Atomically Dispersed Fe–N4 Site as a Conductive Bridge Enables Efficient and Stable Activation of Peroxymonosulfate: Active Site Renewal, Anti-Oxidative Capacity, and Pathway Alternation Mechanism

• DOI: 10.1021/acs.est.3c06229
• Publication Date: 2023-11-13T19:07:45Z
• Authors: Tao Zeng; Xiaofeng Tang; Zheqing Huang; Hong Chen; Sijia Jin; Feilong Dong; Jia He; Shuang Song; Haiyan Zhang
• Keywords: Moiety; Chemisorption

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 (FeSA-NC) via a micropore confinement strategy are fabricated initiate PMS oxidation reaction, achieving specific activity 5.16 × 103 L·min-1·g-1 for degradation bisphenol A (BPA), which outperforms most state-of-the-art single-atom (SA) catalysts. Mechanism inquiry reveals enhanced chemisorption and electron transfer between FeSA-NC, enabling an inner shuttle mechanism in serves conductive bridge. The reduce energy barrier formation SO5* H*, thereby transforming reaction pathway from directly adjacent into reactive oxygen species (ROS)-dominated oxidation. Theoretical calculations dynamic simulations reveal that induce facilitated desorption intermediates (PMS*/BPA*), collectively contribute renewal eventually enhance catalytic durability. This work offers reasonable interpretation important role moiety altering activation enhancing antioxidative capacity materials, fundamentally furnishes theoretical support SA material design.