Reconstructing MOF Nanoarrays Into Ternary Metallic Sites via Electronic Push‐Pull for Electro‐Oxidative O/S‐H Cleavage

ABSTRACT The electrochemical cleavage of O─H and S─H bonds are essential for sustainable energy and synthesis but suffer from high overpotentials and slow kinetics. Here, we develop an “electron push‐pull” strategy to reconstruct self‐supported ferrocene‐integrated Ce/Co metal‐organic framework (MOF) nanoarrays into highly active ternary Ce‐CoFeOOH. The synergy between electron‐rich ferrocene units and electron‐withdrawing Ce 3+ /Ce 4+ ions enables this rapid transformation at low potentials. The resulting catalyst exhibits outstanding oxygen evolution performance, requiring only 204 mV overpotential at 10 mA cm −2 in 1 m KOH, with excellent stability. Simultaneously, it achieves efficient electrocatalytic oxidation of L‐Cysteine to solid L‑Cystine at 3.89 mmol g −1 h −1 , demonstrating enhanced S–H activation kinetics. Experimental and theoretical analyses reveal that the ternary Ce─O─Co─O─Fe sites, with an upshifted d‐band center, facilitate the intermediate adsorption and lower the energy barrier of the rate‐determining step, thereby boosting both oxygen evolution and L‐Cysteine oxidation. This work provides a robust approach for designing high‐performance electrocatalysts that cleave challenging bonds efficiently.