d a2468-823100aRole of metal-support interaction for atmospheric pressure CO2 hydrogenation over Pd/(Ti)-SBA-15 catalyst: effect of titanium composition on products selectivity0 aRole of metalsupport interaction for atmospheric pressure CO2 hy cJUL a1117320 v5113 aThe potential role of metal-support interaction for tuning the product selectivity during atmospheric pressure CO2 hydrogenation has been demonstrated on Pd/(Ti)-SBA-15 catalyst. Highly dispersed Pd NPs on SBA-15 (Pd/ SBA-15) was synthesized and further modified with titanium of varying composition. Comparison of catalytic activity of Pd/Ti-SBA-15 with its counterparts (Pd/SBA-15 and Pd/TiO2) illustrated the significance of strong PdTi interface in this catalyst and its role in tuning the product selectivity of CO2 hydrogenation. The generation of an ample amount of oxygen vacancies in the Pd/Ti-SBA-15 catalyst with maximum metallic Pd sites in close vicinity of Ti is proposed to boost the CO2 hydrogenation activity.10aCO2 hydrogenation10aMetal-support interaction10aModified deposition precipitation10aoxygen vacancies10aTitanosilicates1 aSoni, Yogita1 aGupta, Sharad1 aVinod, C., P. uhttps://library.ncl.res.in/content/role-metal-support-interaction-atmospheric-pressure-co2-hydrogenation-over-pdti-sba-1501889nas a2200181 4500008004100000022001400041245011200055210006900167260000800236300001600244490000800260520123600268100001801504700001701522700002301539700001801562856012701580 2023 eng d a1932-744700aMorphology-dependent catalysis by Co3O4 nanostructures in atmospheric pressure carbon dioxide hydrogenation0 aMorphologydependent catalysis by Co3O4 nanostructures in atmosph cJUL a13055-130640 v1273 a

In this work, three Co3O4 nanostructureswith different morphologies (cubes, rods, and sheets) were synthesizedusing a hydrothermal method and tested for the CO2 hydrogenationreaction. The physicochemical properties of the structured Co3O4 were well characterized by X-ray diffraction(XRD), Raman spectroscopy, field-emission scanning electron microscopy(FESEM), transmission electron microscopy (TEM), high-resolution transmissionelectron microscopy (HRTEM), hydrogen temperature-programmed reduction(H-2-TPR), and X-ray photoelectron spectroscopy (XPS) techniques.Based on the characterization, cube, rod, and sheet Co3O4 nanostructures were found to expose the (100), (110),and (112) planes, respectively. The effect of cobalt oxide morphologieswith different exposed surfaces on the activity and selectivity towardCO(2) hydrogenation reaction in a plug-flow reactor operatedbetween 200 and 400 & DEG;C under atmospheric pressure conditionswas explored. The results establish a correlation of the catalyticactivity with morphological structures in the order rods > sheets> cubes. H-2-TPR and XPS studies demonstrated that thehighreducibility of Co3O4 rod makes it an excellentcatalyst for CO2 hydrogenation.

1 aGupta, Sharad1 aJain, Preeti1 aJagadeesan, Dinesh1 aVinod, C., P. uhttps://library.ncl.res.in/content/morphology-dependent-catalysis-co3o4-nanostructures-atmospheric-pressure-carbon-dioxide00915nas a2200253 4500008004100000022001400041245012200055210006900177260000900246300001400255490000700269653001700276653003100293653002900324100002500353700001700378700001800395700002300413700002300436700002200459700003200481700001800513856013000531 2024 eng d a2168-048500aAtmospheric-pressure continuous-flow methane oxidation to methanol and acetic acid using H2O2 over the Au-Fe catalyst0 aAtmosphericpressure continuousflow methane oxidation to methanol cMAY  a8958-89670 v1210aCO oxidation10aHIGHLY SELECTIVE OXIDATION10ametal-organic frameworks1 aJagtap, Anuradha, V.1 aKumar, Pawan1 aGupta, Sharad1 aNagendra, Abharana1 aJha, Shambhu, Nath1 aBhattacharyya, D.1 aAjithkumar, Thalasseril, G.1 aVinod, C., P. uhttps://library.ncl.res.in/content/atmospheric-pressure-continuous-flow-methane-oxidation-methanol-and-acetic-acid-using-h2o201380nas a2200169 4500008004100000022001400041245011100055210006900166260000800235300001600243490000800259520076200267100001801029700002101047700001801068856012401086 2024 eng d a1932-744700aExploring the CeO2 support morphology for the carbon dioxide hydrogenation reaction using nickel catalysts0 aExploring the CeO2 support morphology for the carbon dioxide hyd cOCT a18782-187920 v1283 a

