Bifunctional Pt-based alloys for furfural electro-oxidation coupled with green hydrogen production.

The electrochemical oxidation of furfural (FF) to furoic acid (FFA) offers a sustainable pathway for upgrading biomass-derived platform molecules into high-value chemicals. In this study, density functional theory (DFT) calculations were employed to investigate the activity, selectivity, and mechanistic features of Pt-based intermetallic alloys (XPt, X = 3d transition metal) for furfural oxidation. Among the studied alloys, ZnPt exhibits the most favorable performance, with a significantly lower free energy change (0.33 eV) for the potential-determining step (hydroxyl adsorption) compared to pure Pt (0.84 eV). Electronic structure analysis reveals that Zn doping induces a downshift in the d-band center, reduces the work function, and enhances charge transfer to the adsorbed furfural, thereby facilitating dehydrogenation and subsequent transformation steps. Additionally, ZnPt suppresses competing reactions such as deep oxidation, non-selective dehydrogenation pathways, and oxygen evolution, ensuring high selectivity toward furoic acid. Furthermore, ZnPt also exhibits high activity for hydrogen evolution at the cathode, suggesting its potential as a bifunctional catalyst for coupling anodic furfural oxidation with cathodic H generation. These insights highlight ZnPt as a promising and cost-effective catalyst for integrated electrochemical biomass valorization.