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 Ti 3 C 2 T x MXene balls with abundant Ti vacancies for Pt confinement via a spray-drying process. The as-prepared Pt clusters/Ti 3 C 2 T x (Ptc/Ti 3 C 2 T 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/Ti 3 C 2 T x even after the 3000 min operative time. In situ spectroscopy and theoretical calculations reveal that an electric field-induced repulsion on the Ptc/Ti 3 C 2 T x interface accelerates the combination of OH − and CO adsorption intermediates (CO ads ) in kinetics and thermodynamics. Besides, this Ptc/Ti 3 C 2 T x also efficiently electrocatalyze ethanol, ethylene glycol, and glycerol oxidation reactions with comparable activity and stability to commercial Pt/C.

Platinum (Pt)‐based electrocatalysts are the benchmark catalysts for hydrogen evolution reaction (HER); however, they are limited by the scarcity and high price. Introducing an adequate substrate to disperse and anchor Pt‐based species is a feasible pathway to improve the utilization efficiency. Herein, a quick and continuous spray drying route is proposed to fabricate 3D crumpled Ti3C2Tx MXene loaded with sub‐nanometer platinum clusters (Pt/MXene). The 3D crumpled structure inhibits the restacking of layered MXene nanosheets and guarantees the fully exposure of Pt clusters. The as‐prepared catalyst exhibits excellent HER performances comparable to commercial Pt/C, including a low overpotential of 34 mV to reach a current density of 10 mA cm−2, a superior mass activity (1847 mA mgPt−1), a small Tafel slope (29.7 mV dec−1), and a high turnover frequency (10.66 H2 s−1). The improved activity of Pt/MXene can be attributed to the charge transfer from Pt clusters to MXene, which weakens the hydrogen adsorption, as evidenced by the density functional theory calculations. The present contribution proposes a novel strategy to anchor low‐mass‐loading sub‐nanometer precious metal clusters on crumpled MXene with fully exposed active sites for catalysis.

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