Carbon-Confined FeCo@Pt Nanocatalysts Derived from Metal–Organic Frameworks for Pt-Economical, High-Performance, and CO-Tolerant Methanol Electrooxidation

A major challenge in developing direct methanol fuel cells (DMFCs) is to design Pt-based electrocatalysts that reduce Pt consumption while maintaining high activity, durability, and resistance to carbonaceous poisoning during the methanol oxidation reaction (MOR). Herein, a metal–organic framework (MOF)-derived confinement strategy is proposed to construct FeCo@Pt core–shell nanocatalysts embedded in nitrogen-doped porous carbon (NPC). This architecture integrates three key functions within one catalyst platform: an FeCo alloy core for electronic modulation of the Pt shell, a Pt-rich surface for efficient methanol oxidation, and an NPC matrix for nanoparticle confinement, structural stabilization, and accelerated mass/charge transport. Benefiting from this cooperative design, the optimized FeCo@Pt/NPC-T₈₀₀-X₁₅-t₂₀ catalyst delivered a mass activity of 663.84 mA mg_Pt^–1, which was 1.92 times that of commercial Pt/C. It maintained a current density 5.81 times higher than that of Pt/C after 3600 s of operation. CO-stripping measurements further revealed a 66 mV negative shift in the CO oxidation peak, indicating enhanced oxidative removal of CO-like intermediates. Moreover, in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) provided direct mechanistic evidence for the enhanced formation of OH_ads species, the generation of C–OH and *COOH intermediates, and the suppression of the accumulation of linearly adsorbed CO on Pt sites during MOR. These results demonstrate that the FeCo core facilitates the formation and spillover of oxygenated species, while the electronic interaction between FeCo and Pt weakens CO adsorption, thereby accelerating CO_ads oxidation and improving poisoning resistance. This work highlights the effectiveness of coupling alloy-core modulation, Pt-shell utilization, and MOF-derived carbon confinement for developing Pt-economical, CO-tolerant, and durable MOR electrocatalysts.