Intensifying uneven charge distribution via geometric distortion engineering in atomically dispersed M-N_(x)/S sites for efficient oxygen electroreduction

作     者：Zhuting Zhang Simin Yang Rui Jiang Tian Sheng Chunfeng Shi Yueguang Chen Leyu Wang Zhuting Zhang;Simin Yang;Rui Jiang;Tian Sheng;Chunfeng Shi;Yueguang Chen;Leyu Wang

作者机构：State Key Laboratory of Chemical Resource EngineeringCollege of ChemistryBeijing University of Chemical TechnologyBeijing 100029China College of Chemistry and Materials ScienceAnhui Normal UniversityWuhu 214000China Research Institute of Petroleum ProcessingSINOPECBeijing 100083China 

出 版 物：《Nano Research》 (纳米研究（英文版）)

年 卷 期：2022年第15卷第10期

页      面：8928-8935页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China(Nos.21701005 and 21903001) the Fundamental Research Funds for the Central Universities(No.XK2020-02) China Petroleum&Chemical Corporation(SINOPEC)(No.421028) 

主　　题：single-atomic sites geometric distortion engineering seed encapsulation-decomposition strategy charge distribution oxygen reduction reaction 

摘      要：Fine regulation of geometric structures has great promise to acquire specific electronic structures and improve the catalytic performance of single-atom catalysts,yet it remains a ***,a novel seed encapsulation–decomposition strategy is proposed for the geometric distortion engineering and thermal atomization of a series of Cu-N_(x)/S moieties anchored on carbon *** pyrolysis,seeds(Cu^(2+),CuO,or Cu_(7)S_(4) nanoparticles)confined in metal organic framework can accommodate single Cu atoms with Cu–N or Cu–S coordination bonds and simultaneously induce C–S or C–N bond cleavage in the second coordination shell of Cu centers,which are identified to manipulate the distortion degree of Cu-N_(x)/S *** severely distorted Cu-N3S molecular structure endows the resultant catalyst with excellent oxygen reduction reaction activity(E_(1/2)=0.885 V)and zinc-air battery performance(peak power density of 210 mW·cm^(−2)),outperforming the asymmetrical and symmetrical Cu-N4 structures.A combined experimental and theoretical study reveals that the geometric distortion of Cu-N_(x)/S moieties creates uneven charge distribution by a unique topological correlation effect,which increases the metal charge and shifts the d-band center toward the Fermi level,thereby optimizing the inter-mediate adsorption energy.