Novel two-dimensional thermoelectric materials have attracted significant attention in the field of thermoelectric due to their low lattice thermal conductivity.A comprehensive understanding of their microscopic struc...Novel two-dimensional thermoelectric materials have attracted significant attention in the field of thermoelectric due to their low lattice thermal conductivity.A comprehensive understanding of their microscopic structures is crucial for driving further the optimization of materials properties and developing novel functional materials.Here,by using in situ scanning tunneling microscopy,we report the atomic layer evolution and surface reconstruction on the cleaved thermoelectric material KCu_(4)Se_(3) for the first time.We clearly revealed each atomic layer,including the naturally cleaved K atomic layer,the intermediate Se^(2-)atomic layer,and the Se^(-)atomic layer that emerges in the thermodynamic-stable state.Departing from the maj ority of studies that predominantly concentrate on macroscopic measurements of the charge transport,our results reveal the coexistence of potassium disorder and complex reconstructed patterns of selenium,which potentially influences charge carrier and lattice dynamics.These results provide direct insight into the surface microstructures and evolution of KCu_(4)Se_(3),and shed useful light on designing functional materials with superior performance.展开更多
Considering their superior theoretical capacity and low voltage plateau,bismuth(Bi)-based materials are being widely explored for application in potassium-ion batteries(PIBs).Unfortunately,pure Bi and Bibased compound...Considering their superior theoretical capacity and low voltage plateau,bismuth(Bi)-based materials are being widely explored for application in potassium-ion batteries(PIBs).Unfortunately,pure Bi and Bibased compounds suffer from severe electrochemical polarization,agglomeration,and dramatic volume fluctuations.To develop an advanced bismuth-based anode material with high reactivity and durability,in this work,the pyrolysis of Bi-based metal-organic frameworks and in-situ selenization techniques have been successfully used to produce a Bi-based composite with high capacity and unique structure,in which Bi/Bi_(3)Se_(4)nanoparticles are encapsulated in carbon nanorods(Bi/Bi_(3)Se_(4)@CNR).Applied as the anode material of PIBs,the Bi/Bi_(3)Se_(4)@CNR displays fast potassium storage capability with 307.5 m A h g^(-1)at 20 A g^(-1)and durable cycle performance of 2000 cycles at 5 A g^(-1).Notably,the Bi/Bi_(3)Se_(4)@CNR also showed long cycle stability over 1600 cycles when working in a full cell system with potassium vanadate as the cathode material,which further demonstrates its promising potential in the field of PIBs.Additionally,the dual potassium storage mechanism of the Bi/Bi_(3)Se_(4)@CNR based on conversion and alloying reaction has also been revealed by in-situ X-ray diffraction.展开更多
Paired electrolysis in anion-exchange membrane(AEM)electrolyzers toward the cathodic nitrate reduction reaction(NO_(3)RR)and anodic benzylamine oxidation reaction(BOR)could generate high value-added N-containing compo...Paired electrolysis in anion-exchange membrane(AEM)electrolyzers toward the cathodic nitrate reduction reaction(NO_(3)RR)and anodic benzylamine oxidation reaction(BOR)could generate high value-added N-containing compounds simultaneously.The key challenge is to develop bifunctional electrocatalysts with a wide potential window,which can achieve highly efficient conversion of anode and cathode reactants.Herein,Ni_(3)Se_(4)with Se vacancies was prepared and employed as the cathode and anode of AEM electrolyzers for NO_(3)RR and BOR.^(15)N isotope-labeling online differential electrochemical mass spectrometry(DEMS)proved that ammonium was reduced from nitrates and revealed the reaction pathway of NO_(3)RR.The density functional theory calculation clarified that Se vacancies regulate d-band centers,and then further modulate the adsorption energy of adsorbed hydrogen,NO_(3)^(-)and intermediates on the Ni_(3)Se_(4)-60s surface in NO_(3)RR,so as to optimize the hydrogenation of NO_(3)^(-)into ammonia.Moreover,during the BOR,the Se vacancy can promote the adsorption of OH^(-),which is easier to form the active species of Ni OOH.The technical and economic evaluation exhibited that the cost of paired electrolysis is 1.21 times lower and the profit is 1.42 times higher than that of the unpaired electrolysis,which shows the economic attraction of paired electrolysis.This work delivers the guidance for the design of efficient catalysts for paired electrolysis in AEM electrolyzer toward the sustainable synthesis of value-added chemicals.展开更多
基金Project supported by the National Natural Science Foundation of China (Grant Nos.12374196,92165201,11634011,and 22109153)the Innovation Program for Quantum Science and Technology (Grant No.2021ZD0302800)+4 种基金the CAS Project for Young Scientists in Basic Research (Grant No.YSBR-046)the Fundamental Research Funds for the Central Universities (Grant Nos.WK3510000006 and WK3430000003)the Fund of Anhui Initiative in Quantum Information Technologies (Grant No.AHY170000)the University Synergy Innovation Program of Anhui Province,China (Grant No.GXXT-2022-008)the National Synchrotron Radiation Laboratory Joint Funds of University of Science and Technology of China (Grant No.KY2060000241)。
文摘Novel two-dimensional thermoelectric materials have attracted significant attention in the field of thermoelectric due to their low lattice thermal conductivity.A comprehensive understanding of their microscopic structures is crucial for driving further the optimization of materials properties and developing novel functional materials.Here,by using in situ scanning tunneling microscopy,we report the atomic layer evolution and surface reconstruction on the cleaved thermoelectric material KCu_(4)Se_(3) for the first time.We clearly revealed each atomic layer,including the naturally cleaved K atomic layer,the intermediate Se^(2-)atomic layer,and the Se^(-)atomic layer that emerges in the thermodynamic-stable state.Departing from the maj ority of studies that predominantly concentrate on macroscopic measurements of the charge transport,our results reveal the coexistence of potassium disorder and complex reconstructed patterns of selenium,which potentially influences charge carrier and lattice dynamics.These results provide direct insight into the surface microstructures and evolution of KCu_(4)Se_(3),and shed useful light on designing functional materials with superior performance.
