A Graphene‐Supported Single‐Atom FeN5 Catalytic Site for Efficient Electrochemical CO2 Reduction

作者：Huinian Zhang, Jing Li, Shibo Xi, Yonghua Du, Hai Lian Xiao, Junying Wang, Junying Wang, Haomin Xu, Gang Wu, Jia Zhang, Jiong Ping Lu, Junzhong Wang, Junzhong Wang · 发表于：Angewandte Chemie International Edition · 年份：2019 · DOI：10.1002/anie.201906079 · 被引用次数：492 · 研究领域：CO2 Reduction Techniques and Catalysts、Carbon dioxide utilization in catalysis、Ionic liquids properties and applications

Abstract Electrochemical conversion of CO2 into valued products is one of the most important issues but remains a great challenge in chemistry. Herein, we report a novel synthetic approach involving prolonged thermal pyrolysis of hemin and melamine molecules on graphene for the fabrication of a robust and efficient single‐iron‐atom electrocatalyst for electrochemical CO2 reduction. The single‐atom catalyst exhibits high Faradaic efficiency (ca. 97.0 %) for CO production at a low overpotential of 0.35 V, outperforming all Fe‐N‐C‐based catalysts. The remarkable performance for CO2‐to‐CO conversion can be attributed to the presence of highly efficient singly dispersed FeN5 active sites supported on N‐doped graphene with an additional axial ligand coordinated to FeN4. DFT calculations revealed that the axial pyrrolic nitrogen ligand of the FeN5 site further depletes the electron density of Fe 3d orbitals and thus reduces the Fe–CO π back‐donation, thus enabling the rapid desorption of CO and high selectivity for CO production.