平面与非平面型钴基分子催化剂的二氧化碳电还原行为特征
收稿日期: 2026-01-22
修回日期: 2026-03-05
录用日期: 2026-04-09
网络出版日期: 2026-04-09
Distinct CO2 Electroreduction Behaviors over Planar and Non-Planar Cobalt Molecular Catalysts
Ru Jia was responsible for the experimental design, implementation, data analysis, and writing of the original draft. Cheng-Biao Zhu and Zi-Mo Zhang conducted the in-situ HRMS measurements. Tuo Wang, Kai-Cong Yang, Guang-Zhe Wang, Yang Hu, Ting-Ting Zhang, Zhen-Wei Wei, and Li Xiao assisted in experimental implementation and data analysis. Gong-Wei Wang and Lin Zhuang supervised the research and revised the manuscript.
Received date: 2026-01-22
Revised date: 2026-03-05
Accepted date: 2026-04-09
Online published: 2026-04-09
分子催化剂凭借其结构明确、易于调控的优势，为电催化反应机理研究提供了理想平台。然而，当前研究主要集中于中心金属或外围配体的调控作用，空间构型对分子催化剂性能的影响仍缺乏系统探索。基于此，本文合成了两种具有相似配位环境但空间构型不同的钴基配合物——平面型六氮杂大环钴配合物（CoHAM）与非平面型不成环钴配合物Co(phen)2Cl2，并系统考察了二者在电催化二氧化碳还原反应中的特征行为。结果发现，平面型CoHAM的二氧化碳还原性能显著优于非平面型Co(phen)2Cl2。为了理解性能差异的根源，进一步结合原位紫外可见光谱、高分辨质谱以及拉曼光谱技术，揭示出二者催化二氧化碳还原中不同的关键中间体与反应路径。这些发现指明分子催化剂空间构型对电催化性能的关键影响，亦为高效二氧化碳还原催化剂的理性设计提供了新思路。
贾茹 , 朱成标 , 张子墨 , 王托 , 杨铠聪 , 王光喆 , 胡杨 , 张婷婷 , 魏振威 , 肖丽 , 王功伟 , 庄林 . 平面与非平面型钴基分子催化剂的二氧化碳电还原行为特征[J]. 电化学, 2026 , 32(6) : 2601221 . DOI: 10.61558/2993-074X.3610
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.
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