Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the in...Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the intrinsic activity of Ni and Co catalytic centers.However,the dynamic evolution and atomic-scale synergy between these centers remain elusive.Herein,we fabricated NiCo_(2)O_(4)nanosheets supported on nickel foam,where Ni preferentially occupies tetrahedral sites to regulate the electronic configuration of octahedral Co.Experimental and theoretical results demonstrate that the incorporation of tetrahedral Ni induces low-to-intermediate spin transition in octahedral Co,thereby optimizing eg orbital occupancy and stabilizing active sites.This spin-state engineering establishes Ni-Co synergistic catalytic centers for the selective oxidation of glucose to formate(FA).At higher potential(≥1.4 V vs.RHE),octahedral Co undergoes reconstruction into excessive active CoOOH and CoO_(2)species,resulting in glucose overoxidation to CO_(2)and intensified competitive oxygen evolution.In contrast,at lower potentials(<1.4 V vs.RHE),tetrahedral Ni facilitates electron delocalization across the Ni–O–Co lattice,thereby stabilizing octahedral Co for glucose adsorption and oxidation.Subsequently,a coupled electrocatalytic system was constructed,achieving 80.7%FA yield with 91.3%Faradaic efficiency(FE)at NiCo_(2)O_(4)anode and H2 evolution rate of 696μmol h^(−1)with 99.9%FE at Pt cathode for 2 h under 1.35 V vs.RHE.This work provides a deep insight into spin-state regulation of the catalytic center,offering valuable guidance for rational catalyst design.展开更多
Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electro...Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.展开更多
Photoreforming poly(lactic acid)(PLA)plastics into pyruvic acid(PA)coupled with hydrogen evolution is of great significance for sustainable development.However,a significant challenge lies inα-OH bond cleaving of lac...Photoreforming poly(lactic acid)(PLA)plastics into pyruvic acid(PA)coupled with hydrogen evolution is of great significance for sustainable development.However,a significant challenge lies inα-OH bond cleaving of lactic acid(LA).Herein,CdS/Bi_(4)Ti_(3)O_(12)composite is fabricated,bridged by Bi−S bonds,through in-situ growth of CdS nanoparticles on Bi_(4)Ti_(3)O_(12)nanoflowers for the successive removal of hydrogen fromα-C in LA.In-situ X-ray photoelectron spectroscopy confirms the S-scheme carriers transfer route and interfacial Bi−S bond in CdS/Bi_(4)Ti_(3)O_(12).Consequently,the photo-electrons and holes with extended lifetimes and strong redox potential accumulate in the CdS conduction band and Bi_(4)Ti_(3)O_(12)valence band,respectively,as evidenced by in-situ electron spin resonance and time-resolved photoluminescence.This facilitates the generation of·OH radicals,which further participate in the successive dehydrogenation reaction of LA.Consequently,the photoreforming efficiencies of converting PLA into PA and H_(2)by CdS/Bi_(4)Ti_(3)O_(12)are 1.7 and 3.16 mmol g^(-1)h^(-1),which are respectively 2.8 and 22 times higher than that by pristine Bi_(4)Ti_(3)O_(12).The present work provides a new approach for designing S-scheme to achieve hydrogen production and value-added conversion of plastics.展开更多
Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demons...Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demonstrated substantial potential for the advancement of electrocatalytic CO_(2) reduction to formate.However,due to the weak bonding of protons(H^(*)) of Bi,the available protonate of CO_(2) on Bi is insufficient,which limits the formation of OCHO^(*).Prediction by theoretical calculation,chlorine doping can effectively promote the dissociation of H_(2)O and thus achieve effective proton supply.We prepare chlorine-doped Bi(Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO_(2) .An obvious improvement of faradaic efficiency(FE) of formate(96.7% at-0.95 V vs.RHE) can be achieved on Cl-Bi,higher than that of Bi(89.4%).Meanwhile,Cl-Bi has the highest formate production rate of 275 μmol h^(-1)cm^(-2)at-0.95 V vs.RHE,which is 1.2 times higher than that of Bi(224 μmol h^(-1)cm^(-2)).In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H_(2)O and supply sufficient protons to promote the protonation of CO_(2) to OCHO^(*),which is consistent with theoretical calculation.The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.展开更多
