Anchoring platinum catalysts on appropriate supports, e.g., MXenes, is a feasible pathway to achieve a desirable anode for direct methanol fuel cells. The authentic performance of Pt is often hindered by the occupancy and poisoning of active sites, weak interaction between Pt and supports, and the dissolution of Pt. Herein, we construct three-dimensional (3D) crumpled Ti₃C₂T_x MXene balls with abundant Ti vacancies for Pt confinement via a spray-drying process. The as-prepared Pt clusters/Ti₃C₂T_x (Ptc/Ti₃C₂T_x) show enhanced electrocatalytic methanol oxidation reaction (MOR) activity, including a relatively low overpotential, high tolerance to CO poisoning, and ultrahigh stability. Specifically, it achieves a high mass activity of up to 7.32 A mg_Pt^-1, which is the highest value reported to date in Pt-based electrocatalysts, and 42% of the current density is retained on Ptc/Ti₃C₂T_x even after the 3000 min operative time. In situ spectroscopy and theoretical calculations reveal that an electric field-induced repulsion on the Ptc/Ti₃C₂T_x interface accelerates the combination of OH^- and CO adsorption intermediates (CO_ads) in kinetics and thermodynamics. Besides, this Ptc/Ti₃C₂T_x also efficiently electrocatalyze ethanol, ethylene glycol, and glycerol oxidation reactions with comparable activity and stability to commercial Pt/C.

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