Manipulating d-d orbital hybridization induced by Mo-doped Co_(9)S_(8) nanorod arrays for high-efficiency water electrolysis  

作　　者：Xue Zhou Jing Li Guangyao Zhou Weiran Huang Yucan Zhang Jun Yang Huan Pang Mingyi Zhang Dongmei Sun Yawen Tang Lin Xu 

机构地区：[1]Jiangsu Key Laboratory of New Power Batteries,Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials,School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,Jiangsu,China [2]'College of Science,Jinling Institute of Technology,Nanjing 211169,Jiangsu,China [3]State Key Laboratory of Multiphase Complex Systems,Institute of Process Engineering,Chinese Academy of Sciences,Beijing 100190,China [4]Nanjing IPE Institute of Green Manufacturing Industry,Nanjing 211100,Jiangsu,China [5]School of Chemistry and Chemical Engineering,Yangzhou University,Yangzhou 225009,Jiangsu,China [6]Key Laboratory for Photonic and Electronic Bandgap Materials,Ministry of Education,School of Physics and Electronic Engineering,Harbin Normal University,Harbin 150025,Heilongjiang,China

出　　处：《Journal of Energy Chemistry》2024年第6期592-600,I0015,共10页能源化学（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(21972068,22072067,22232004);the High-level Talents Project of Jinling Institute of Technology(jit-b-202164)。

摘　　要：Precisely refining the electronic structure of electrocatalysts represents a powerful approach to further optimize the electrocatalytic performance.Herein,we demonstrate an ingenious d-d orbital hybridization concept to construct Mo-doped Co_(9)S_(8) nanorod arrays aligned on carbon cloth(CC)substrate(abbreviated as Mo-Co_(9)S_(8)@CC hereafter)as a high-efficiency bifunctional electrocatalyst toward water electrolysis.It has experimentally and theoretically validated that the 4d-3d orbital coupling between Mo dopant and Co site can effectively optimize the H_(2)O activation energy and lower H^(*)adsorption energy barrier,thereby leading to enhanced hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activities.Thanks to the unique electronic and geometrical advantages,the optimized Mo-Co_(9)S_(8)@CC with appropriate Mo content exhibits outstanding bifunctional performance in alkaline solution,with the overpotentials of 75 and 234 mV for the delivery of a current density of 10 mA cm^(-2),small Tafel slopes of 53.8 and 39.9 mV dec~(-1)and long-term stabilities for at least 32 and 30 h for HER and OER,respectively.More impressively,a water splitting electrolylzer assembled by the self-supported Mo-Co_(9)S_(8)@CC electrode requires a low cell voltage of 1.53 V at 10 mA cm^(-2)and shows excellent stability and splendid reversibility,demonstrating a huge potential for affordable and scalable electrochemical H_(2) production.The innovational orbital hybridization strategy for electronic regulation herein provides an inspirable avenue for developing progressive electrocatalysts toward new energy systems.

关 键 词：d-d orbital hybridization Transition metal sulfides Nanorods arrays Water electrolysis 

分 类 号：TQ116.21[化学工程—无机化工] TB383.1[一般工业技术—材料科学与工程] TQ426