Sulfur Bridge Geometry Boosts Selective FeIV═O Generation for Efficient Fenton‐Like Reactions

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.