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 (XPt₃, X = 3d transition metal) for furfural oxidation. Among the studied alloys, ZnPt₃ 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, ZnPt₃ suppresses competing reactions such as deep oxidation, non-selective dehydrogenation pathways, and oxygen evolution, ensuring high selectivity toward furoic acid. Furthermore, ZnPt₃ also exhibits high activity for hydrogen evolution at the cathode, suggesting its potential as a bifunctional catalyst for coupling anodic furfural oxidation with cathodic H₂ generation. These insights highlight ZnPt₃ as a promising and cost-effective catalyst for integrated electrochemical biomass valorization.