The use of Cu_(2)O-based photocathodes has demonstrated the promising activity of these earth-abundant materials for the photoelectrochemical CO_(2)reduction reaction(CO_(2)RR),particularly in producing methanol.Howev...The use of Cu_(2)O-based photocathodes has demonstrated the promising activity of these earth-abundant materials for the photoelectrochemical CO_(2)reduction reaction(CO_(2)RR),particularly in producing methanol.However,their application in long-term devices is hindered by severe photocorrosion.To address this limitation,photocathode designs incorporating Schottky barriers,heterojunctions,and scaffolding layers have been explored.In this work,a CuBi_(2)O_(4)/CuO thin layer was employed as a scaffold to support Cu_(2)O films with either seeded or grown morphologies for enhanced photoelectrochemical CO_(2)RR.Photoelectrochemical testing in CO_(2)-saturated electrolyte revealed that 0.55 V vs.reversible hydrogen electrode(RHE)yielded the highest activity and stability for methanol(CH_(3)OH)production,outperforming more negative potentials.Furthermore,the present work highlighted that electrolyte engineering can be used to promote the generation of alternative products such as methyl acetate(CH_(3)COOCH_(3)).The presence of CuBi_(2)O_(4)/CuO scaffold was critical for allowing this pathway,providing both enhanced stability and improved charge transfer on the Cu_(2)O surface.The generation of CH_(3)COOCH_(3)is attributed to locally modified microenvironments that facilitate the esterification reaction when acetate is present in solution.These findings highlight the role of scaffold engineering in improving photocathode performance and electrolyte tuning in steering product selectivity toward scarcely explored,added-value compounds such as methyl acetate.展开更多
基金financially supported by the National Natural Science Foundation of China (22472199)Chinese Universities Scientific Fund (15055009)Central University Guided Funds for Building World-Class Universities (Disciplines) and Advancing Characteristic Development
文摘Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the intrinsic activity of Ni and Co catalytic centers.However,the dynamic evolution and atomic-scale synergy between these centers remain elusive.Herein,we fabricated NiCo_(2)O_(4)nanosheets supported on nickel foam,where Ni preferentially occupies tetrahedral sites to regulate the electronic configuration of octahedral Co.Experimental and theoretical results demonstrate that the incorporation of tetrahedral Ni induces low-to-intermediate spin transition in octahedral Co,thereby optimizing eg orbital occupancy and stabilizing active sites.This spin-state engineering establishes Ni-Co synergistic catalytic centers for the selective oxidation of glucose to formate(FA).At higher potential(≥1.4 V vs.RHE),octahedral Co undergoes reconstruction into excessive active CoOOH and CoO_(2)species,resulting in glucose overoxidation to CO_(2)and intensified competitive oxygen evolution.In contrast,at lower potentials(<1.4 V vs.RHE),tetrahedral Ni facilitates electron delocalization across the Ni–O–Co lattice,thereby stabilizing octahedral Co for glucose adsorption and oxidation.Subsequently,a coupled electrocatalytic system was constructed,achieving 80.7%FA yield with 91.3%Faradaic efficiency(FE)at NiCo_(2)O_(4)anode and H2 evolution rate of 696μmol h^(−1)with 99.9%FE at Pt cathode for 2 h under 1.35 V vs.RHE.This work provides a deep insight into spin-state regulation of the catalytic center,offering valuable guidance for rational catalyst design.
基金the financial support from the National Natural Science Foundation of China(52172110,52472231,52311530113)Shanghai"Science and Technology Innovation Action Plan"intergovernmental international science and technology cooperation project(23520710600)+1 种基金Science and Technology Commission of Shanghai Municipality(22DZ1205600)the Central Guidance on Science and Technology Development Fund of Zhejiang Province(2024ZY01011)。
文摘Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.
基金supported by the National Natural Science Foundation of China(Nos.52161145409,21976116)SAFEA of China("Belt and Road"Innovative Talent Exchange Foreign Expert Project No.2023041004L)+1 种基金(High-end Foreign Expert Project No.G2023041021L)Alexander-von-Humboldt Foundation of Germany(Group-Linkage Program).
