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

Abstract 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.