Generation of FeIV=O and its Contribution to Fenton-Like Reactions on a Single-Atom Iron-N-C Catalyst

作者：Cheng, Cheng; Ren, Wei; Miao, Fei; Chen, Xuantong; Chen, Xiaoxiao; Zhang, Hui^*

来源：Angewandte Chemie - International Edition, 2023, 62(10).

DOI：10.1002/anie.202218510

• Atomic Distance
• Fenton-Like Reactions
• High-Valent Iron-Oxo Species
• Peroxymonosulfate Activation
• Single-Atom Catalysts

Generating Fe-IV=O on single-atom catalysts by Fenton-like reaction has been established for water treatment; however, the Fe-IV=O generation pathway and oxidation behavior remain obscure. Employing an Fe-N-C catalyst with a typical Fe-N-4 moiety to activate peroxymonosulfate (PMS), we demonstrate that generating Fe-IV=O is mediated by an Fe-N-C-PMS* complex-a well-recognized nonradical species for induction of electron-transfer oxidation-and we determined that adjacent Fe sites with a specific Fe-1-Fe-1 distance are required. After the Fe atoms with an Fe-1-Fe-1 distance <4 angstrom are PMS-saturated, Fe-N-C-PMS* formed on Fe sites with an Fe-1-Fe-1 distance of 4-5 angstrom can coordinate with the adjacent Fe-II-N-4, forming an inter-complex with enhanced charge transfer to produce Fe-IV=O. Fe-IV=O enables the Fenton-like system to efficiently oxidize various pollutants in a substrate-specific, pH-tolerant, and sustainable manner, where its prominent contribution manifests for pollutants with higher one-electron oxidation potential.

• 单位
  武汉大学; 南昌航空大学