Crystal Faces-Tailored Oxygen Vacancy in Au/CeO₂ Catalysts for Efficient Oxidation of HMF to FDCA

Developing an efficient catalyst to upgrade 5-hydroxymethylfurfural (HMF) to high-value-added downstream chemicals is of great significance in biomass conversion. Nanorod (110)-, nanocube (100)-, and nanooctaheron (111)-CeO₂ -supported Au nanoparticles were prepared to investigate the intrinsic effect of CeO₂ crystal faces on the oxidation of HMF to 2,5-furandicarboxylic acid (FDCA). The experimental results and density functional theory calculation revealed that the concentration of oxygen vacancy (V_O ) for exposed specific crystal faces was crucial to the oxygen adsorption ability, and Au/nanorod-CeO₂ with the highest V_O concentration promoted the formation of more oxygen active species (superoxide radical) on CeO₂ (110) crystal face than (100) and (111) crystal faces. Besides, the higher V_O concentration could provide a strong adsorption ability of HMF, greatly boosting the activation of HMF. Thus, these results led to a superior catalytic activity for HMF oxidation over Au/nanorod-CeO₂ (FDCA yield of 96.5 %). In-situ Fourier-transform (FT)IR spectroscopy uncovered the HMF oxidation pathway, and the possible catalytic mechanism was proposed. The deep insight into the role of regulation for crystal faces provides a basis for the rational design of highly active facets for the oxidation of HMF and related reactions.