文章基本信息

标题：Theoretical study of the effect of coordination environment on the activity of metal macrocyclic complexes as electrocatalysts for oxygen reduction
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作者：Ziqi Tian ; Yuan Wang ; Yanle Li 等
期刊名称：iScience
印刷版ISSN：2589-0042
出版年度：2022
卷号：25
期号：7
页码：1-14
DOI：10.1016/j.isci.2022.104557
语种：English
出版社：Elsevier
摘要：SummaryTransition metal macrocyclic complexes are appealing catalysts for electrochemical oxygen reduction reaction (ORR). Here, we perform first-principles calculations to gain a comprehensive understanding on the structure-property relationship of the metal macrocyclic complex systems. Various modifications of the complexes are considered, including centered metal, axial ligand, coordination atom, substituent, and macrocycles. Based on simulation, introduction of appropriate apical ligand can improve the performance of all the three metals, whereas replacement of nitrogen with oxygen or carbon as the coordination atoms may enhance the Ni-centered systems. The antiaromatic ring stabilizes the ∗OOH intermediate, whereas the macrocycle with reduced electron density inhibits the binding with oxygen. By regulating the coordination environment, the overpotential can be significantly reduced. This work may assist the rational design of ORR catalysts and is of great significance for the future development of oxygen reduction catalysts.Graphical abstractDisplay OmittedHighlights•Metal macrocyclic complexes are potential electrocatalysts for ORR•An understanding on structure-property relationship is gained based on simulation•Various modifications are considered to improve the performanceChemistry; Catalysis; Electrochemistry; Computational chemistry