01712nas a2200217 4500008004100000245009600041210006900137260000800206300001200214490000700226520099500233653001801228653002401246653002001270653001301290653002301303653001801326100001701344700001801361856011501379 2018 eng d00aOne pot conversion of furfural to 2-methylfuran in the presence of PtCo bimetallic catalyst0 aOne pot conversion of furfural to 2methylfuran in the presence o cMAY a703-7130 v203 a

Biomass-derived furfural (FAL) is the platform chemical for synthesis of various value-added chemicals and fuels. One of the FAL-derived chemicals, i.e., 2-methylfuran (2-MF), is the potential biofuel due to its attractive chemical and physical properties. Various methods are reported for conversion of FAL to 2-MF which are operated at high temperature and high H2 pressure. In present work, one pot catalytic method was developed in batch mode process for conversion of FAL to 2-MF. Reactions are carried out in the presence of PtCo/C bimetallic catalyst under 0.5–1 MPa H2 pressure. Monometallic and bimetallic catalysts with different Pt and Co loading were prepared by wet impregnation method, and catalysts were characterized by transmission electron microscopy, BET surface area, X-ray photoelectron spectroscopy, X-ray diffraction and inductive coupled plasma atomic emission spectroscopy techniques. 59% 2-MF yield was achieved at 180 °C and lower (0.5 MPa) H2 pressure.

10a2-Methylfuran10aBimetallic catalyst10aCo-impregnation10afurfural10aHydrodeoxygenation10aHydrogenation1 aDohade, M.G.1 aDhepe, P., L. uhttps://library.ncl.res.in/content/one-pot-conversion-furfural-2-methylfuran-presence-ptco-bimetallic-catalyst02147nas a2200217 4500008004100000022001400041245016000055210006900215260000800284300001600292490000800308520134400316653001701660653002301677653001101700653002101711653002901732100002201761700002201783856012401805 2020 eng d a2468-823100aUnderstanding the influence of alumina supported ruthenium catalysts synthesis and reaction parameters on the hydrodeoxygenation of lignin derived monomers0 aUnderstanding the influence of alumina supported ruthenium catal cJAN aUNSP 1105250 v4803 a

Up-gradation of lignin derived monomers to value-added and fuel grade products is important to make overall bio-refinery process economical. Although, few studies are devoted on this work yet, systematic study on commercially viable (low loading of metal, recyclable catalyst, mild conditions, high selectivities etc.) is scarce and typically done under harsh conditions. Herein, we report, the methodical effect of support (SiO2, Al2O3 (acidic, basic and neutral), SiO2-Al2O3) on the hydrodeoxygenation (HDO) of lignin derived various monomers, guaiacol, veretrol, eugenol, phenol using very low loading (0.5 wt%) Ru catalyst. Very high yield (82%) of cyclohexanol from guaiacol could be achieved in presence of cyclohexane as a solvent and Ru/Al2O3-Acidic catalyst at 225 degrees C and under 1 MPa H-2 pressure. The detailed study on the effect of solvent, stability and adsorption of reactant & products etc. is done and it was observed that products are more prone to adsorb and undergo further reactions. The complete characterization of fresh and spent catalysts revealed that lower catalyst reduction temperature and presence of Ru in partially higher oxidation state proved by XPS, helps in enhancing the cyclohexanol formation. Subsequently, role of Ru particle size and support on the activity was also investigated.

10aCyclohexanol10aHydrodeoxygenation10alignin10areaction pathway10asupported metal catalyst1 aSingh, Dheerendra1 aDhepe, Paresh, L. uhttps://library.ncl.res.in/content/understanding-influence-alumina-supported-ruthenium-catalysts-synthesis-and-reaction01530nas a2200217 4500008004100000022001400041245014900055210006900204260000900273300001100282490000800293520071800301653004301019653001701062653002301079653001101102653003001113100002201143700002201165856012501187 2021 eng d a1566-736700aEfficient catalytic transfer hydrogenation-hydrodeoxygenation of lignin derived monomers: investigating catalyst properties-activity correlation0 aEfficient catalytic transfer hydrogenationhydrodeoxygenation of  cJAN  a1062200 v1493 a

Reduction of O/C ratio of lignin derived monomers via hydrodeoxygenation (HDO) pathway is conventionally furnished using molecular hydrogen under severe conditions. Nonetheless, due to a prerequisite to accomplish HDO through commercially attractive methodology we report, HDO reactions of various phenolic compounds via catalytic transfer hydrogenation (CTH) pathway using very low loading of Ru (0.5 wt%) on neutral and acidic Al2O3 under nitrogen atmosphere. With guaiacol as a substrate, 74% cyclohexanol yield at 225 degrees C in the presence of IPA is realized. Bi-functionality of metal state, acidity of support and nature of alcohol are perceived to be responsible for the variation in activity.

