In Situ Fabrication of Sulfate‐Grafted Mo‐Doped NiOOH for Electrocatalytic Methanol Oxidation Coupled With Hydrogen Production at Industrial‐Level Current Density

ABSTRACT Developing efficient and sustainable energy conversion technologies is crucial for addressing the global energy and environmental challenges. As a promising clean energy conversion strategy, the electrocatalytic methanol oxidation coupled with cathodic hydrogen production provides a pivotal path to solve the above problems. Herein, we report the synthesis of a sulfate‐grafted Mo‐NiOOH@SO 4 2− /NF bifunctional catalyst via a hydrothermal‐sulfurization‐electrochemical reconstruction strategy for coupled electrocatalytic methanol oxidation reaction (MOR) and hydrogen evolution reaction (HER). For MOR, the catalyst achieves a formate production rate of 7.34 mmol cm −2 h −1 at 1.67 V (vs. RHE) with a partial current density of 790 mA cm −2 and a Faradaic efficiency (FE) of 94.2%. In situ characterizations and density functional theory (DFT) calculations reveal that sulfate grafting elevates the d‐band center of Ni sites, enhances substrate adsorption, generates hydroxyl radicals (·OH) as reactive oxygen species, and reduces the energy barrier of the *CH 3 OH→*CH 3 O dehydrogenation step. When integrated into a two‐electrode flow cell for MOR || HER, the Mo‐NiOOH@SO 4 2− /NF achieves a current density of 830 mA cm −2 at 3.25 V with 91.8% formate FE and demonstrates exceptional stability (> 65 h at 300 mA cm −2 ). This work highlights the potential of a surface modification strategy for advancing integrated electrosynthesis systems.