Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via lo...Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via low-temperature coprecipitation,exhibiting excellent performance for the selective hydrogenation of 5-hydroxymethylfurfural(HMF).A linear correlation is first observed between solvent polarity(E_(T)(30))and product selectivity within both polar aprotic and protic solvent classes,suggesting that solvent properties play a vital role in directing reaction pathways.Among these,1,4-dioxane(aprotic)favors the formation of 2,5-bis(hydroxymethyl)furan(BHMF)with 97.5%selectivity,while isopropanol(iPrOH,protic)promotes 2,5-dimethylfuran production with up to 99.5%selectivity.Mechanistic investigations further reveal that beyond polarity,proton-donating ability is critical in facilitating hydrodeoxygenation.iPrOH enables a hydrogen shuttle mechanism where protons assist in hydroxyl group removal,lowering the activation barrier.In contrast,1,4-dioxane,lacking hydrogen bond donors,stabilizes BHMF and hinders further conversion.Density functional theory calculations confirm a lower activation energy in iPrOH(0.60 eV)compared to 1,4-dioxane(1.07 eV).This work offers mechanistic insights and a practical strategy for solvent-mediated control of product selectivity in biomass hydrogenation,highlighting the decisive role of solvent-catalyst-substrate interactions.展开更多
Co-based materials usually undergo in-situ surface reconstruction during oxidation reactions,forming high-valent Co_(3)+/Co4+species as the true active sites.However,conventional bulk structures of Co-based materials ...Co-based materials usually undergo in-situ surface reconstruction during oxidation reactions,forming high-valent Co_(3)+/Co4+species as the true active sites.However,conventional bulk structures of Co-based materials hinder deep phase transformation,limiting the utilization of internal Co sites and suppressing catalytic efficiency.Here,we report the hollow engineering of cobalt phosphide(CoP)to facilitate exposure of Co sites and promote in-situ transformation to Co_(3+)/Co^(4+)active species for enhanced oxidation activity.Hollow CoP(H-CoP)is derived from ZIF-67 via controlled etching and phosphorization,with electrochemically active surface area 2.1 times that of conventional solid CoP(S-CoP).H-CoP achieves a current density of 10 mA·cm^(-2) at a lower potential(1.26 V vs.reversible hydrogen electrode(RHE))in 5-hydroxymethylfurfural oxidation reaction(HMFOR),with a HMF conversion of 99.5%,2,5-furandicarboxylic acid yield of 98.6%,and Faraday efficiency of 97.5% at 1.45 V(vs.RHE),much superior to S-CoP.When applied as a bifunctional catalyst in the HMFOR coupled with hydrogen evolution reaction(HER)electrolyzer,H-CoP requires an ultralow voltage of 1.64 V to reach 10 mA·cm^(-2),with the cell voltage reduced by 190 mV compared to the conventional oxygen evolution reaction coupled with HER water splitting system.展开更多
基金the National Nature Science Foundation of China for Excellent Young Scientists Fund(32222058)Fundamental Research Foundation of CAF(CAFYBB2022QB001).
文摘Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via low-temperature coprecipitation,exhibiting excellent performance for the selective hydrogenation of 5-hydroxymethylfurfural(HMF).A linear correlation is first observed between solvent polarity(E_(T)(30))and product selectivity within both polar aprotic and protic solvent classes,suggesting that solvent properties play a vital role in directing reaction pathways.Among these,1,4-dioxane(aprotic)favors the formation of 2,5-bis(hydroxymethyl)furan(BHMF)with 97.5%selectivity,while isopropanol(iPrOH,protic)promotes 2,5-dimethylfuran production with up to 99.5%selectivity.Mechanistic investigations further reveal that beyond polarity,proton-donating ability is critical in facilitating hydrodeoxygenation.iPrOH enables a hydrogen shuttle mechanism where protons assist in hydroxyl group removal,lowering the activation barrier.In contrast,1,4-dioxane,lacking hydrogen bond donors,stabilizes BHMF and hinders further conversion.Density functional theory calculations confirm a lower activation energy in iPrOH(0.60 eV)compared to 1,4-dioxane(1.07 eV).This work offers mechanistic insights and a practical strategy for solvent-mediated control of product selectivity in biomass hydrogenation,highlighting the decisive role of solvent-catalyst-substrate interactions.
基金the National Natural Science Foundation of China(Nos.22422806,22378136,and 22138003)the Guangdong Pearl River Talents Program(Nos.2021QN02C847 and 2021ZT09Z109)+4 种基金the Natural Science Foundation of Guangdong Province(Nos.2024A1515011196 and 2023B1515040005)the Guangzhou Municipal Science and Technology Project(No.2025A04J5244)the Fundamental Research Funds for the Central Universities(No.2024ZYGXZR011)the State Key Laboratory of Pulp and Paper Engineering(Nos.2023PY06 and 2024ZD09)the TCL Young Talent Program.
文摘Co-based materials usually undergo in-situ surface reconstruction during oxidation reactions,forming high-valent Co_(3)+/Co4+species as the true active sites.However,conventional bulk structures of Co-based materials hinder deep phase transformation,limiting the utilization of internal Co sites and suppressing catalytic efficiency.Here,we report the hollow engineering of cobalt phosphide(CoP)to facilitate exposure of Co sites and promote in-situ transformation to Co_(3+)/Co^(4+)active species for enhanced oxidation activity.Hollow CoP(H-CoP)is derived from ZIF-67 via controlled etching and phosphorization,with electrochemically active surface area 2.1 times that of conventional solid CoP(S-CoP).H-CoP achieves a current density of 10 mA·cm^(-2) at a lower potential(1.26 V vs.reversible hydrogen electrode(RHE))in 5-hydroxymethylfurfural oxidation reaction(HMFOR),with a HMF conversion of 99.5%,2,5-furandicarboxylic acid yield of 98.6%,and Faraday efficiency of 97.5% at 1.45 V(vs.RHE),much superior to S-CoP.When applied as a bifunctional catalyst in the HMFOR coupled with hydrogen evolution reaction(HER)electrolyzer,H-CoP requires an ultralow voltage of 1.64 V to reach 10 mA·cm^(-2),with the cell voltage reduced by 190 mV compared to the conventional oxygen evolution reaction coupled with HER water splitting system.
