ScholarWorks@숙명여자대학교

초록

The catalytic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) offers a sustainable pathway for biomass valorization; however, achieving base-free, efficient, and recyclable catalysis remains challenging. Herein, we report the rational design of chromium-modified Pt@Fe2-xCrxO3 nanocatalysts, synthesized via ethanolamine-assisted coprecipitation followed by platinum nanoparticle (approximate to 2.6 nm) deposition, for the aerobic oxidation of HMF under mild conditions. The isovalent substitution of Fe3+ with Cr3+ enhanced the oxygen vacancy concentration and surface acidity while strengthening the Pt-O interactions. The optimized Pt@Fe1.7Cr0.3O3 catalyst achieved nearly 100% HMF conversion with a 78.7% FDCA yield at 120 degrees C and 1 bar O-2 within 12 h, compared to only 41% yield over Pt@Fe2O3. Kinetic studies revealed first-order behavior with activation energies of 67.9 kJ mol(-1) for HMF conversion and 36.3 kJ mol(-1) for FDCA formation. The catalyst retained >90% of its activity after five consecutive cycles, demonstrating its excellent recyclability. Density functional theory calculations further confirmed that Cr doping increased the HMF adsorption energy (-67.0 vs -56.6 kcal mol(-1)) and raised the Pt d-band center, thereby promoting the generation of reactive oxygen species. This study establishes a quantitative and generalizable strategy for designing robust and recyclable catalysts for sustainable biomass conversion.

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