化学
催化作用
活动站点
电子转移
部分
反应机理
化学工程
纳米技术
光化学
材料科学
立体化学
有机化学
工程类
作者
Tao Zeng,Xiaojun Tang,Zheqing Huang,Hong Chen,Sijia Jin,Feilong Dong,Jia He,Lingxiangyu Li,Haiyan Zhang
标识
DOI:10.1021/acs.est.3c06229
摘要
Atomically dispersed metal sites anchored on nitrogen-doped carbonaceous substrates (M-NCs) have emerged as promising alternatives to conventional peroxymonosulfate (PMS) activators; however, the exact contribution of each site still remains elusive. Herein, isolated Fe–N4 active site-decorated three-dimensional NC substrates (FeSA-NC) via a micropore confinement strategy are fabricated to initiate PMS oxidation reaction, achieving a specific activity of 5.16 × 103 L·min–1·g–1 for the degradation of bisphenol A (BPA), which outperforms most of the state-of-the-art single-atom (SA) catalysts. Mechanism inquiry reveals enhanced chemisorption and electron transfer between PMS and FeSA-NC, enabling an inner electron shuttle mechanism in which Fe–N4 serves as a conductive bridge. The Fe–N4 sites reduce the energy barrier for the formation of SO5* and H*, thereby transforming the reaction pathway from directly adjacent electron transfer into reactive oxygen species (ROS)-dominated oxidation. Theoretical calculations and dynamic simulations reveal that the Fe–N4 sites induce facilitated desorption of reaction intermediates (PMS*/BPA*), which collectively contribute to the renewal of active sites and eventually enhance the catalytic durability. This work offers a reasonable interpretation for the important role of the Fe–N4 moiety in altering the activation mechanism and enhancing the antioxidative capacity of NC materials, which fundamentally furnishes theoretical support for SA material design.
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