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

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

doi:10.61558/2993-074X.3610

Journal of Electrochemistry ›› 2026, Vol. 32 ›› Issue (6) :2601221 DOI: 10.61558/2993-074X.3610

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

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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.

Keywords

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

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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. Journal of Electrochemistry, 2026, 32 (6) : 2601221 DOI:10.61558/2993-074X.3610

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