Distinct CO₂ Electroreduction Behaviors over Planar and Non-Planar Cobalt Molecular Catalysts

Authors

• Ru Jia, College of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, China
• Cheng-Biao Zhu, College of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, China
• Zi-Mo Zhang, College of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, China
• Tuo Wang, College of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, China
• Kai-Cong Yang, College of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, China
• Guang-Zhe Wang, College of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, China
• Yang Hu, College of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, China
• Ting-Ting Zhang, College of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, China
• Zhen-Wei Wei, College of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, China
• Li Xiao, College of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, China
• Gong-Wei Wang, College of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, ChinaFollow
• Lin Zhuang, College of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, ChinaFollow

Corresponding Author

Gong-Wei Wang (gwwang@whu.edu.cn);
Lin Zhuang (lzhuang@whu.edu.cn)

Abstract

Molecular catalysts serve as ideal platforms for studying electrocatalytic reaction mechanisms. While current research mainly focuses on modulating central metals or surrounding ligands, the influence of molecular spatial configuration remains largely unexplored. Herein, we synthesized two cobalt complexes with similar ligand environments but distinct spatial geometries, a planar cobalt hexaazamacrocyclic complex (CoHAM) and a non-planar acyclic Co(phen)₂Cl₂, and evaluated their performance in CO₂ reduction reaction (CO₂RR). The planar CoHAM exhibited dramatically superior CO₂RR performance compared to the non-planar Co(phen)₂Cl₂. Through a series of combined analyses using in-situ UV-vis spectroscopy, high-resolution mass spectrometry (HRMS), and Raman spectroscopy, we elucidated the origins of this performance gap by identifying key intermediates and reaction pathways. These findings underscore the critical role of the spatial configuration of molecular catalysts in governing electrocatalytic performance and provide a strategic direction for the rational design of efficient CO₂RR catalysts.

Graphical Abstract

Keywords

Molecular catalyst, Spatial configuration, Cobalt hexaazamacrocyclic complex, CO2 reduction reaction, Catalytic mechanism

DOI Link

https://doi.org/10.61558/2993-074X.3610

Creative Commons License

This work is licensed under a Creative Commons Attribution 4.0 International License.

Publication Date

2026-06-28

Online Available Date

2026-04-09

Revised Date

2026-03-05

Received Date

2026-01-22

Recommended Citation

Ru Jia, Cheng-Biao Zhu, Zi-Mo Zhang, Tuo Wang, Kai-Cong Yang, Guang-Zhe Wang, Yang Hu, Ting-Ting Zhang, Zhen-Wei Wei, Li Xiao, Gong-Wei Wang, Lin Zhuang. Distinct CO₂ Electroreduction Behaviors over Planar and Non-Planar Cobalt Molecular Catalysts[J]. Journal of Electrochemistry, 2026, 32(6): 2601221.
DOI: 10.61558/2993-074X.3610
Available at: https://jelectrochem.xmu.edu.cn/journal/vol32/iss6/3