Theoretical study of the effect of coordination environment on the activity of metal macrocyclic complexes as electrocatalysts for oxygen reduction
Ziqi Tian,
Yuan Wang,
Yanle Li,
Ge Yao,
Qiuju Zhang,
Liang Chen
Affiliations
Ziqi Tian
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China; University of Chinese Academy of Sciences, 100049 Beijing, China; Corresponding author
Yuan Wang
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China; University of Chinese Academy of Sciences, 100049 Beijing, China; Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, China
Yanle Li
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China; University of Chinese Academy of Sciences, 100049 Beijing, China; Corresponding author
Ge Yao
School of Physics, Collaborative Innovation Center of Advanced Microstructures, and National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, China
Qiuju Zhang
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China; University of Chinese Academy of Sciences, 100049 Beijing, China
Liang Chen
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China; University of Chinese Academy of Sciences, 100049 Beijing, China; Corresponding author
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.
