Theoretical study of the effect of coordination environment on the activity of metal macrocyclic complexes as electrocatalysts for oxygen reduction

iScience

Yanle Li¹  Liang Chen²  Yuan Wang³  Qiuju Zhang³  Ge Yao⁴  Ziqi Tian⁴ 

[1] Corresponding author;Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, China;University of Chinese Academy of Sciences, 100049 Beijing, China;Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China;

关键词: chemistry;    catalysis;    electrochemistry;    computational chemistry;   

DOI  :  

来源: DOAJ

【 摘 要 】

Summary: Transition 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.

【 授权许可】

Unknown