基金financially supported by the National Natural Science Foundation of China (22209057)the Guangdong Basic and Applied Basic Research Foundation (2021A1515010362)+1 种基金the Guangzhou Basic and Applied Basic Research Foundation (202102020995)the Open Fund of Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications (2020B121201005)。
文摘Considering their superior theoretical capacity and low voltage plateau,bismuth(Bi)-based materials are being widely explored for application in potassium-ion batteries(PIBs).Unfortunately,pure Bi and Bibased compounds suffer from severe electrochemical polarization,agglomeration,and dramatic volume fluctuations.To develop an advanced bismuth-based anode material with high reactivity and durability,in this work,the pyrolysis of Bi-based metal-organic frameworks and in-situ selenization techniques have been successfully used to produce a Bi-based composite with high capacity and unique structure,in which Bi/Bi_(3)Se_(4)nanoparticles are encapsulated in carbon nanorods(Bi/Bi_(3)Se_(4)@CNR).Applied as the anode material of PIBs,the Bi/Bi_(3)Se_(4)@CNR displays fast potassium storage capability with 307.5 m A h g^(-1)at 20 A g^(-1)and durable cycle performance of 2000 cycles at 5 A g^(-1).Notably,the Bi/Bi_(3)Se_(4)@CNR also showed long cycle stability over 1600 cycles when working in a full cell system with potassium vanadate as the cathode material,which further demonstrates its promising potential in the field of PIBs.Additionally,the dual potassium storage mechanism of the Bi/Bi_(3)Se_(4)@CNR based on conversion and alloying reaction has also been revealed by in-situ X-ray diffraction.
基金supported by the National Natural Science Foundation of China(22162025,22168040)Regional Innovation Capability Leading Program of Shaanxi(2022QFY07-03,2022QFY07-06)Shaanxi Province Training Program of Innovation and Entrepreneurship for Undergraduates(S202210719108,S202110719107,S202010719121)
文摘Paired electrolysis in anion-exchange membrane(AEM)electrolyzers toward the cathodic nitrate reduction reaction(NO_(3)RR)and anodic benzylamine oxidation reaction(BOR)could generate high value-added N-containing compounds simultaneously.The key challenge is to develop bifunctional electrocatalysts with a wide potential window,which can achieve highly efficient conversion of anode and cathode reactants.Herein,Ni_(3)Se_(4)with Se vacancies was prepared and employed as the cathode and anode of AEM electrolyzers for NO_(3)RR and BOR.^(15)N isotope-labeling online differential electrochemical mass spectrometry(DEMS)proved that ammonium was reduced from nitrates and revealed the reaction pathway of NO_(3)RR.The density functional theory calculation clarified that Se vacancies regulate d-band centers,and then further modulate the adsorption energy of adsorbed hydrogen,NO_(3)^(-)and intermediates on the Ni_(3)Se_(4)-60s surface in NO_(3)RR,so as to optimize the hydrogenation of NO_(3)^(-)into ammonia.Moreover,during the BOR,the Se vacancy can promote the adsorption of OH^(-),which is easier to form the active species of Ni OOH.The technical and economic evaluation exhibited that the cost of paired electrolysis is 1.21 times lower and the profit is 1.42 times higher than that of the unpaired electrolysis,which shows the economic attraction of paired electrolysis.This work delivers the guidance for the design of efficient catalysts for paired electrolysis in AEM electrolyzer toward the sustainable synthesis of value-added chemicals.
