Pt/PtO2 heterostructure enable heterolytic H2 activation for low-temperature hydrogenation of industrially relevant concentrated HMF to BHMF in water

The aqueous-phase hydrogenation of concentrated 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) is a crucial transformation for sustainable chemical production. However, this process is often limited by sluggish H 2 activation at low temperatures and poor selectivity arising from over-hydrogenation. Here, we develop a Pt catalyst supported on oxygen-deficient manganese oxide (Pt/MnO x –O v ), featuring finely dispersed Pt/PtO 2 domains in conjunction with abundant Pt–O–Mn interfacial ensembles. Under mild aqueous conditions (30–60 °C), the catalyst efficiently converts HMF at concentrations up to 40 wt%, delivering a BHMF yield of 90.9 %. In addition, continuous-flow operation at 30 °C sustains BHMF yields above 90 % over a cumulative operation time of 80 h, thereby demonstrating promising potential for industrial application. Mechanistic studies suggest that hydrogen is initially activated on Pt nanoparticles and subsequently undergoes in situ spillover, migrating across the Pt/PtO 2 heterostructure toward adjacent Pt–O–Mn interfacial sites. At these interfacial regions, the asymmetric electronic distribution, induced by nearby oxygen vacancies, facilitates the formation of polarized H δ+ –H δ- species. These reactive hydrogen species, together with the preferential adsorption of the carbonyl group, enable selective hydrogenation while suppressing undesired side reactions. This study demonstrates that tailoring interfacial structures is an effective strategy for improving catalytic performance in biomass upgrading.