Single-atomic transition metal-nitrogen codoped carbon(M-N-C)are efficient substitute catalysts for noble metals to catalyze the electrochemical CO_(2) reduction reaction(CO_(2)RR).However,the uncontrolled aggregation...Single-atomic transition metal-nitrogen codoped carbon(M-N-C)are efficient substitute catalysts for noble metals to catalyze the electrochemical CO_(2) reduction reaction(CO_(2)RR).However,the uncontrolled aggregations of metal and serious loss of nitrogen species constituting the M-N_(x) active sites are frequently observed in the commonly used pyrolysis procedure.Herein,single-atomic nickel(Ni)-based sheet-like electrocatalysts with abundant Ni-N_(4) active sites were created by using a novel ammonium chloride(NH_(4)Cl)-assited pyrolysis method.Spherical aberration correction electron microscopy and X-ray absorption fine structure analysis clearly revealed that Ni species are atomically dispersed and anchored by N in Ni-N_(4) structure.The addition of NH_(4)Cl optimized the mesopore size to 7-10 nm and increased the concentrations of pyridinic N(3.54 wt%)and Ni-N_(4)(3.33 wt%)species.The synergistic catalytic effect derived from Ni-N_(4) active sites and pyridinic N species achieved an outstanding CO_(2) RR performance,presenting a high CO Faradaic efficiency(FE_(CO))up to 98% and a large CO partial current density of 8.5 mA cm^(-2) at a low potential of-0.62 V vs.RHE.Particularly,the FE_(CO) maintains above 80% within a large potential range from -0.43 to -0.73 V vs.RHE.This work provides a practical and feasible approach to building highly active single-atomic catalysts for CO_(2) conversion systems.展开更多
The environment benignity and battery cost are major concerns for grid-scale energy storage applications.The emerging dendrite-free Fe-ion aqueous batteries are promising due to the rich natural abundance,low cost and...The environment benignity and battery cost are major concerns for grid-scale energy storage applications.The emerging dendrite-free Fe-ion aqueous batteries are promising due to the rich natural abundance,low cost and non-toxicity for Fe resources.However,serious passivation reactions on Fe anodes and poor long-term cyclability for matched cathodes still stand in the way for their practical usage.To settle above constraints,we herein use NH_(4)Cl as the electrolyte regulator to elevate the reaction kinetics of passivated Fe anodes,and also propose a special cathode-free design to prolong the cells lifetime over 1,000 cycles.The added NH_(4)Cl can erode/break inert passivation layers and strengthen the ion conductivity of electrolytes,facilitating the reversible Fe plating/stripping and Fe^(2+)shuttling.The highly puffed nano carbon foams function as current collectors and actives anchoring hosts,enabling expedite Fe^(2+)adsorption/desorption,FeII/FeIII redox conversions and FeIII deposition.The configured rocking-chair Fe-ion cells have good environmental benignity and decent energy-storage behaviors,including high reactivity/reversibility,outstanding cyclic stability and far enhanced operation longevity.Such economical,long-cyclic and green cathode-free Fe-ion batteries may hold great potential in near-future energy-storage power stations.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.21571159 and U1704256)the Natural Science Foundation of Henan Province,China(No.212300410299)the Doctoral Research Fund of Zhengzhou University of Light Industry(No.2018BSJJ024).
文摘Single-atomic transition metal-nitrogen codoped carbon(M-N-C)are efficient substitute catalysts for noble metals to catalyze the electrochemical CO_(2) reduction reaction(CO_(2)RR).However,the uncontrolled aggregations of metal and serious loss of nitrogen species constituting the M-N_(x) active sites are frequently observed in the commonly used pyrolysis procedure.Herein,single-atomic nickel(Ni)-based sheet-like electrocatalysts with abundant Ni-N_(4) active sites were created by using a novel ammonium chloride(NH_(4)Cl)-assited pyrolysis method.Spherical aberration correction electron microscopy and X-ray absorption fine structure analysis clearly revealed that Ni species are atomically dispersed and anchored by N in Ni-N_(4) structure.The addition of NH_(4)Cl optimized the mesopore size to 7-10 nm and increased the concentrations of pyridinic N(3.54 wt%)and Ni-N_(4)(3.33 wt%)species.The synergistic catalytic effect derived from Ni-N_(4) active sites and pyridinic N species achieved an outstanding CO_(2) RR performance,presenting a high CO Faradaic efficiency(FE_(CO))up to 98% and a large CO partial current density of 8.5 mA cm^(-2) at a low potential of-0.62 V vs.RHE.Particularly,the FE_(CO) maintains above 80% within a large potential range from -0.43 to -0.73 V vs.RHE.This work provides a practical and feasible approach to building highly active single-atomic catalysts for CO_(2) conversion systems.
基金This work is financially supported by the National Natural Science Foundation of China(No.51802269)Fundamental Research Funds for the Central Universities(Nos.XDJK2020C057 and SYJ2021011)Venture&Innovation Support Program for Chongqing overseas returnees(cx2018027).
文摘The environment benignity and battery cost are major concerns for grid-scale energy storage applications.The emerging dendrite-free Fe-ion aqueous batteries are promising due to the rich natural abundance,low cost and non-toxicity for Fe resources.However,serious passivation reactions on Fe anodes and poor long-term cyclability for matched cathodes still stand in the way for their practical usage.To settle above constraints,we herein use NH_(4)Cl as the electrolyte regulator to elevate the reaction kinetics of passivated Fe anodes,and also propose a special cathode-free design to prolong the cells lifetime over 1,000 cycles.The added NH_(4)Cl can erode/break inert passivation layers and strengthen the ion conductivity of electrolytes,facilitating the reversible Fe plating/stripping and Fe^(2+)shuttling.The highly puffed nano carbon foams function as current collectors and actives anchoring hosts,enabling expedite Fe^(2+)adsorption/desorption,FeII/FeIII redox conversions and FeIII deposition.The configured rocking-chair Fe-ion cells have good environmental benignity and decent energy-storage behaviors,including high reactivity/reversibility,outstanding cyclic stability and far enhanced operation longevity.Such economical,long-cyclic and green cathode-free Fe-ion batteries may hold great potential in near-future energy-storage power stations.
