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

High-valent iron-oxo species (FeIV═O) is a fascinating enzymatic agent with excellent anti-interference abilities in various oxidation processes. However, selective and high-yield production of FeIV═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 FeIV═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.