催化作用
活动站点
密度泛函理论
氧化还原
电化学
化学
选择性
机制(生物学)
反应机理
动力学蒙特卡罗方法
Atom(片上系统)
吸附
组合化学
化学物理
纳米技术
计算化学
材料科学
蒙特卡罗方法
计算机科学
无机化学
物理化学
物理
有机化学
电极
嵌入式系统
统计
量子力学
数学
作者
Nam V. Tran,Jiyuan Liu,Shuzhou Li
标识
DOI:10.1002/anie.202411765
摘要
Single‐atom iron embedded in N‐doped carbon (Fe‐N‐C) is among the most representative single‐atomic catalysts (SACs) for electrochemical CO2 reduction reaction (CO2RR). Despite the simplicity of the active site, the CO2‐to‐CO mechanism on Fe‐N‐C remains controversial. Firstly, there is a long debate regarding the rate‐determining step (RDS) of the reactions. Secondly, recent computational and experimental studies are puzzled by the fact that the CO‐poisoned Fe centers still remain highly active at high potentials. Thirdly, there are ongoing challenges in elucidating the high selectivity of hydrogen evolution reaction (HER) over CO2RR at high potentials. In this work, we introduce a novel CO2RR mechanism on Fe‐N‐C, which was inspired by the dynamic of active sites in biological systems. By employing grand‐canonical density functional theory and kinetic Monte‐Carlo, we found that the RDS is not fixed but changes with the applied potential. We demonstrated that our proposed dual‐side mechanisms could clarify the reason behind the high catalytic activity of CO‐poisoned metal centers, as well as the high selectivity of HER over CO2RR at high potential. This study provides a fundamental explanation for long‐standing puzzles of an important catalyst and calls for the importance of considering the dynamic of active sites in reaction mechanisms.
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