Cascaded p–d Orbital Hybridization Interaction in Ultrathin High‐Entropy Alloy Nanowires Boosts Complete Non‐CO Pathway of Methanol Oxidation Reaction

Designing high efficiency platinum (Pt)‐based catalysts for methanol oxidation reaction (MOR) with high “non‐CO” pathway selectivity is strongly desired and remains a grand challenge. Herein, PtRuNiCoFeGaPbW HEA ultrathin nanowires (HEA‐8 UNWs) are synthesized, featuring unique cascaded p – d orbital hybridization interaction by inducing dual p ‐block metals (Ga and Pb). In comparison with Pt/C, HEA‐8 UNWs exhibit 15.0‐ and 4.2‐times promotion of specific and mass activity for MOR. More importantly, electrochemical in situ FITR spectroscopy reveals that the production/adsorption of CO (CO * ) intermediate is effectively avoided on HEA‐8 UNWs, leading to the complete “non‐CO” pathway for MOR. Theoretical calculations demonstrate the optimized electronic structure of HEA‐8 UNWs can facilitates a lower energy barrier for the “non‐CO” pathway in the MOR.