Phosphorus Induced Electron Localization of Single Iron Sites for Boosted CO<sub>2</sub> Electroreduction Reaction
Xiaohui Sun, Yongxiao Tuo, Chenliang Ye, Chen Chen, Qing Lü, Guanna Li, Peng Jiang, Shenghua Chen, Peng Zhu, Ming Ma, Jun Zhang, Johannes H. Bitter, Dingsheng Wang, Yadong Li
Abstract
Abstract Electrochemical reduction of carbon dioxide (CO 2 ) into chemicals and fuels has recently attracted much interest, but normally suffers from a high overpotential and low selectivity. In this work, single P atoms were introduced into a N‐doped carbon supported single Fe atom catalyst (Fe‐SAC/NPC) mainly in the form of P−C bonds for CO 2 electroreduction to CO in an aqueous solution. This catalyst exhibited a CO Faradaic efficiency of ≈97 % at a low overpotential of 320 mV, and a Tafel slope of only 59 mV dec −1 , comparable to state‐of‐the‐art gold catalysts. Experimental analysis combined with DFT calculations suggested that single P atom in high coordination shells ( n ≥3), in particular the third coordination shell of Fe center enhanced the electronic localization of Fe, which improved the stabilization of the key *COOH intermediate on Fe, leading to superior CO 2 electrochemical reduction performance at low overpotentials.