10aCatalytic transfer hydrogenation (CTH)10aCyclohexanol10aHydrodeoxygenation10alignin10aSupported metal catalysts1 aSingh, Dheerendra1 aDhepe, Paresh, L. uhttps://library.ncl.res.in/content/efficient-catalytic-transfer-hydrogenation-hydrodeoxygenation-lignin-derived-monomers02878nas a2200277 4500008004100000022001400041245014900055210006900204260000800273300001600281490000600297520188700303653003702190653001702227653000802244653002302252653001302275653002002288653003002308100002502338700002202363700002902385700002602414700002902440856013102469 2021 eng d a2168-048500aMechanistic investigations on the catalytic transfer hydrogenation of lignin-derived monomers over Ru catalysts: theoretical and kinetic studies0 aMechanistic investigations on the catalytic transfer hydrogenati cOCT a14040-140500 v93 aThe hydrodeoxygenation (HDO) reaction of oxygenated compounds such as lignin-derived phenolics is well studied using molecular H-2 as a hydrogen source, yet the use of high pressures discourages its use on an industrial scale. As an alternative, the catalytic transfer hydrogenation (CTH) pathway provides in situ hydrogenation species, which reduces the need for the high-pressure infrastructure required when molecular hydrogen is used. Nevertheless, this strategy is scantly studied, and in lieu with this, herein we report the kinetic and mechanistic investigations of the CTH strategy for the HDO of guaiacol, phenol, anisole veratrole, and eugenol to their respective products. For potential commercialization purposes, low loading of metal, milder reaction conditions, and high selectivity toward desired products with a high H/C ratio were considered while designing catalysts (0.5 wt % Ru on SiO2-Al2O3, SiO2, Al2O3-acidic, Al2O3-basic, and Al2O3-neutral) for these reactions. As high as 74% cyclohexanol yield from guaiacol was achieved at 225 degrees C in the presence of isopropyl alcohol (IPA) as the hydrogen source and over the Ru/Al2O3-acidic catalyst reduced at 150 degrees C. A detailed kinetic study is carried out to understand the interaction of the substrate and intermediates with the catalyst and the influence of reaction parameters on the product formation. It was observed that the cisisomer of 2-methoxycyclohexanol rapidly undergoes further conversion than the trans-isomer. The experimental observations are substantiated through density functional theory (DFT) studies on Ru(0001) and guaiacol molecule complexes. DFT studies indicate that the adsorption of the cis-isomer is more exothermic as compared to that of the trans counterpart, and the underlying electronic factors are elucidated using charge density difference and density of states plots.10acatalytic transfer hydrogenation10aCyclohexanol10aDFT10aHydrodeoxygenation10akinetics10alignin monomers10aSupported metal catalysts1 aKhan, Tufeil, Sartaj1 aSingh, Dheerendra1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja1 aDhepe, Paresh, Laxmikant uhttps://library.ncl.res.in/content/mechanistic-investigations-catalytic-transfer-hydrogenation-lignin-derived-monomers-over-ru01669nas a2200253 4500008004100000245009700041210006900138260000800207300000900215490000700224520088900231653000901120653001501129653001301144653002301157653000701180653001101187653000601198100002101204700002501225700002001250700002101270856012401291 2022 eng d00aC-O hydrogenolysis of C3-C4 polyols selectively to terminal diols over Pt/W/SBA-15 catalysts0 aCO hydrogenolysis of C3C4 polyols selectively to terminal diols  cSEP a10700 v123 a

Pt/W/SBA-15 catalysts (with Pt-loading = 0.5-4 wt% and W-loading = 1 wt%) prepared by the sequential impregnation method were evaluated for selective C-O cleavage of erythritol and glycerol in an aqueous medium. The Pt and W particles dispersed on SBA-15 approached close proximity at higher Pt loadings and afforded synergistic enhancement in C-O hydrogenolysis activity/selectivity. 1,4-Butanediol yields of 30.9% (at 190 degrees C, 50 bar H-2 and 24 h) and 1,3-propanediol yields of 34.4% (at 190 degrees C, 50 bar H-2 and 12 h of reaction) were obtained over these catalysts. Pt nanoparticles (facilitating dissociative H-2 adsorption and spillover) and W (present as acidic oligomeric WOx species; activating and coordinating the polyol via 1 degrees-OH group) worked in tandem for the selective hydrogenolysis of polyols yielding terminal diols of industrial demand.

