Electronegativity Induced d-Band Center Offset for Pt-Rh Dual Sites in High-Entropy Alloy Boosts Liquid Fuels Electrooxidation

Investigating the catalytic behavior of the liquid fuels on well-defined dual sites is crucial in understanding electrocatalytic reactions. Herein, concept holding bidirectional electronegativity dominant d-band center regulation on Pt-Rh dual sites is proposed to tailor the catalytic behaviors toward methanol oxidation reaction (MOR). The Pt-Rh dual sites are engineered by introducing the low-electronegativity Ga/Ni and high-electronegativity W elements in PtRhGaNiW high-entropy alloy (HEA), which can drive the electron cloud of Pt-Rh dual sites redispersing over a wide orbit window. The optimized Pt-Rh dual sites in PtRhGaNiW HEA nanowire achieve a high current density of 5.61 mA cm⁻² toward MOR, which is 3.38 and 9.75 times than that of PtRh alloy (1.66 mA cm⁻²) and Pt/C (0.57 mA cm⁻²), as well as remarkably stability and CO_ads poisonous resistance. The theoretical calculations further disclose that the redistribution of surface localized electron around Pt-Rh dual sites can promote direct oxidation of ─OH, and accelerate the CO_ads oxidation/removal. This work presents a breakthrough in designing advanced dual site electrocatalysts for complex catalytic reactions.