Selective upgrading of biomass-derived benzylic ketones by (formic acid)–Pd/HPC–NH2 system with high efficiency under ambient conditions

•(FA)–Pd/HPC–NH2 achieves the selective HDO of benzyl ketones from mixed oxygenates•H+/H? species accelerates hydrogenation C=O bond in ketones•Formate intermediates expedite cleavage Cbenzyl–O via an EDDO pathway•Proposing a green route to produce biofuels or chemicals only biomass Producing value-added and renewable rather than fossil fuels is reckoned as effective recipe against global warming. However, bio-oils derived pyrolysis with high oxygen content (10–45 wt %) cannot be directly utilized. Hydrodeoxygenation (HDO) commonly regarded most upgrading strategy. Nevertheless, traditional process using H2 hydrogen source produced by water-gas-shift reaction (WGS) energy consuming non-selective under harsh conditions (100°C?300°C, 1 ?30 MPa H2, acid sites). Instead, current work uses biomass-derived formic reductant situ generate H+/H? on Pd/HPC–NH2 catalyst, realizing oxygenates ambient conditions. Therefore, environmentally friendly valuable products mild proposed, which very instructive for carbon neutralization. Upgrading phenolic compounds provides approach production higher-value-added chemicals. established catalytic systems display low hydrodeoxygenation activities even Here, we found that Pd supported –NH2-modified hierarchically porous (Pd/HPC–NH2) (FA) exhibits unprecedented performance benzylic crude lignin-derived oxygenates. Designed experiments theoretical calculations reveal generated FA decomposition nucleophilic attack carbonyl formate formed esterification intermediate alcohol expedites C–O bonds, achieving TOF 152.5 h?1 at 30°C vanillin upgrading, 15 times higher processes (?10 h?1, 100°C–300°C). This intriguing transportation IntroductionWith fast depletion resources, lignocellulosic increasingly becoming well-accepted substitute clean chemicals.1Tan S. Zhang Z. Sun J. Wang Q. Recent progress HZSM-5.Chin. 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Coupling specific functions achieved p-creosol yield 99% 30°C, respectively 1B). Notably, also biomass-related substrates, syringaldehyde, acetosyringone, stearic indicating broader range subjects batch reality. Moreover, exhibited stability anchoring uniform NPs amino groups. 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