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High Resolution Image Download MS PowerPoint Slide The sustainable production of biobased fuels and chemicals necessitates energy-efficient catalytic processes for biomass upgrading. As a pivotal biorefinery platform compound, 2,5-furandicarboxylic acid (FDCA) synthesis via 5-hydroxymethylfurfural (HMF) oxidation requires highly active catalytic systems for high-yield production under mild conditions. This study systematically investigates the structure–activity relationship of morphology-controlled cerium oxide (CeO 2 ) in tert -butyl hydroperoxide (TBHP)-mediated oxidation of HMF to FDCA using Au/CeO 2 catalysts. Remarkably, the rod-shaped Au/CeO 2 catalyst exhibited exceptional performance with 82.59% FDCA yield achieved within merely 2 min at 90 °C, significantly outperforming cubic (22.59%) and octahedral (10.61%) counterparts. Through comprehensive characterization, we established that the enhanced catalytic efficiency directly correlates with the facet-dependent oxygen vacancy (V O ) concentration. The rod-CeO 2 predominantly exposing (110)/(100) facets demonstrated the highest V O density, which facilitated optimal Au nanoparticle dispersion (2.99 nm) and catalytic activity. In contrast, cubic and octahedral CeO 2 with lower V O concentrations suffered from Au nanoparticle aggregation, leading to a diminished performance. Kinetic studies revealed a sequential oxidation pathway (HMF→HMFCA→FFCA→FDCA), where the HMFCA→FFCA transition was identified as the rate-determining step. The catalyst maintained excellent stability (>78% FDCA yield after five consecutive cycles). These findings provide fundamental insights into facet-dependent catalysis in peroxide-mediated oxidation systems and establish actionable design principles for morphology-controlled catalysts in next-generation biomass valorization technologies.
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