Delicately Regulating the Adsorption Balance of *OH and *CO on Ru cluster @PtMo Electrocatalysts With d‐d Orbital Hybridization for Efficient Methanol Oxidation Reaction

The kinetics of methanol oxidation reaction (MOR) are severely constrained by the strong adsorption of *CO and the sluggish deprotonation of *OH on Pt‐based catalysts. Modulating the kinetic balance of the adsorption of *CO and *OH intermediates is an efficient route. Herein, we delicately regulate the adsorption balance of *OH and *CO on a novel Ru nanocluster anchoring onto PtMo (Ru cluster @PtMo) electrocatalyst via d‐d orbital hybridization based on density functional theory (DFT) calculations. The strong Pt‐5d/Mo‐4d/Ru‐4d orbital hybridization downshifts the Pt d‐band center to −2.25 eV, which weakens *CO adsorption while enhancing *OH supply kinetics. As a proof of concept, Ru cluster @PtMo nanowire assemblies (NWAs) was synthesized for exploring the MOR performance. Consequently, Ru cluster @PtMo NWAs with 5 at% Ru achieve record‐high activities (14.74 mA cm −2 and 5.54 A mg −1 ) for alkaline MOR. Multiple characterizations and DFT calculations results elucidate that electron‐rich Pt sites are responsible for the dehydrogenation of methanol and Ru nanocluster affords the adsorption site for activating H 2 O molecule, and the synergy of multi‐sites facilitates the removal of *CO being the rate‐determining step. This study would provide deep insights for the rational design of multi‐metal site catalysts by utilizing the d‐d orbital hybridization of metal nanoclusters anchored heterogeneous structure.