Heterojunction‐Guided Reconstruction Toward Ru‐Co Bridged Dual Sites for Efficient Oxide‐Path Water Electrolysis

ABSTRACT The oxide path mechanism (OPM) offers a compelling route to bypass the activity–stability trade‐off of conventional oxygen evolution catalysis. However, its deliberate activation has largely relied on doping strategies to create heterometallic dual sites, which suffer from limited electronic tunability. Here, we demonstrate a fundamentally different approach that combines heterojunction engineering with guided in situ reconstruction. By integrating ruthenium oxide with a cobalt–nickel telluride heterostructure, we exploit the pronounced surface reconstruction of tellurides under anodic potentials to in situ generate a metastable CoO 2 phase featuring high‐valent cobalt. This reconstructed phase intimately couples with neighboring RuO 2 to form well‐defined Co–O–Ru bridged dual sites, which are proposed as the pivotal centers for OPM‐enabled O─O coupling. The telluride framework further acts as an electronic modulator, stabilizing ruthenium while promoting high‐valent cobalt formation. This synergy yields a catalyst with an overpotential of 213 mV at 100 mA cm −2 and a mass activity 103 times that of commercial RuO 2 . When deployed in an anion‐exchange membrane electrolyzer, it operates at 1 A cm −2 with a cell voltage of 1.78 V for over 800 h. Our work establishes heterojunction‐induced reconstruction as a powerful strategy to unlock OPM catalysis, moving beyond conventional doping toward dynamically assembled active interfaces.