Sulfur Bridge Geometry Boosts Selective Fe<sup>IV</sup>═O Generation for Efficient Fenton‐Like Reactions
Xunheng Jiang, Zhongyuan Guo, Jiang Xu, Zhiyu Pan, Chen Miao, Yue Chen, Hao Li, Hiroshi Oji, Yi‐Tao Cui, Graeme Henkelman, Xinhua Xu, Lizhong Zhu, Daohui Lin
Abstract
Abstract High‐valent iron–oxo species (Fe IV ═O) is a fascinating enzymatic agent with excellent anti‐interference abilities in various oxidation processes. However, selective and high‐yield production of Fe IV ═O remains challenging. Herein, Fe diatomic pairs are rationally fabricated with an assisted S bridge to tune their neighbor distances and increase their loading to 11.8 wt.%. This geometry regulated the d ‐band center of Fe atoms, favoring their bonding with the terminal and hydroxyl O sites of peroxymonosulfate (PMS) via heterolytic cleavage of O─O, improving the PMS utilization (70%), and selective generation of Fe IV ═O (>90%) at a high yield (63% of PMS) offers competitive performance against state‐of‐the‐art catalysts. These continuous reactions in a fabricated device and technol‐economic assessment further verified the catalyst with impressive long‐term activity and scale‐up potential for sustainable water treatment. Altogether, this heteroatom‐bridge strategy of diatomic pairs constitutes a promising platform for selective and efficient synthesis of high‐valent metal–oxo species.