文献类型：期刊文献

英文题名：Reactant-Induced Dynamic Catalysis in Co Single Atom Catalyst for Efficient Water Remediation

作者：Chen, Huan[1];Zhao, Yan[1];Zhang, Zhe[1];Pan, Yukun[1];Song, Dawei[1];Shi, Yaqin[1];Huang, Yanan[1];Niu, Bo[1,2];Zhang, Yayun[1,2];Long, Donghui[1,2]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]Suzhou Lab, Struct Mat Res Dept, Suzhou 215000, Peoples R China

年份：2025

卷号：15

期号：23

起止页码：19954

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20254719547175);WOS:【SCI-EXPANDED(收录号:WOS:001618597400001)】；

基金：This work was financially supported by National Natural Science Foundation of China (No. 22008073, No. 22478123, No. U2341291, No. 52472095), Shanghai Sailing Program (No. 20YF1410600), Shanghai Talent Development Fund (2021026), and Natural Science Foundation of Shanghai (24ZR1417200).

语种：英文

外文关键词：single-atom catalysts; dynamic coordination; orbital rearrangement; high-valent cobalt-oxo; water remediation

摘要：Elucidating the dynamic evolution of single-atom catalytic sites remains a fundamental challenge in advancing single-atom catalysis. While current studies primarily focus on stimulus-responsive structural transformations induced by external perturbations (e.g., electrochemical potential variations), the intrinsic self-adaptive mechanisms of active sites under ambient reaction conditions remain largely unexplored. Here, we report a reactant-induced dynamic coordination evolution in a nitrogen/oxygen dual-coordinated cobalt single-atom catalyst (Co-N3O1) during peroxymonosulfate-based advanced oxidation processes (PMS-AOPs). Through operando X-ray absorption spectroscopy (XAS) combined with density functional theory (DFT) calculations, we identify a two-step reversible structural transition from the initial Co-N3Ocat configuration to an O-PMS=Co-N-3 intermediate upon PMS activation, which subsequently reverts to the original Co-N3Ocat state during phenol oxidation. This dynamic restructuring arises from a spontaneous d-p orbital rearrangement between Co 3d orbitals and O 2p orbitals of coordinating oxygen species, which selectively stabilize high-valent Co(IV)=O species. The optimized catalyst exhibits a 4-fold increase in activity compared to conventional Co-N-4 SACs, along with stable operation exceeding 120 h and effective treatment of real industrial coal chemical wastewater. This work provides atomically resolved evidence of stimulus-free, reactant-induced active-site dynamics and establishes a paradigm for designing adaptive single-atom catalysts with broad applicability in environmental and energy-related applications.