High-entropy alloy(HEA)-based materials are expected to be promising oxygen electrocatalysts due to their exceptional properties.The electronic structure regulation of HEAs plays a pivotal role in enhancing their elct...High-entropy alloy(HEA)-based materials are expected to be promising oxygen electrocatalysts due to their exceptional properties.The electronic structure regulation of HEAs plays a pivotal role in enhancing their elctrocatalytic ability.Herein,PtFeCoNiMn nanoparticles(NPs)with subtle lattice distortions are constructed on metal-organic framework-derived nitrogen-doped carbon by an ultra-rapid Joule heating process.Thanks to the modulated electronic structure and the inherent cocktail effect of HEAs,the as-synthesized PtFeCoNiMn/NC exhibits superior bifunctional electrocatalytic performance with a positive half-wave potential of 0.863 V vs.reversible hydrogen electrode(RHE)for oxygen reduction reaction and a low overpotential of 357 mV at 10 mA·cm^(-2)for oxygen evolution reaction.The assembled quasi-solid-state zinc-air battery using PtFeCoNiMn/NC as air electrode shows a high peak power density of 192.16 mW·cm^(-2),low charge−discharge voltage gap,and excellent durability over 500 cycles at 5 mA·cm^(-2).This work demonstrates an effective route for rational design of bifunctional nanostructured HEA electrocatalysts with favorable electronic structures,and opens up a fascinating directions for energy storage and conversion,and beyond.展开更多
Two-dimensional metal–organic frameworks(2D MOFs),as a new type of 2D materials,have been widely applied in various applications because of their unique structures and exposed active sites.Herein,we reported two low-...Two-dimensional metal–organic frameworks(2D MOFs),as a new type of 2D materials,have been widely applied in various applications because of their unique structures and exposed active sites.Herein,we reported two low-cost 2D MOFs constructed by a raw chemical succinic acid(SA),M-SA(M=Ni or Co),which served as efficient photocatalysts for the reduction of CO_(2)to CO.Taking advantage of the thinness and open metal sites,the ultrathin Ni-SA nanosheets(ca.3.6 nm)exhibited excellent CO production of 6.96(7)mmol·g^(−1)·h^(−1)and CO selectivity of 96.6%.Photoelectrochemical tests and theoretical calculations further confirmed the higher charge transfer efficiency and unsaturated metal sites for promoting photocatalytic performances.More importantly,Ni-SA can also be synthesized in large-scale by an energy-saving method under room temperature,strongly suggesting its promising future and potential for practical applications.展开更多
Cu-based materials are seldom reported as oxygen evolution reaction(OER)electrocatalysts due to their inherent electron orbital configuration,which makes them difficult to adsorb oxygen-intermediates during OER.Reason...Cu-based materials are seldom reported as oxygen evolution reaction(OER)electrocatalysts due to their inherent electron orbital configuration,which makes them difficult to adsorb oxygen-intermediates during OER.Reasonably engineering the hierarchical architectures and the electronic structures can improve the performance of Cu-based OER catalysts,such as constructing multilevel morphology,inducing the porous materials,improving the Cu valence,building heterostructures,doping heteroatoms,etc.In this work,copper-1,3,5-benzenetricarboxylate(HKUST-1)octahedra in-situ grow on the Cu nanorod(NR)-supported N-doped carbon microplates,meanwhile an active layer of Cu(OH)_(2)forms on the surface of the original conductive Cu NRs.The octahedral HKUST-1,serving as a spacer between the microplates,greatly improves the porosity and increases the available active sites,facilitating the mass transport and electron transfer,thus resulting in greatly enhanced OER performance.展开更多
Transition metal-based single-atom catalysts(TM-SACs)are promising alternatives to Au-and Ag-based electrocatalysts for CO production through CO_(2)reduction reaction.However,developing TM-SACs with high activity and ...Transition metal-based single-atom catalysts(TM-SACs)are promising alternatives to Au-and Ag-based electrocatalysts for CO production through CO_(2)reduction reaction.However,developing TM-SACs with high activity and selectivity at low overpotentials is challenging.Herein,a novel Fe-based SAC with Si doping(Fe-N-C-Si)was prepared,which shows a record-high electrocatalytic performance toward the CO_(2)-to-CO conversion with exceptional current density(>350.0 mA cm^(−2))and~100%Faradaic efficiency(FE)at the overpotential of<400 mV,far superior to the reported Fe-based SACs.Further assembling Fe-N-C-Si as the cathode in a rechargeable Zn-CO_(2)battery delivers an outstanding performance with a maximal power density of 2.44 mW cm^(−2)at an output voltage of 0.30 V,as well as high cycling stability and FE(>90%)for CO production.Experimental combined with theoretical analysis unraveled that the nearby Si dopants in the form of Si-C/N bonds modulate the electronic structure of the atomic Fe sites in Fe-N-C-Si to markedly accelerate the key pathway involving^(*)CO intermediate desorption,inhibiting the poisoning of the Fe sites under high CO coverage and thus boosting the CO_(2)RR performance.This work provides an efficient strategy to tune the adsorption/desorption behaviors of intermediates on singleatom sites to improve their electrocatalytic performance.展开更多
基金the financial support of the Shenzhen Key Laboratory of Micro/Nano-Porous Functional Materials(No.ZDSYS20210709112802010)the Shenzhen Science and Technology Innovation Commission(No.GJHZ20220913142610020)+1 种基金Guangdong Grants(No.2021ZT09C064)the National Key Research and Development Program of China(Nos.2022YFA1503900 and 2023YFA1506600)。
文摘High-entropy alloy(HEA)-based materials are expected to be promising oxygen electrocatalysts due to their exceptional properties.The electronic structure regulation of HEAs plays a pivotal role in enhancing their elctrocatalytic ability.Herein,PtFeCoNiMn nanoparticles(NPs)with subtle lattice distortions are constructed on metal-organic framework-derived nitrogen-doped carbon by an ultra-rapid Joule heating process.Thanks to the modulated electronic structure and the inherent cocktail effect of HEAs,the as-synthesized PtFeCoNiMn/NC exhibits superior bifunctional electrocatalytic performance with a positive half-wave potential of 0.863 V vs.reversible hydrogen electrode(RHE)for oxygen reduction reaction and a low overpotential of 357 mV at 10 mA·cm^(-2)for oxygen evolution reaction.The assembled quasi-solid-state zinc-air battery using PtFeCoNiMn/NC as air electrode shows a high peak power density of 192.16 mW·cm^(-2),low charge−discharge voltage gap,and excellent durability over 500 cycles at 5 mA·cm^(-2).This work demonstrates an effective route for rational design of bifunctional nanostructured HEA electrocatalysts with favorable electronic structures,and opens up a fascinating directions for energy storage and conversion,and beyond.
