Modulating d-band center to construct Ptδ–Cuδ+ pairs for selective hydrogenation of renewable furfural

Addressing the key challenges of controllable hydrogen transfer and directional C O bond activation in Meerwein-Ponndorf-Verley (MPV) reactions, this study constructed a Pt-CuO/Al 2 O 3 catalyst featuring Pt δ- Lewis acid-metal pairs for selective hydrogenation of biomass-derived furfural via the MPV reduction pathway. Under optimized conditions, the catalyst achieved 99.9% conversion with 98.0% selectivity. Density functional theory (DFT) analysis revealed that compared to isolated Pt, the d -band center of Pt in Pt-CuO/Al 2 O 3 shifts downward by 0.14 eV, while the d -band center of Cu shifts upward by 0.28 eV. Combined with the distinct metal-support interactions observed in EXAFS spectra, these results confirm that d -band center modulation creates a synergistic electronic structure of Pt δ– Cu δ+ : the upshifted d -band center of Cu δ+ enhances oxygen affinity, promoting co-adsorption of carbonyl and hydroxyl groups and facilitating six-membered ring transition state formation, while the downshifted d -band center of Pt δ- optimizes hydrogen transfer through interfacial electron transfer (Cu → Pt). These findings demonstrate the stable coordination environment of these Lewis acid-metal pairs. This work reveals the synergistic mechanism of Pt δ– Cu δ+ active sites and elucidates the cooperative “metal electron enrichment-oxide electron deficiency” effect in MPV reactions, providing new insights for designing highly efficient and selective biomass hydrogenation catalysts.