Tuning d-band center of platinum enables selective hydrogenative rearrangement of furfural
The hydrogenative rearrangement of biomass-derived furfural offers a sustainable pathway to produce cyclopentanol (CPL) and cyclopentanone (CPO), which are traditionally obtained from fossil resources. Achieving selective synthesis of either product requires precise control over catalyst electronic structure and adsorption behavior, yet it still remains challenging. Herein, we report that both doping and tuning the spatial distance between Pt clusters effectively regulate the d -band center of active sites, enabling selective synthesis of CPO and CPL with high yields of 97.2 % and 96.0 %, respectively. Mechanistic studies suggest that reducing the spatial distance between Pt nanoclusters elevates the d -band center, thereby reducing the occupancy of antibonding states and strengthening the Pt-O bond between Pt and CPO, thus favoring CPL formation. By contrast, doping Pt with NiP lowers the d -band center, thus weakening CPO adsorption and promoting its selective synthesis. These results highlight d -band center regulation as a promising strategy for achieving selective hydrogenation.
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