The catalytic activity and stability are examined for the hydrogenation of carbon dioxide under atmospheric pressure over 2 wt % Ni/CeO2 nanorods (2Ni-CeNRs), nanocubes (2Ni-CeNCs), and nanopolyhedra (2Ni-CeNPs). The 2Ni-CeNR catalysts display excellent catalytic activity and higher stability compared with 2Ni-CeNC and 2Ni-CeNP catalysts. A comprehensive understanding of the surface atomic and electronic structure versus activity has been derived using high-resolution electron microscopy and spectroscopy techniques. High metal dispersion, strong metal-support interaction (SMSI) effect and abundant oxygen vacancies are deduced to play a crucial role in determining the catalytic activity and selectivity of the CO2 hydrogenation reaction.

1 aGupta, Sharad1 aJagtap, Anuradha1 aVinod, C., P. uhttps://library.ncl.res.in/content/exploring-ceo2-support-morphology-carbon-dioxide-hydrogenation-reaction-using-nickel02307nas a2200337 4500008004100000022001400041245015300055210006900208260000900277300001100286490000800297520117300305653002001478653002401498653002201522653000901544653002301553653001201576653002501588653004301613100002401656700001801680700001901698700002001717700002501737700001701762700001801779700002501797700001801822856012901840 2025 eng d a1385-894700aExploring the electronic modulation in controlling the activity and selectivity of Ni-Au-In based catalyst in atmospheric pressure CO2 hydrogenation0 aExploring the electronic modulation in controlling the activity  cSEP  a1659210 v5203 a

Nickel-based catalysts are widely used for the hydrogenation of CO2 but encounter stability challenges during prolonged reactions and at elevated temperatures. At atmospheric pressure, nickel primarily promotes methane formation in CO2 hydrogenation reactions. In this work, we demonstrate that the stability and activity of nickel can be significantly enhanced through gold (Au) modification. Furthermore, we achieve a near-complete selectivity switch from methane to CO by incorporating indium (In), mediated through the formation of Au-In alloy. This catalyst exhibits excellent CO2 conversion and CO selectivity at relatively lower temperatures (400 degrees C), addressing a major bottleneck in the Reverse Water-Gas Shifts (RWGS) reaction. XPS studies demonstrate an interesting electron transfer mechanism facilitated by gold, which involves the formation of electronrich Au species (Au delta-) and the development of Au-In alloys. This process improves the reducibility of nickel oxide while allowing a fraction of nickel to remain in its metallic form, managing a facile hydrogenation process and regulating the shift in selectivity from CH4 to CO.

10aAlloy formation10aBimetallic catalyst10aCO2 hydrogenation10aRWGS10aSelectivity switch10asynergy10aTrimetallic catalyst10aXPS (X-ray photoelectron spectroscopy)1 aBajpai, Jyotsna, P.1 aGupta, Sharad1 aGoud, Devender1 aDeka, Diku, Raj1 aJagtap, Anuradha, V.1 aKumar, Pawan1 aAhamed, Momin1 aPeter, Sebastian, C.1 aVinod, C., P. uhttps://library.ncl.res.in/content/exploring-electronic-modulation-controlling-activity-and-selectivity-ni-au-based-catalyst01795nas a2200181 4500008004100000022001400041245010900055210006900164260000800233300001600241490000700257520114000264100001801404700001801422700002301440700002301463856012701486 2025 eng d a0887-062400aHydrogenation of CO2 catalyzed by thermally decomposed cobalt-containing alkaline earth metal carbonates0 aHydrogenation of CO2 catalyzed by thermally decomposed cobaltcon cJUN a12982-129910 v393 a

