Regulating d-Band Center in Pt-Pd Metallene Aerogels for Enhanced Electrochemical Ethanol Reforming to Hydrogen

The ethanol oxidation reaction (EOR) serves as an attractive alternative to the sluggish oxygen evolution reaction in electrochemical hydrogen production cells. However, developing high-performance bifunctional electrocatalysts for EOR and the hydrogen evolution reaction (HER) remains a significant challenge. Herein, by introducing Pt into Pd metallene aerogels (MAs) (Pd₁₂Pt MAs) to construct bimetallic active sites, we regulated the d-band center of Pd MAs, achieving dual enhancement in both activity and stability for both HER and EOR. Specifically, Pd₁₂Pt MAs can be further utilized for coupled HER/EOR reaction to avoid large overpotentials from sluggish OER, requiring only 0.95 V to reach 10 mA·cm^-2 compared to 2.08 V for water splitting. Density functional theory calculations demonstrate that the incorporation of Pt into Pd MAs modulates the d-band center while creating dual active sites, thereby optimizing the adsorption energy of *CH₃CO and *H as well as reducing the energy barrier for the reactions. Additionally, Pt balances the electronic structure of adjacent Pd sites, effectively weakening the adsorption of hydrogen protons on the catalysts and promoting the reaction progression. Our work demonstrates that d-band center regulation of Pd-based MAs is conducive to improving the coupled electrolysis reactions of biomass upgrading and H₂ evolution with low energy demand.