文摘Photoreforming poly(lactic acid)(PLA)plastics into pyruvic acid(PA)coupled with hydrogen evolution is of great significance for sustainable development.However,a significant challenge lies inα-OH bond cleaving of lactic acid(LA).Herein,CdS/Bi_(4)Ti_(3)O_(12)composite is fabricated,bridged by Bi−S bonds,through in-situ growth of CdS nanoparticles on Bi_(4)Ti_(3)O_(12)nanoflowers for the successive removal of hydrogen fromα-C in LA.In-situ X-ray photoelectron spectroscopy confirms the S-scheme carriers transfer route and interfacial Bi−S bond in CdS/Bi_(4)Ti_(3)O_(12).Consequently,the photo-electrons and holes with extended lifetimes and strong redox potential accumulate in the CdS conduction band and Bi_(4)Ti_(3)O_(12)valence band,respectively,as evidenced by in-situ electron spin resonance and time-resolved photoluminescence.This facilitates the generation of·OH radicals,which further participate in the successive dehydrogenation reaction of LA.Consequently,the photoreforming efficiencies of converting PLA into PA and H_(2)by CdS/Bi_(4)Ti_(3)O_(12)are 1.7 and 3.16 mmol g^(-1)h^(-1),which are respectively 2.8 and 22 times higher than that by pristine Bi_(4)Ti_(3)O_(12).The present work provides a new approach for designing S-scheme to achieve hydrogen production and value-added conversion of plastics.
基金financially supported by the Natural Science Foundation of Shandong Province (No.ZR2022QE076)the National Natural Science Foundation of China (No.52202092)the Science and Technology Support Plan for Youth Innovation of Colleges and Universities of Shandong Province of China (No.2023KJ104)。
文摘Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demonstrated substantial potential for the advancement of electrocatalytic CO_(2) reduction to formate.However,due to the weak bonding of protons(H^(*)) of Bi,the available protonate of CO_(2) on Bi is insufficient,which limits the formation of OCHO^(*).Prediction by theoretical calculation,chlorine doping can effectively promote the dissociation of H_(2)O and thus achieve effective proton supply.We prepare chlorine-doped Bi(Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO_(2) .An obvious improvement of faradaic efficiency(FE) of formate(96.7% at-0.95 V vs.RHE) can be achieved on Cl-Bi,higher than that of Bi(89.4%).Meanwhile,Cl-Bi has the highest formate production rate of 275 μmol h^(-1)cm^(-2)at-0.95 V vs.RHE,which is 1.2 times higher than that of Bi(224 μmol h^(-1)cm^(-2)).In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H_(2)O and supply sufficient protons to promote the protonation of CO_(2) to OCHO^(*),which is consistent with theoretical calculation.The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.
基金funding support from the INCT-DATREM:FAPESP:2014/50945-4,CNPq|:465571/2014-0,and Capes:88887136426/2017/10Programa Nacional de Investigación Científica y Estudios Avanzados(PROCIENCIA)with grant number 237-2015-FONDECYT+2 种基金We thank the support from Vicerrectorado de Investigación(VRI-UNI).Serrapilheira Institute[Grant number Serra–2211-41925]São Paulo Research Foundation,FAPESP[Grant number#2023/10027-5][Grant numbers#406156/2022-0,180111/2023-0]。
文摘The use of Cu_(2)O-based photocathodes has demonstrated the promising activity of these earth-abundant materials for the photoelectrochemical CO_(2)reduction reaction(CO_(2)RR),particularly in producing methanol.However,their application in long-term devices is hindered by severe photocorrosion.To address this limitation,photocathode designs incorporating Schottky barriers,heterojunctions,and scaffolding layers have been explored.In this work,a CuBi_(2)O_(4)/CuO thin layer was employed as a scaffold to support Cu_(2)O films with either seeded or grown morphologies for enhanced photoelectrochemical CO_(2)RR.Photoelectrochemical testing in CO_(2)-saturated electrolyte revealed that 0.55 V vs.reversible hydrogen electrode(RHE)yielded the highest activity and stability for methanol(CH_(3)OH)production,outperforming more negative potentials.Furthermore,the present work highlighted that electrolyte engineering can be used to promote the generation of alternative products such as methyl acetate(CH_(3)COOCH_(3)).The presence of CuBi_(2)O_(4)/CuO scaffold was critical for allowing this pathway,providing both enhanced stability and improved charge transfer on the Cu_(2)O surface.The generation of CH_(3)COOCH_(3)is attributed to locally modified microenvironments that facilitate the esterification reaction when acetate is present in solution.These findings highlight the role of scaffold engineering in improving photocathode performance and electrolyte tuning in steering product selectivity toward scarcely explored,added-value compounds such as methyl acetate.