CO2 hydrogenation over Co catalysts supported on alkaline earth metal oxides was investigated. The catalysts were prepared by thermally decomposing alkaline metal carbonates CoMCO3, where M = Mg, Ca, Sr, and Ba, in H2. During the thermal activation, contingent upon the thermal stability of the precursor, it transformed into a composite of metal oxides, metals, and undecomposed metal carbonates. The thermal activation temperature, the ratio of CO2 to H2, the composition, and the basicity of the catalyst all played a significant role in influencing the conversion of CO2 and the selectivity to CH4. Among the various Co-containing alkaline earth metal carbonate precursors, CoCaCO3 activated at 400 degrees C yielded the highest steady-state CO2 conversion of 54% with a CH4 selectivity of 89.8% throughout 28 h in the reaction stream containing a 1:4 ratio of CO2 and H2. Detailed characterization showed that the CaCo-400 catalyst contained metallic Co, CaO, and undecomposed CaCO3 phases. The study assumes significance in understanding the role of the composition of catalysts in the formation of CO2 hydrogenation.

1 aGupta, Sharad1 aVinod, C., P.1 aPoupin, Christophe1 aJagadeesan, Dinesh uhttps://library.ncl.res.in/content/hydrogenation-co2-catalyzed-thermally-decomposed-cobalt-containing-alkaline-earth-metal02243nas a2200313 4500008004100000022001400041245015900055210006900214260000800283300001100291490000800302520113800310653002401448653001901472653002301491653002001514653002001534653003501554653002301589100002801612700002601640700002201666700002901688700001801717700002301735700002201758700001801780856013101798 2025 eng d a1385-894700aUnravelling the Cu-Co nanoparticle synergy over Ceria-Zirconia support toward efficient reverse water gas shift (RWGS) conversion under H2 lean conditions0 aUnravelling the CuCo nanoparticle synergy over CeriaZirconia sup cMAR a1607050 v5083 a

CO2 emissions leading to global warming and environmental and socio-economic issues have propelled the research community to develop technologies capable of capturing and converting CO2 into valuable products. Controlling the selectivity toward platform molecules like CO, methanol, or methane is a fundamental challenge in CO2 hydrogenation. Supported cobalt nanoparticles are known for hydrocarbon production through FischerTropsch (FT) reaction, and Cu-based catalysts are known for reverse water gas shift (RWGS) reaction. Here, we show that d-band centre can be carefully modulated by making bimetallic combinations of Cu and Co for a highly active RWGS catalyst. An oxygen vacancy-rich nanostructured ceria-zirconia (CZ) support with Cu nanoparticles (2 wt%) modified with as low as 0.05 wt% Co shows excellent conversion for CO2 hydrogenation and selectivity for CO below 500 degrees C. The optimized catalyst shows CO2 conversion even under hydrogen lean conditions (H2/ CO2 ratio 0.5:1), with a breakthrough rate of 206023 mmol/gmetal/h for CO at 600 degrees C, having H2 utilization of 80% for the RWGS process.

10aBimetallic catalyst10aCeria-zirconia10aCO 2 hydrogenation10aCobalt catalyst10aCopper catalyst10aReverse water gas shift (RWGS)10asynergistic effect1 aJagtap, Anuradha, Vijay1 aBamnia, Mahesh, Kumar1 aMaibam, Ashakiran1 aBajpai, Jyotsna, Paliwal1 aGupta, Sharad1 aThomas, Sharon, K.1 aDabke, Niteen, B.1 aVinod, C., P. uhttps://library.ncl.res.in/content/unravelling-cu-co-nanoparticle-synergy-over-ceria-zirconia-support-toward-efficient-reverse