Rational design of electrochemical sulfide oxidation reaction(SOR)catalysts is a prerequisite to fully recycling hydrogen(H_(2))and elemental sulfur(S0)resources,realizing the bridge between environment and energy fie...Rational design of electrochemical sulfide oxidation reaction(SOR)catalysts is a prerequisite to fully recycling hydrogen(H_(2))and elemental sulfur(S0)resources,realizing the bridge between environment and energy fields,as well as enlightening the optimization of metal‒sulfur battery applications.While transition metal catalysts often suffer from sulfur poisoning,single-atom catalysts(SACs)offer a promising solution,where the precise coordination environment of metal centers becomes a critical determinant of catalytic performance.Herein,for the first time,we develop a Ni single-atom catalyst for SOR with unique Ni-N_(3)O_(1) coordination anchored on hierarchically porous carbon(Ni1@HPC),which demonstrates remarkable advantages over conventional Ni-N_(4) or Ni-O4 configurations,exhibiting a superior SOR activity(0.37 V vs.RHE at 100 mA·cm^(-2))that surpasses reported carbon-based catalysts and is comparable to most metal-based catalysts.In situ Raman and density functional theory(DFT)results reveal that the HPC facilitates rapid product S0 desorption while the Ni-N3O1 coordination enables appropriate reactant sulfide(S^(2-))adsorption,striking a critical balance between activity and stability that other coordination geometries fail to achieve.Additionally,the practical application of coupling hydrogen evolution reaction(HER)and SOR is realized on Ni1@HPC with low power consumption,which is a promising alternative to the traditional overall water splitting(OWS)process.This work not only establishes a structure–activity relationship for single-atom catalysts in SOR but also provides a general strategy for optimizing metal coordination in electrocatalytic systems.展开更多
基金supported by the National Key Technologies R&D Program of China(Nos.2018YFA0209301 and 2018YFA0209303)the National Natural Science Foundation of China(Nos.22272027,U21A20326,U1905214,21425309,21761132002,21961142019,and 21861130353)+1 种基金the Chang Jiang Scholars Program of China(No.T2016147)the 111 Project(No.D16008).
文摘Rational design of electrochemical sulfide oxidation reaction(SOR)catalysts is a prerequisite to fully recycling hydrogen(H_(2))and elemental sulfur(S0)resources,realizing the bridge between environment and energy fields,as well as enlightening the optimization of metal‒sulfur battery applications.While transition metal catalysts often suffer from sulfur poisoning,single-atom catalysts(SACs)offer a promising solution,where the precise coordination environment of metal centers becomes a critical determinant of catalytic performance.Herein,for the first time,we develop a Ni single-atom catalyst for SOR with unique Ni-N_(3)O_(1) coordination anchored on hierarchically porous carbon(Ni1@HPC),which demonstrates remarkable advantages over conventional Ni-N_(4) or Ni-O4 configurations,exhibiting a superior SOR activity(0.37 V vs.RHE at 100 mA·cm^(-2))that surpasses reported carbon-based catalysts and is comparable to most metal-based catalysts.In situ Raman and density functional theory(DFT)results reveal that the HPC facilitates rapid product S0 desorption while the Ni-N3O1 coordination enables appropriate reactant sulfide(S^(2-))adsorption,striking a critical balance between activity and stability that other coordination geometries fail to achieve.Additionally,the practical application of coupling hydrogen evolution reaction(HER)and SOR is realized on Ni1@HPC with low power consumption,which is a promising alternative to the traditional overall water splitting(OWS)process.This work not only establishes a structure–activity relationship for single-atom catalysts in SOR but also provides a general strategy for optimizing metal coordination in electrocatalytic systems.
