Antagonism effect of residual S triggers the dual-path mechanism for water oxidation  

作　　者：Li Liu Jinming Cao Siqi Hu Tinghui Liu Can Xu Wensheng Fu Xinguo Ma Xiaohui Yang 

机构地区：[1]Chongqing Key Laboratory of Green Catalytic Materials and Technology,College of Chemistry,Chongqing Normal University,Chongqing 401331,China [2]School of Science,Hubei University of Technology,Wuhan 430068,Hubei,China [3]Chongqing Institute of Green and Intelligent Technology,Chinese Academy of Sciences,Chongqing 400714,China

出　　处：《Journal of Energy Chemistry》2024年第6期568-579,I0014,共13页能源化学（英文版）

基　　金：supported by the Science and Technology Research Program of Chongqing Municipal Education Commission(KJQN202200550);the Natural Science Foundation Joint Fund for Innovation and Development of Chongqing Municipal Education Commission(CSTB2022NSCQ-LZX0077);the National Natural Science Foundation of China(No.52100065);the Science and Technology Research Program of Natural Science Foundation of Chongqing(cstc2021ycjh-bgzxm0037);the Science and Technology Research Program of Chongqing Municipal Education Commission(KJZD-M202200503);the Chongqing Innovation Research Group Project(No.CXQT21015);the Doctor Start/Talent Introduction Program of Chongqing Normal University(No.02060404/2020009000321)。

摘　　要：Transition metal chalcogenides(TMCs)are recognized as pre-catalysts,and their(oxy)hydroxides derived from electrochemical reconstruction are the active species in the water oxidation.However,understanding the role of the residual chalcogen in the reconstructed layer is lacking in detail,and the corresponding catalytic mechanism remains controversial.Here,taking Cu_(1-x)Co_(x)S as a platform,we explore the regulating effect and existence form of the residual S doped into the reconstructive layer for oxygen evolution reaction(OER),where a dual-path OER mechanism is proposed.First-principles calculations and operando~(18)O isotopic labeling experiments jointly reveal that the residual S in the reconstructive layer of Cu_(1-x)Co_(x)S can wisely balance the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM)by activating lattice oxygen and optimizing the adsorption/desorption behaviors at metal active sites,rather than change the reaction mechanism from AEM to LOM.Following such a dual-path OER mechanism,Cu_(0.4)Co_(0.6)S-derived Cu_(0.4)Co_(0.6)OSH not only overcomes the restriction of linear scaling relationship in AEM,but also avoids the structural collapse caused by lattice oxygen migration in LOM,so as to greatly reduce the OER potential and improved stability.

关 键 词：Electrochemical reconstruction Adsorbate evolution mechanism Lattice oxygen oxidation mechanism Oxygen evolution reaction Residual sulfur 

分 类 号：TQ031[化学工程]