Sun Xiaohui, Tuo Yongxiao, Ye Chenliang, Chen Chen, Lu Qing, Li Guanna, Jiang Peng, Chen Shenghua, Zhu Peng, Ma Ming, Zhang Jun, Bitter Johannes H, Wang Dingsheng, Li Yadong
Department of Chemistry, Tsinghua University, Beijing, 100084, P. R. China.
Department of Materials Science and Engineering, China University of Petroleum (East China), Qingdao, 266580, P. R. China.
Angew Chem Int Ed Engl. 2021 Oct 25;60(44):23614-23618. doi: 10.1002/anie.202110433. Epub 2021 Oct 1.
Electrochemical reduction of carbon dioxide (CO ) 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 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 , 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 electrochemical reduction performance at low overpotentials.
二氧化碳（CO₂）电化学还原为化学品和燃料最近引起了广泛关注，但通常存在高过电位和低选择性的问题。在这项工作中，单磷原子主要以P-C键的形式引入到氮掺杂碳负载的单铁原子催化剂（Fe-SAC/NPC）中，用于在水溶液中将CO₂电还原为CO。该催化剂在320 mV的低过电位下表现出约97%的CO法拉第效率，塔菲尔斜率仅为59 mV dec⁻¹，与最先进的金催化剂相当。实验分析与密度泛函理论（DFT）计算表明，高配位壳层（n≥3）中的单磷原子，特别是铁中心的第三配位壳层增强了铁的电子局域化，从而改善了关键*COOH中间体在铁上的稳定性，导致在低过电位下具有优异的CO₂电化学还原性能。
