Molybdenum-induced interfacial electron pump stabilizes γ-NiOOH for efficient electrooxidation conversion of methanol into formate.

The intrinsic instability of the active γ-NiOOH phase severely limits the performance of nickel-based electrocatalysts for the methanol oxidation reaction (MOR). Herein, we report a Mo-induced interfacial electron pump strategy to stabilize the γ-NiOOH lattice and boost MOR efficiency. Via a distinctive two-step strategy of electrolysis and subsequent solvothermal reaction, we construct NiMo/graphene (NiMo/G) composites rich in Ni-O-Mo interfaces, where Mo centers continuously withdraw electrons from adjacent Ni sites, functioning as efficient electron sinks. This precise electronic modulation lowers the thermodynamic barrier for γ-NiOOH formation by ∼150 mV and optimizes the adsorption energetics for intermediates, reducing the energy barrier of the rate-determining *CH3O → *CH2O step from 0.68 to 0.46 eV, thereby directing the reaction along a low-overpotential formate pathway. Consequently, this optimized NiMo/G catalyst achieves exceptional area activity of 320.6 ± 5.2 mA cm-2 and mass activity of 15,638.9 ± 254.1 mA mgNi-1, respectively. This work establishes interfacial electron pump engineering as a general and powerful strategy for stabilizing high-valent active phases in advanced energy conversion and storage technologies.