Single-atom sites regulation by the second-shell doping for efficient electrochemical CO_(2)reduction  

作　　者：Qian-Qian Tang Li-Fang Feng Zhi-Peng Li Shi-Hao Wu Long-Shuai Zhang Qing Sun Mei-Feng Wu Jian-Ping Zou 

机构地区：[1]Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle,Nanchang Hangkong University,Nanchang 330063,China [2]National-Local Joint Engineering Research Center of Heavy Metals Pollutants Control and Resource Utilization,Nanchang Hangkong University,Nanchang 330063,China

出　　处：《Chinese Chemical Letters》2024年第9期360-363,共4页中国化学快报（英文版）

基　　金：financial support of the National Natural Science Foundation of China(Nos.52100186,52170082,51938007 and 52063024);the Jiangxi Provincial Natural Science Foundation(Nos.20225BCJ23003 and 20212ACB203008)。

摘　　要：Nitrogen-doped carbon loaded single-atom catalysts(SACs)are promising candidates for electrocatalytic conversion of CO_(2)into high-valuable chemicals,and the modification of catalysts by heteroatom-doping strategy is an effective approach to enhance the CO_(2)reduction performance.However,the large difference exists in atomic radius between nitrogen atoms and the doped heteroatoms may lead to the poor stability of active sites.In this study,we have synthesized a Ni single atom catalyst with S doping at the secondshell on the ultrathin carbon nanosheets support(Ni-N_(4)-SC)by solid-phase pyrolysis.The S atom in the second-shell contributes to the higher efficiency of CO_(2)conversion at lower potentials while the Ni-N_(4)-SC can be more stable.The experimental results and theoretical calculations indicate that the S atom in second-shell breaks the uniform charge distribution and reduces the free energy of hydrogenation,which can increase the adsorption of CO_(2),accelerate charge transfer,and reduce the reaction energy barrier.This work reveals the close relationship between the second-shell and the electrocatalytic activity of single atom sites,which also provides a new perspective to design efficient single atom catalysts.

关 键 词：Single-atom catalyst Heteroatom-doping Second shell CO_(2)electroreduction Electronic structure regulation 

分 类 号：O643.36[理学—物理化学] X701[理学—化学]