02494nas a2200241 4500008004100000022001400041245012400055210006900179260000900248300001100257490000800268520163700276653002601913653002701939653002701966653001901993653002802012100001902040700002102059700001802080700002202098856013202120 2021 eng d a0926-337300aFacile transfer of excited electrons in Au/SnS2 nanosheets for efficient solar-driven selective organic transformations0 aFacile transfer of excited electrons in AuSnS2 nanosheets for ef cJUN  a1199270 v2863 a

Solar driven aerial oxidation processes have gained importance in organic transformations leading to the development of many nanocrystalline photocatalysts. Although such nanomaterials have many potential advantages, they often underperform due to poor visible light absorption and rapid recombination of excitons. Incorporation of plasmonic nanoparticles (NPs) on the catalyst surfaces can extend their response to visible light and improve photocatalytic efficiency by the `hot-electron' injection mechanism. Nanostructures of SnS2 too absorb a part of the visible light to induce many photocatalytic reactions, though their ability to perform the selective and controlled organic transformations has not yet been observed. Herein, we demonstrate the first example of such transformation with the oxidative coupling of various benzylamine (BA) derivatives to imines under ambient conditions using SnS2 nanosheets (NSs). The reaction rate improves manifold and shows similar to 98 % conversion (>99 % selectivity) in 2 h under direct sunlight and open-air when the NSs were decorated with 1.5 wt% Au NPs on (Au/SnS2), making it one of the best catalysts for this reaction. We found that the large enhancement in activity upon Au loading is accompanied by a noticeable change in photo-induced charge accumulation behaviour in Au/SnS2 from the usual ``spike and overshoot'' one and contributed by facile transfer of excited electrons across the Au-SnS2 heterojunction in which Au NPs act as both sources and sinks for the photo-excited electrons. Finally, a detailed mechanism of the oxidation reaction has been proposed.

10aBenzylamine oxidation10aHot-electron injection10aPlasmonic nanoparticle10aSnS2 nanosheet10aSolar energy harvesting1 aMondal, Sanjit1 aSahoo, Lipipuspa1 aVinod, C., P.1 aGautam, Ujjal, K. uhttps://library.ncl.res.in/content/facile-transfer-excited-electrons-ausns2-nanosheets-efficient-solar-driven-selective-organic01981nas a2200193 4500008004100000022001400041245011900055210006900174260000800243300001400251490000600265520128500271100002201556700002601578700001801604700001601622700002301638856012601661 2024 eng d a2516-023000aFacile synthesis of nanostructured Ni/NiO/N-doped graphene electrocatalysts for enhanced oxygen evolution reaction0 aFacile synthesis of nanostructured NiNiONdoped graphene electroc cMAY a2813-28220 v63 a

Electrocatalysts containing a Ni/NiO/N-doped graphene interface have been synthesised using the ligand-assisted chemical vapor deposition technique. NiO nanoparticles were used as the substrate to grow N-doped graphene by decomposing vapours of benzene and N-containing ligands. The method was demonstrated with two nitrogen-containing ligands, namely dipyrazino[2,3-f:2 `,3 `-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (L) and melamine (M). The structure and composition of the as-synthesized composites were characterized by XRD, Raman spectroscopy, SEM, TEM and XPS. The composite prepared using the ligand L had NiO sandwiched between Ni and N-doped graphene and showed an overpotential of 292 mV at 10 mA cm-2 and a Tafel slope of 45.41 mV dec-1 for the OER, which is comparable to the existing noble metal catalysts. The composite prepared using the ligand M had Ni encapsulated by N-doped graphene without NiO. It showed an overpotential of 390 mV at 10 mA cm-2 and a Tafel slope of 78.9 mV dec-1. The ligand-assisted CVD route demonstrates a facile route to control the microstructure of the electrocatalysts. Electrocatalysts containing a Ni/NiO/N-doped graphene interface have been synthesised using the ligand-assisted chemical vapor deposition technique.

1 aMadampadi, Roshni1 aPatel, Avit, Bhogilal1 aVinod, C., P.1 aGupta, Ritu1 aJagadeesan, Dinesh uhttps://library.ncl.res.in/content/facile-synthesis-nanostructured-ninion-doped-graphene-electrocatalysts-enhanced-oxygen02902nas a2200289 4500008004100000022001400041245012300055210006900178260000800247300001100255490000800266520195400274653001802228653000802246653003102254653001302285653002902298653001902327100001902346700002202365700001902387700002302406700001602429700001902445700001802464856013002482 2025 eng d a1385-894700aFacet dependence for solvent-modulated proton-coupled electron transfer in furfural acetalization on Pd nanostructures0 aFacet dependence for solventmodulated protoncoupled electron tra cJUN a1631590 v5143 a

Furfural dialkyl acetals prepared via acetalization reaction of furfural and alcohols are promising biofuels. Using defined experiments and density functional theory (DFT) simulations, the structure-dependent activity and selectivity for furfural acetalization reaction in the presence of alcohols (methanol, ethanol, propanol and butanol) as solvents was studied over well-defined supported Pd nanostructures (octahedra (111), cubes (100) and spheres (both (111) and (100)). Pd cubes supported over TiO2 in the presence of ethanol as a solvent (at 303 K and balloon pressure H-2) exhibited 78 % conversion and 100 % selectivity for furfural diethyl acetal product in a short time (similar to 180 min). In contrast, Pd octahedra (111) and Pd spheres showed low conversions (18 % and 6 %) at the same reaction conditions. Interestingly, when used as a solvent, methanol showed the highest conversion (90 %) and selectivity (100 %) for furfural acetalization over Pd cubes. DFT simulations provided mechanistic insight into the reactivity of the two different Pd facets (111) and (100) in the presence of alcohol molecules towards furfural acetalization reaction. A three-step reaction mechanism was proposed for furfural acetalization with alcohols: (i) alcohol hydroxyl-dehydrogenation (ii) hydrogenation of furfural carbonyl oxygen, and (iii) formation of hemiacetal product. For all three steps, Pd (100) exhibited low activation barriers (51.6, 26.7 and 76.2 kJ/mol) compared to Pd (111) surface (78.6, 35.8 and 92.2 kJ/mol) in the presence of ethanol. The activation barriers for the above steps were further reduced to 47.8, 23.9 and 64.6 kJ/mol on Pd (100) in the presence of methanol, explaining the experimental high reactivity aided by methanol. DFT calculations elucidated the role of the hydrogen bonding network between the solvent molecules and adsorbate, enabling proton-coupled electron transfer for accelerated reactions.

10aAcetalization10aDFT10afacet-dependent reactivity10afurfural10aFurfural dialkyl acetals10asolvent effect1 aPorwal, Govind1 aDandekar, Pallavi1 aGorai, Twinkle1 aKhan, Tuhin, Suvra1 aHaider, Ali1 aGupta, Shelaka1 aVinod, C., P. uhttps://library.ncl.res.in/content/facet-dependence-solvent-modulated-proton-coupled-electron-transfer-furfural-acetalization