Identification of the highly active Zn-N_(4) sites with pyrrole/pyridine-N synergistic coordination by dz^(2)+s-band center for electrocatalytic H_(2)O_(2) production  

作　　者：Rui Chen Wei Liu Zhiyuan Sang Jingjing Jia Zhenxin Li Jiahuan Nie Qiao Jiang Zixian Mao Baitong Guo Qiuying Wang Feng Hou Lichang Yin De'an Yang Ji Liang 

机构地区：[1]Key Laboratory of Advanced Ceramics and Machining Technology of Ministry of Education School of Materials Science and Engineering,Tianjin University,Tianjin 300072,China [2]Shenyang National Laboratory for Materials Science,Institute of Metal Research,Chinese Academy of Science,Shenyang 110016,Liaoning,China

出　　处：《Journal of Energy Chemistry》2024年第11期105-113,共9页能源化学（英文版）

基　　金：National Natural Science Foundation of China(No.22379111 and 22179093)。

摘　　要：Single metal atoms anchored on nitrogen-doped carbon materials(M-N_(4))have been identified as effective active sites for catalyzing the two-electron oxygen reduction reaction(2e-ORR).However,the relationship between the local atomic/electronic environments of the M-N_(4) sites(metal atoms coordinated with different types of N species)and their catalytic activity for 2e-ORR has rarely been elaborated clearly,which imposes significant ambiguity for the rational design of catalysts.Herein,guided by the comprehensive density-functional theory calculations and predictions,a series of Zn-N_(4) single-atom catalysts(SACs)are designed with pyrrole/pyridine-N(N_(Po)/N_(Pd))synergistic coordination and prepared by controlling the pyrolysis temperature(600,700,and 800℃),Among them,the dominated Zn-N_(4) configurations with rationally combined N_(Po)/N_(Pd)coordination show~*OOH adsorption strength close to the optimal value,much superior to those with mono N species.Thus,the as-prepared catalyst exhibits a high H_(2)O_(2) selectivity of over 90%both in neutral and alkaline environments,with a superb H_(2)O_(2) yield of up to 33.63 mol g^(-1)h^(-1)in an alkaline with flow cell.More importantly,a new descriptor,dz^(2)+s band center,has been proposed,which is especially feasible for predicting the activity for metal types with fully occupied s and d orbitals.This work thus presents clear guidance for the rational design of highly active SACs toward ORR and provides a complement to the d-band theory for more accurately predicting the catalytic activity of the materials.

关 键 词：Zinc single-atom catalysts Hydrogen peroxide Local coordination environments d+s-Band modulation 

分 类 号：TQ426[化学工程] TQ123.6