Reaction Mechanisms of Well‐Defined Metal–N 4 Sites in Electrocatalytic CO 2 Reduction

作者：Zheng Zhang, Jianping Xiao, Xue‐Jiao Chen, Song Yu, Liang Yu, Rui Si, Yong Wang, Su-Heng Wang, Xianguang Meng, Ye Wang, Zhong‐Qun Tian, Dehui Deng · 发表于：Angewandte Chemie International Edition · 年份：2018 · DOI：10.1002/anie.201808593 · 被引用次数：428 · 研究领域：CO2 Reduction Techniques and Catalysts、Covalent Organic Framework Applications、Carbon dioxide utilization in catalysis

Abstract Electrocatalytic CO 2 reduction to CO emerges as a potential route of utilizing emitted CO 2 . Metal‐N‐C hybrid structures have shown unique activities, however, the active centers and reaction mechanisms remain unclear because of the ambiguity in true atomic structures for the prepared catalysts. Herein, combining density‐functional theory calculations and experimental studies, the reaction mechanisms for well‐defined metal–N 4 sites were explored using metal phthalocyanines as model catalysts. The theoretical calculations reveal that cobalt phthalocyanine exhibits the optimum activity for CO 2 reduction to CO because of the moderate *CO binding energy at the Co site, which accommodates the *COOH formation and the *CO desorption. It is further confirmed by experimental studies, where cobalt phthalocyanine delivers the best performance, with a maximal CO Faradaic efficiency reaching 99 %, and maintains stable performance for over 60 hours.