Engineering electron-deficient Pt sites and hydroxyl-rich interfaces in high-entropy intermetallics for synergistically accelerated methanol electrooxidation

Ordered Pt-InSnGaPb high-entropy intermetallic is developed. • Multi-element coordination creates electron-deficient Pt interfaces. • OH-rich interfaces synergistically accelerate methanol oxidation. • In-situ FTIR and DFT reveal the catalytic mechanism. • Efficient H₂ production and methanol valorization are achieved. Electrochemical methanol oxidation reaction (MOR) represents a promising route for value-added chemical production coupled with on-demand hydrogen production, yet its practical deployment is hindered by the sluggish kinetics and the poisoning susceptibility of conventional Pt-based catalysts. Herein, we demonstrate that a high-entropy intermetallic Pt-InSnGaPb catalyst breaks this limitation by reconfiguring the local catalytic environment. The high-entropy intermetallic framework induces electron-deficient Pt sites and simultaneously creates hydroxyl-rich interfacial domains, establishing a cooperative microenvironment for methanol activation and intermediate oxidation. This dual regulation accelerates charge transfer and enables efficient removal of carbonaceous species. The catalyst exhibits a favorable MOR onset potential of 0.33 V and a high mass activity of 9.96 A mg Pt ⁻ 1 . It also delivers excellent hydrogen evolution performance with an overpotential of 23 mV at 10 mA cm⁻ 2 in acidic media. Mechanistic investigations reveal that the coupled electronic and interfacial effects shift the reaction pathway toward rapid oxidative conversion of intermediates, effectively suppressing CO poisoning. Furthermore, a hybrid acid/alkali methanol-hydrogen fuel cell incorporating this catalyst enables simultaneous hydrogen production, formate generation, and electricity output with stable operation over 250 h. This work provides a general strategy for integrating electronic and interfacial regulation in high-entropy intermetallics for efficient energy conversion. Download: Download high-res image (260KB) Download: Download full-size image Synergistic electron-deficient Pt sites and hydroxyl-rich interfaces in a high-entropy intermetallic catalyst enable kinetically accelerated methanol oxidation for efficient hydrogen and formate co-production.