Carbon materials with hierarchical morphologies, pores, and compositions have attracted extraordinary attention due to their unique structural advantages and widespread applications. However, their controllable synthesis remains a grand challenge. Herein, a solvent-mediated strategy was demonstrated for the preparation of an urchin-like superstructure via modulating the hydrothermal condition (acetic acid/water ratio) of metal-organic frameworks (MOFs). The direct pyrolysis of a hierarchical NUS-6 precursor produced a well-defined carbon-based composite consisting of sulfur-doped carbon (SC) and HfO2 with an urchin-like morphology and micro-/mesoporosity, while the doped S sites and oxygen vacancies of HfO2 can help to anchor and activate Pd nanoparticles (NPs) through the strong host-guest interaction, which was further confirmed by the calculated results of the binding energy and differential charge density through density functional theory (DFT). The synthesized Pd@SC/HfO2 composite exhibited extremely high catalytic activity and stability toward the water-phase hydrodeoxygenation of vanillin (conversion >99%, selectivity >99%), as well as good universality for the hydrogenation of a series of unsaturated hydrocarbons in an aqueous system. Remarkably, the catalytic activity and structural stability of Pd@SC/HfO2 were largely maintained even after successive 10 cycles.
Keywords: MOFs; carbon composites; hierarchy; host−guest interaction; hydrogenation catalysis.