Decrypting the Influence of Axial Coordination on the Electronic Microenvironment of Co-N_(5)Site for Enhanced Electrocatalytic Reaction
作者机构：Institute of Polymers and Energy Chemistry(IPEC)College of Chemistry and Chemical EngineeringNanchang UniversityNanchang 330031 The meso-Entropy Matter LabSchool of Chemistry and Chemical EngineeringShanghai Jiao Tong UniversityShanghai 200240 School of Materials Science and EngineeringNanchang UniversityNanchang 330031 Faculty of Mathematics and Natural Sciences-Physics DepartmentBergische Universität WuppertalWuppertal D-42119 Institute of Advanced Scientific Research(iASR)Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of EducationJiangxi Normal UniversityNanchang 330022
出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)
年 卷 期：2023年第5卷第8期
页 面：1876-1887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]
主 题：porphyrin axial coordination pentacoordination structureactivity correlation oxygen reduction reaction
摘 要：Metal porphyrins are star molecules that possess welldefined coordination metal centers for versatile catalytic ***,most previous work has focused on the correlations between in-plane symmetric configuration of metal-N_(4)sites and their catalytic *** the catalytic contribution of additional axial coordination to such symmetric configuration remains a *** calculations revealed that axially anchoring an extra pyridine on the tetra-coordinated cobalt porphyrin(Co-N4)to construct penta-coordinated cobalt porphyrin(Co-N_(5))renders cobalt a higher electron density,thereby favoring the rate-determining O_(2)adsorption/activation and reducing the oxygen electroreduction ***,a well-defined Co-N_(5)site is rationally introduced into the azo-linked polymer framework for a fundamental structure-catalytic performance correlation ***-prepared Co-N_(5)catalyst exhibits a 26 mV positive shift in half-wave potential compared with the pyridine-free Co-N_(4)counterpart,discloses a markedly higher power density(141.4 mW cm^(−2)),and possesses better long-term durability(over 160 h cycles)in a Zn-air ***,such a Co-N_(5)catalyst also showcases potential applications for CO_(2)reduction with high CO_(2)-to-CO conversion faradic efficiency and better selectivity than the Co-N_(4)counterpart because coordination of the fifth pyridine evokes electronic localization that suppresses a competitive side *** work proves the positive electrocatalytic contribution of axial penta-coordination on well-defined metalporphyrin-based catalysts and offers atomic understanding of the structure-performance correlation on single atom catalysts for future catalyst design.
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