The hydroxide‐mediated non‐ CO pathway: Overcoming CO poisoning in methanol electrolysis at 500  mA  cm −2

Abstract Replacing the oxygen evolution reaction with the methanol oxidation reaction (MOR) is a promising strategy for energy‐efficient H 2 production, yet it is severely hampered by CO poisoning of Pt‐based catalysts. We introduce a strategy to intrinsically prevent CO formation by reshaping the reaction landscape via a hydroxide‐rich interface. The designed catalyst, featuring a PtRu nanoalloy anchored on in situ grown Ni(OH) 2 nanosheets, provides abundant OH* species. These OH* intercept the CHO* intermediate, diverting the reaction toward a formate pathway and completely bypassing CO* formation. In situ spectroscopy and mass spectrometry confirm this exclusive non‐CO route, showing no CO species formation. Consequently, the catalyst delivers ultrahigh MOR mass activity of 3.31 A mg −1 Pt . When assembled into a hybrid electrolyzer, it sustains 500 mA cm −2 for >92 h at an ultralow cell voltage (0.80 V). This work validates a robust hydroxide‐mediated design principle that eliminates CO poisoning at its source, enabling practical, high‐current H 2 production.