Atomically Ordered PtBi2 Intermetallic as Catalyst for Ultrahigh Efficiency and Durability in Methanol Electro‐Oxidation

Abstract Pt‐based nanomaterials are deemed as state‐of‐the‐art electrocatalysts for methanol oxidation reaction (MOR) in fuel cell. However, it still suffers from the low mass activity and poisonous effect of *CO intermediate. Herein, an efficient and durable cubic PtBi 2 intermetallic (c‐PtBi 2 IMCs) catalysts are developed, enabling an ultrahigh mass activity of 13.85 A mg Pt −1 and specific activity of 33.45 mA cm −2 (8.5 and 13.3 times higher than those of commercial Pt/C), with negligible activity decay after 50 h of potentiostatic electrolysis. In situ Fourier transform infrared spectroscopy results demonstrate the weakened adsorption of *CO and significantly enhanced *OH adsorption on c‐PtBi 2 IMCs accelerates the detoxication of *CO, which is crucial to the superb MOR performance of c‐PtBi 2 . Density functional theory (DFT) calculations elucidate that Bi integration into the electronic structure of Pt optimizes the adsorption of *OH species while concurrently reducing the adsorption of *CO. Consequently, the MOR on c‐PtBi 2 proceeds via a smooth pathway with a small Gibbs free energy barrier. Moreover, cubic PtBi 2 exhibits promising potential as a versatile fuel cell anode catalyst for the oxidation of various liquid fuels. This work presents a marvelous MOR catalyst that ensures ultra‐highly efficient and durable methanol electro‐oxidation.