d-Orbital steered FeN_(4)moiety through N,S dual-site adjustation for zinc-air flow battery

作     者：Chunzhu Bao Mingwei Tong Xueli Li Zhonghua Xiang Chunzhu Bao;Mingwei Tong;Xueli Li;Zhonghua Xiang

作者机构：State Key Laboratory of Organic-Inorganic CompositesBeijing University of Chemical TechnologyBeijing 100029China 

出 版 物：《Journal of Energy Chemistry》 (能源化学（英文版）)

年 卷 期：2024年第92卷第5期

页      面：8-15页

核心收录：

学科分类：0808[工学-电气工程] 081705[工学-工业催化] 08[工学] 0817[工学-化学工程与技术] 

基　　金：supported by the National Key Research and Development Program of China(2022YFB3807500) the Natural Science Foundation of China(22220102003) the Beijing Natural Science Foundation(JL23003) "Double-First-Class"construction projects(XK180301 and XK1804-02) China Postdoctoral Science Foundation 2023TQ0020 Dostdoctoral Fellowship Program of CPSF(GZC20230199) 

主　　题：Nitrogen/sulfurdual sites Metal-coordinated nitrogen sites Covalent organic polymer Oxygen reduction reaction Zn-airflow battery 

摘      要：The implementation of pristine covalent organic polymer(CO_(2)P)with well-defined structure as air electrode may spark fresh vitality to rechargeable zinc-air flow batteries(ZAFBs),but it still remains challenges in synergistically regulating their electronic states and structural porosity for the great device ***,we conquer these issues by exploiting N and S co-doped graphene with COP rich in metal-ligand nitrogen to synergistically construct an effective catalyst for oxygen reduction reaction(ORR).Among them,the N and S co-doped sites with high electronegativity properties alter the number of electron occupations in the d orbital of the iron centre and form electron-transfer bridges,thereby boosting the selectivity of the ORR-catalysed four-electron ***,the introduction of COP materials aids the formation of pore interstices in the graphene lamellae,which both adequately expose the active sites and facilitate the transport of reactive *** from the synergistic effect,as-prepared catalyst exhibits excellent half-wave potentials(E_(1/2)=912 mV)and stability(merely 8.8%drop after a long-term durability test of 50000 s).Further,ZAFBs assembled with the N/SG@CO_(2)P catalyst demonstrate exceptional power density(163.8 mW cm^(-2))and continuous charge and discharge for approximately 140 h at 10 mA cm^(-2),outperforming the noble-metal benchmarks.