Pt single atoms anchored on CoOx nanoislands for efficient biomass-derived 5-methylfurfural production

Abstract

The targeted hydrogenolysis of lignocellulose-derived 5-hydroxymethylfurfural (HMF) to 5-methylfurfural (5-MF) is challenged by competitive activation of aldehyde (CO) versus hydroxyl (C–OH) groups. Here, we designed a novel atomically precise Pt₁-CoO_x#TiO₂ catalyst, featuring Pt single atoms (Pt SAs) anchored on TiO₂-supported CoO_x nanoislands (∼5–10 nm), which achieves exceptional HMF conversion (95%) and high 5-MF selectivity (>99%) under given conditions. Through advanced structural characterization and controlled experiments, we revealed a cooperative metal–acid synergy: the Co²⁺-rich CoO_x nanoislands provide oxygen vacancies and Lewis acidic sites for selective C–OH activation, while Pt SAs enriched on the CoO_x nanoisland form high-density active metal centers that significantly enhance hydrogen dissociation. This dual functionality synergistically promotes dehydroxylation while simultaneously suppressing undesired aldehyde hydrogenation through weak CO adsorption on both Pt SAs and CoO_x sites. The precisely engineered single-atom/nanoisland architecture demonstrates an efficient strategy to enable functional-group-selective transformations, offering a sustainable strategy for biomass upgrading.