基金Shenzhen Key Laboratory of Micro/Nano-Porous Functional Materials(SKLPM)(No.ZDSYS20210709112802010)China Postdoctoral Science Foundation(No.2022M711483).
文摘Two-dimensional metal–organic frameworks(2D MOFs),as a new type of 2D materials,have been widely applied in various applications because of their unique structures and exposed active sites.Herein,we reported two low-cost 2D MOFs constructed by a raw chemical succinic acid(SA),M-SA(M=Ni or Co),which served as efficient photocatalysts for the reduction of CO_(2)to CO.Taking advantage of the thinness and open metal sites,the ultrathin Ni-SA nanosheets(ca.3.6 nm)exhibited excellent CO production of 6.96(7)mmol·g^(−1)·h^(−1)and CO selectivity of 96.6%.Photoelectrochemical tests and theoretical calculations further confirmed the higher charge transfer efficiency and unsaturated metal sites for promoting photocatalytic performances.More importantly,Ni-SA can also be synthesized in large-scale by an energy-saving method under room temperature,strongly suggesting its promising future and potential for practical applications.
基金the National Natural Science Foundation of China(Nos.U1904215 and 21875207)the Natural Science Foundation of Jiangsu Province(No.BK20200044)the Shenzhen Key Laboratory of Micro/Nano-Porous Functional Materials(SKLPM,No.ZDSYS20210709112802010).
文摘Cu-based materials are seldom reported as oxygen evolution reaction(OER)electrocatalysts due to their inherent electron orbital configuration,which makes them difficult to adsorb oxygen-intermediates during OER.Reasonably engineering the hierarchical architectures and the electronic structures can improve the performance of Cu-based OER catalysts,such as constructing multilevel morphology,inducing the porous materials,improving the Cu valence,building heterostructures,doping heteroatoms,etc.In this work,copper-1,3,5-benzenetricarboxylate(HKUST-1)octahedra in-situ grow on the Cu nanorod(NR)-supported N-doped carbon microplates,meanwhile an active layer of Cu(OH)_(2)forms on the surface of the original conductive Cu NRs.The octahedral HKUST-1,serving as a spacer between the microplates,greatly improves the porosity and increases the available active sites,facilitating the mass transport and electron transfer,thus resulting in greatly enhanced OER performance.
基金This work was financially supported by the National Institute of Advanced Industrial Science and Technology(AIST),Jiangsu University(4023000046)Shenzhen Key Laboratory of Micro/Nano-Porous Functional Materials(SKLPM)(ZDSYS20210709112802010)+2 种基金China Postdoctoral Science Foundation(2022TQ0126 and 2022M721375)Guangdong Grants(2021ZT09C064)the National Key Research and Development Project(2022YFA1503900).
基金This work was supported by the National Key R&D Program of China(2021YFA1500402)the National Natural Science Foundation of China(NSFC)(22105203 and 22175174)+1 种基金the Natural Science Foundation of Fujian Province(2020J01116 and 2021J06033)the China Postdoctoral Science Foundation(2021TQ0332 and 2021M703215).
文摘Transition metal-based single-atom catalysts(TM-SACs)are promising alternatives to Au-and Ag-based electrocatalysts for CO production through CO_(2)reduction reaction.However,developing TM-SACs with high activity and selectivity at low overpotentials is challenging.Herein,a novel Fe-based SAC with Si doping(Fe-N-C-Si)was prepared,which shows a record-high electrocatalytic performance toward the CO_(2)-to-CO conversion with exceptional current density(>350.0 mA cm^(−2))and~100%Faradaic efficiency(FE)at the overpotential of<400 mV,far superior to the reported Fe-based SACs.Further assembling Fe-N-C-Si as the cathode in a rechargeable Zn-CO_(2)battery delivers an outstanding performance with a maximal power density of 2.44 mW cm^(−2)at an output voltage of 0.30 V,as well as high cycling stability and FE(>90%)for CO production.Experimental combined with theoretical analysis unraveled that the nearby Si dopants in the form of Si-C/N bonds modulate the electronic structure of the atomic Fe sites in Fe-N-C-Si to markedly accelerate the key pathway involving^(*)CO intermediate desorption,inhibiting the poisoning of the Fe sites under high CO coverage and thus boosting the CO_(2)RR performance.This work provides an efficient strategy to tune the adsorption/desorption behaviors of intermediates on singleatom sites to improve their electrocatalytic performance.