02878nas 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-ru01879nas a2200253   4500008004100000022001400041245011500055210006900170260000800239300001100247490000800258520105200266653001601318653001101334653002701345653000801372653001401380653001901394653001401413100002901427700001101456700002601467856013201493       2021                        eng d  a0169-433200aSubstrate augmented catalytic activity towards NRR: a case study of Li doped Al clusters on defective graphene0 aSubstrate augmented catalytic activity towards NRR a case study   cNOV  a1505860 v5663 aDensity Functional Theory (DFT) based methods are applied to examine the potential of lithium doped aluminium clusters consisting of 3-13 atoms for dinitmgen molecule activation in terms of N N bond length, redshift in N N bond stretching frequency, nitrogen interaction energy and frontier molecular orbitals analysis. The present work highlights the role of monovacant C-3 defective graphene as a support in fine tuning the catalytic activity of Li doped Al clusters for reduction of N-2. Fundamental insights to synergic binding of clusters with defective graphene is brought out and its role in enhancing activation of dinitmgen molecule is explained. Supported Aln-1Li clusters with six or more atoms are noted to be more active towards N-2 molecule activation as compared to the clusters without support. Dinitrogen molecule undergoes a maximum bond elongation of 1.56 angstrom corresponding to redshift of 1690 cm(-1) on Al7Li@graphene and Al12Li@graphene. This is maximum value reported in context of activation for N-2 molecule till date.10aAl clusters10aAl12Li10aC-3 defective graphene10aDFT10aLi Doping10aN-2 activation10aRed-shift1 aSamal, Pragnya, Paramita1 aPoonam1 aKrishnamurty, Sailaja  uhttps://library.ncl.res.in/content/substrate-augmented-catalytic-activity-towards-nrr-case-study-li-doped-al-clusters-defective