化学
活性氧
选择性
电子转移
表面改性
氧气
硫黄
激进的
反应中间体
光化学
氧化还原
催化作用
无机化学
有机化学
生物化学
物理化学
作者
Yuan Xu,Yuanjie Ma,Xinghua Chen,Kaiqing Wu,Li Wang,Yanfei Shen,Songqin Liu,Xuejiao J. Gao,Yuanjian Zhang
标识
DOI:10.1002/anie.202408935
摘要
Reactive oxygen species (ROS) regulation for single‐atom nanozymes (SAzymes), e.g., Fe–N–C, is a key scientific issue that determines the activity, selectivity, and stability of aerobic reaction. However, the poor understanding of ROS formation mechanism on SAzymes greatly hampers their wider deployment. Herein, inspired by cytochromes P450 affording bound ROS intermediates in O2 activation, we report Fe–N–C containing the same FeN4 but with tunable second‐shell coordination can effectively regulate ROS production pathways. Remarkably, compared to the control Fe–N–C sample, the second‐shell sulfur functionalized Fe–N–C delivered a·2.4‐fold increase of oxidase‐like activity via the bound Fe=O intermediate. Conversely, free ROS (•O2‐) release was significantly reduced after functionalization, down to only 17% of that observed for Fe–N–C. The detailed characterizations and theoretical calculations revealed that the second‐shell sulfur functionalization significantly altered the electronic structure of FeN4 sites, leading to an increase of electron density at Fermi level. It enhanced the electron transfer from active sites to the key intermediate *OOH, thereby ultimately determining the type of ROS in aerobic oxidation process. The proposed Fe–N–Cs with different second‐shell anion were further applied to three aerobic oxidation reactions with enhanced activity, selectivity, and stability.
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