The steps of NO_(3)^(-)adsorption,deoxygenation,nitrogen species hydrogenation and ammonia desorption are vital for electrocatalytic nitrate reduction(NO_(3)^(-)RR)to ammonia,and lowering their Gibbs free energy chan...The steps of NO_(3)^(-)adsorption,deoxygenation,nitrogen species hydrogenation and ammonia desorption are vital for electrocatalytic nitrate reduction(NO_(3)^(-)RR)to ammonia,and lowering their Gibbs free energy change(ΔG)is the essential approach for improving NO_(3)^(-)RR.The copper-based alloys are considered as the outstanding catalysts thanks to the tunable d-band center,reconstruction and synergistic effect of multiple metal atoms in the past decades.Here,we synthesized a single-phase coppernickel alloy by electrodeposition and optimized itsΔG during NO_(3)^(-)RR through tuning the electrodeposition potential to regulate the metal component ratio.The atomic ratio of Ni/Cu in CuNi alloys is gradually increased as the negative shift of deposition potential from-1.0 to-1.2 V versus SCE,thus achieving the fast modulation of intermediate adsorption energy for NO_(3)^(-)RR.According to density functional theory,profited by a strong NO_(3)^(-)adsorption and a weak NH_(3)desorption energy barrier,the optimized CuNi alloy(Cu_(3)Ni_(1)/CF)exhibits an ideal ammonia yield of 364.1μmol cm^(-2)h^(-1)and Faradaic efficiency of 92.25%at-0.23 V versus RHE.Further applying Cu_(3)Ni_(1)/CF as the cathode material,a novel Znnitrate battery exhibits a maximum power density of5.85 mW cm^(-2)with a NH_(3)yield of 92.50μmol cm^(-2)h^(-1)and Faradaic efficiency of 99.15%at 20 mA cm^(-2)for NH_(3)production.This work not only offers a rational design concept with clear guidance for efficient modulation of intermediate adsorption free energy on alloy catalysts prepared by electrodeposition,but also provides the further understanding for efficient developments of NO_(3)^(-)RR and Zn-based batteries.展开更多
Electrochemical CO_(2)/CO reduction(CO_(2)/CORR)driven by renewable electricity offers a sustainable strategy to produce high-value-added products like acetate(CH3COOH).However,the difficulties in regulating CO adsorp...Electrochemical CO_(2)/CO reduction(CO_(2)/CORR)driven by renewable electricity offers a sustainable strategy to produce high-value-added products like acetate(CH3COOH).However,the difficulties in regulating CO adsorption geometries remain a major obstacle to achieving high acetate Faradaic efficiency(FE)at industrially relevant current densities.We rationally reason that the CO replenishment rate must match the high turnover rate at high overpotentials so that the optimal ratio between the two*CO configurations could be maintained to promote the critical C-C coupling for acetate production.To address this dilemma,we designed a Cu-BTA(1H-benzotriazole)nanoisland catalyst through in situ reconstruction,combined with elevated CO pressure to create a confined microenvironment for effective*CO configuration modulation.The designed Cu-BTA catalyst exhibits superior CO-to-acetate selectivity with an 80.8%FE and 180 mg h^(−1)cm^(−2)production rate at−400 mA cm^(−2)under 7 bar CO(1 bar=100 kPa),surpassing most Cu-based catalysts.In situ characterizations and density functional theory(DFT)calculations reveal that elevated CO pressure effectively increases the atop-adsorbed CO/bridge-adsorbed CO(*COatop/*COb)ratio,accelerates the rate-determining step(*CO+*CO to*OCCOH),and promotes the formation of key intermediates such as*CCO and*CH_(2)CO,ultimately boosting CH3COOH production.展开更多
The electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR) represents a promising route for biomass valorization,yet its efficiency is often limited by suboptimal adsorption configurations of reaction intermediat...The electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR) represents a promising route for biomass valorization,yet its efficiency is often limited by suboptimal adsorption configurations of reaction intermediates on conventional catalysts.Herein,we demonstrate that Ce doping effectively modulates both geometric and electronic structures of CuO to achieve exceptional HMFOR performance.The designed Ce-CuO catalyst exhibits remarkable activity and selectivity,achieving nearquantitative FDCA Faradaic efficiency(98.4%) with substantially enhanced production rates(67.0 μmol cm^(-2)h^(-1)) compared to pristine CuO(87.3%,54.0 μmol cm^(-2)h^(-1)),while maintaining over 90% FDCA Faradaic efficiency over 8 cycles.Comprehensive in-situ/ex-situ spectroscopic characterization and theoretical calculations reveal that Ce incorporation induces electron transfer to Cu sites and triggers the coordination geometric restructuring,while simultaneously optimizing the geometric matching between active sites and reaction intermediates.This dual modulation enables key intermediates to adopt thermodynamically favorable adsorption configurations with significantly reduced steric hindrance,thereby lowering the energy barrier of the rate-determining step from 0.99 to 0.46 eV.This work establishes geometric configuration engineering through rational dopant incorporation as a crucial design strategy beyond conventional electronic structure modulation for advanced electrocatalysts in biomass conversion and other complex electrochemical transformations.展开更多
基金financially supported by the National Natural Science Foundation of China(No.U22A20253)High-level Talent Doctoral Scientific Research Foundation of Zhoukou Normal University(No.ZKNUC2023027)Young and Middle-Aged Backbone Teachers of Zhoukou Normal University