10adiol10aErythritol10aGlycerol10aHydrodeoxygenation10aPt10aSBA-1510aW1 aBhowmik, Susmita1 aEnjamuri, Nagasuresh1 aMarimuthu, Banu1 aDarbha, Srinivas uhttps://library.ncl.res.in/content/c-o-hydrogenolysis-c3-c4-polyols-selectively-terminal-diols-over-ptwsba-15-catalysts02074nas a2200277 4500008004100000022001400041245013100055210006900186260000800255300001100263490000800274520114500282653001801427653001701445653001301462653002301475653001901498653002201517100002101539700002501560700001901585700002101604700002001625700002101645856013001666 2022 eng d a2468-823100aInsights into active tungsten species on Pt/W/SBA-15 catalysts for selective hydrodeoxygenation of glycerol to 1,3-propanediol0 aInsights into active tungsten species on PtWSBA15 catalysts for  cOCT a1127040 v5313 a

Diols are important class of industrial chemicals. Their synthesis from bio-resources (instead from fossil feed-stocks) is sustainable. In this study, we probed active tungsten species on Pt/W/SBA-15 catalysts for selective synthesis of 1,3-propanediol (1,3-PDO) from aqueous glycerol through a liquid-phase hydrodeoxygenation re-action. A synergistic enhancement in glycerol conversion and 1,3-PDO selectivity was observed when both Pt and W were present on the catalyst. A volcano-shape variation followed with a gradual increase in glycerol conversion and 1,3-PDO yield with W-loading (0.25-15 wt%) was observed. Pt dispersion and acidity of the catalyst dis-played similar variations with the W-loading confirming their critical role in the reaction. Structure-function relationships inferred that oligomeric WOx with moderate Bro center dot nsted acidity (predominant at 1 wt% W-loading) in contact with dispersed Pt are the active species for 1,3-PDO formation and crystalline WO3 with strong Bro center dot nsted acidity (prevalent above 4 wt% W-loading) in association with Pt nanoparticles lead to 1-propanol formation.

10a3-Propanediol10aActive sites10aGlycerol10aHydrodeoxygenation10aHydrogenolysis10aSupported Pt-WO x1 aBhowmik, Susmita1 aEnjamuri, Nagasuresh1 aSethia, Govind1 aAkula, Venugopal1 aMarimuthu, Banu1 aDarbha, Srinivas uhttps://library.ncl.res.in/content/insights-active-tungsten-species-ptwsba-15-catalysts-selective-hydrodeoxygenation-glycerol02324nas a2200217 4500008004100000022001400041245011700055210006900172260000800241490000700249520155600256653001701812653001301829653002301842653001801865653002501883100002101908700002601929700002301955856012801978 2025 eng d a1867-388000aHydrodeoxygenation of guaiacol to cyclohexanol using noble metal-supported Ni-based perovskite-derived catalysts0 aHydrodeoxygenation of guaiacol to cyclohexanol using noble metal cAUG0 v173 a

This study focuses on the role of noble metal-doped Ni-based perovskites, specifically LaNiO3 and NiTiO3 catalysts in the hydrodeoxygenation (HDO) of guaiacol. The findings demonstrate that reduced Ru-LaNiO3 catalyst achieved superior performance with 100% guaiacol conversion and a 75% selectivity toward cyclohexanol, compared to reduced Ru-NiTiO3, which achieved only 43% conversion and 25% cyclohexanol selectivity under identical conditions (240 degrees C, 30 bar H2, and 4 h). High-resolution transmission electron microscopic (HR-TEM) analysis reveals that LaNiO3-supported catalysts exhibit better metal dispersion and smaller nickel nanoparticle sizes compared to NiTiO3-supported counterparts. X-ray photoelectron spectroscopy (XPS) analysis shows that the reduction of nickel and noble metals is more facile on LaNiO3. Additionally, the O 1s XPS profile for reduced Ru-LaNiO3 indicates a higher proportion of lattice oxygen (OLat similar to 79%) and a lower proportion of oxygen vacancies (OVac similar to 21%) compared to other catalyst systems. The optimized OLat/OVac ratio is shown to be critical for the effective HDO of guaiacol. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) demonstrates a high HDO reaction rate using reduced Ru-LaNiO3 than reduced Ru-NiTiO3, with cyclohexanol formation attributed to the keto-enol tautomerization pathway. Overall, this study underscores the critical roles of oxygen vacancies, metal dispersion, and metal-metal oxide interactions in the HDO of guaiacol.

10aCyclohexanol10aGuaiacol10aHydrodeoxygenation10aIn-situ DRIFT10aNi-based perovskites1 aMarimuthu, Prabu1 aRaja, Thirumalaiswamy1 aVinu, Ravikrishnan uhttps://library.ncl.res.in/content/hydrodeoxygenation-guaiacol-cyclohexanol-using-noble-metal-supported-ni-based-perovskite