Electronic tuning of Pt-shell @ Fe-Core catalysts for high performance in methanol reforming toward hydrogen at low-temperatures

Methanol aqueous-phase reforming (APR) offers a sustainable route for H2 production, yet its efficiency is limited by the high activation barrier for O–H bond cleavage (85 kJ/mol) in methanol and competitive CO poisoning. Conventional Pt/α-MoC catalysts lack precise electronic control to kinetically favor the formation of methoxy (CH3O∗) intermediates—the critical precursor for selective CO2/H2 production. Herein, we report a core-shell Pt-Shell @ Fe-Core/α-MoC catalyst engineered at the atomic scale to achieve breakthrough performance. Electronic modulation elevates the Pt d-band center to −1.70 eV, enhancing methanol adsorption and enabling selective O–H bond activation. This synergy stabilizes the CH3O∗ intermediate via Pt–O bonding and significantly reduces energy barriers for both CH3O∗ formation and O–H cleavage. Consequently, the catalyst achieves high methanol conversion with high CO2 selectivity at only 105 °C, while suppressing CH4 byproduct formation to undetectable levels. Density functional theory (DFT) calculations confirm the preferential adsorption of CH3O∗ through Pt–O coordination, steering the reaction pathway toward CO2/H2 and circumventing methanation. This study demonstrates the precise engineering of Pt-Shell @ Fe-Core structures to regulate electronic configurations, specifically optimizing O-H bond activation efficiency and achieving breakthroughs in low-temperature methanol reforming for hydrogen production. The capacity of electronic structure engineering in core-shell catalysts to guide bond activation thermodynamics offers a scalable strategy for the efficient production of hydrogen from renewable resources.