文摘The steps of NO_(3)^(-)adsorption,deoxygenation,nitrogen species hydrogenation and ammonia desorption are vital for electrocatalytic nitrate reduction(NO_(3)^(-)RR)to ammonia,and lowering their Gibbs free energy change(ΔG)is the essential approach for improving NO_(3)^(-)RR.The copper-based alloys are considered as the outstanding catalysts thanks to the tunable d-band center,reconstruction and synergistic effect of multiple metal atoms in the past decades.Here,we synthesized a single-phase coppernickel alloy by electrodeposition and optimized itsΔG during NO_(3)^(-)RR through tuning the electrodeposition potential to regulate the metal component ratio.The atomic ratio of Ni/Cu in CuNi alloys is gradually increased as the negative shift of deposition potential from-1.0 to-1.2 V versus SCE,thus achieving the fast modulation of intermediate adsorption energy for NO_(3)^(-)RR.According to density functional theory,profited by a strong NO_(3)^(-)adsorption and a weak NH_(3)desorption energy barrier,the optimized CuNi alloy(Cu_(3)Ni_(1)/CF)exhibits an ideal ammonia yield of 364.1μmol cm^(-2)h^(-1)and Faradaic efficiency of 92.25%at-0.23 V versus RHE.Further applying Cu_(3)Ni_(1)/CF as the cathode material,a novel Znnitrate battery exhibits a maximum power density of5.85 mW cm^(-2)with a NH_(3)yield of 92.50μmol cm^(-2)h^(-1)and Faradaic efficiency of 99.15%at 20 mA cm^(-2)for NH_(3)production.This work not only offers a rational design concept with clear guidance for efficient modulation of intermediate adsorption free energy on alloy catalysts prepared by electrodeposition,but also provides the further understanding for efficient developments of NO_(3)^(-)RR and Zn-based batteries.
基金supported by the National Natural Science Foundation of China(22373080,22402163,22078274,22475075,and 52376187)the Natural Science Foundation of Fujian Province of China(2024J08008 and 2022J05009)+3 种基金Fujian Provincial Science and Technology Program for International Cooperation(2025I0002)the Natural Science Foundation of Xiamen,China(3502Z202472001)the Fundamental Research Funds for the Central Universities,China(20720240054)the Nan-qiang Youth Scholar Program of Xiamen University and Xiaomi Young Talents Program/Xiaomi Foundation,and the National Key Research and Development Program,China(2024YFE0211300).
文摘Electrochemical CO_(2)/CO reduction(CO_(2)/CORR)driven by renewable electricity offers a sustainable strategy to produce high-value-added products like acetate(CH3COOH).However,the difficulties in regulating CO adsorption geometries remain a major obstacle to achieving high acetate Faradaic efficiency(FE)at industrially relevant current densities.We rationally reason that the CO replenishment rate must match the high turnover rate at high overpotentials so that the optimal ratio between the two*CO configurations could be maintained to promote the critical C-C coupling for acetate production.To address this dilemma,we designed a Cu-BTA(1H-benzotriazole)nanoisland catalyst through in situ reconstruction,combined with elevated CO pressure to create a confined microenvironment for effective*CO configuration modulation.The designed Cu-BTA catalyst exhibits superior CO-to-acetate selectivity with an 80.8%FE and 180 mg h^(−1)cm^(−2)production rate at−400 mA cm^(−2)under 7 bar CO(1 bar=100 kPa),surpassing most Cu-based catalysts.In situ characterizations and density functional theory(DFT)calculations reveal that elevated CO pressure effectively increases the atop-adsorbed CO/bridge-adsorbed CO(*COatop/*COb)ratio,accelerates the rate-determining step(*CO+*CO to*OCCOH),and promotes the formation of key intermediates such as*CCO and*CH_(2)CO,ultimately boosting CH3COOH production.
基金supported by the National Natural Science Foundation of China (22379071)the Jiangsu Provincial Major Science and Technology Program (BG2024011)+2 种基金the support from the Nanjing “U35” Talent Foundation-Strengthening Projectthe National and Local Joint Engineering Research Center of Biomedical Functional Materialsthe Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘The electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR) represents a promising route for biomass valorization,yet its efficiency is often limited by suboptimal adsorption configurations of reaction intermediates on conventional catalysts.Herein,we demonstrate that Ce doping effectively modulates both geometric and electronic structures of CuO to achieve exceptional HMFOR performance.The designed Ce-CuO catalyst exhibits remarkable activity and selectivity,achieving nearquantitative FDCA Faradaic efficiency(98.4%) with substantially enhanced production rates(67.0 μmol cm^(-2)h^(-1)) compared to pristine CuO(87.3%,54.0 μmol cm^(-2)h^(-1)),while maintaining over 90% FDCA Faradaic efficiency over 8 cycles.Comprehensive in-situ/ex-situ spectroscopic characterization and theoretical calculations reveal that Ce incorporation induces electron transfer to Cu sites and triggers the coordination geometric restructuring,while simultaneously optimizing the geometric matching between active sites and reaction intermediates.This dual modulation enables key intermediates to adopt thermodynamically favorable adsorption configurations with significantly reduced steric hindrance,thereby lowering the energy barrier of the rate-determining step from 0.99 to 0.46 eV.This work establishes geometric configuration engineering through rational dopant incorporation as a crucial design strategy beyond conventional electronic structure modulation for advanced electrocatalysts in biomass conversion and other complex electrochemical transformations.
