Kinetics and mechanism of 5-hydroxymethylfurfural oxidation and their implications for catalyst development

• Kinetics of hydroxymethylfurfural (HMF) oxidation were studied.
• Kinetics of hydroxymethylfurancarboxylic acid oxidation were investigated.
• The mechanism of base-free HMF oxidation over Pt was elucidated.
• Non-microporous carbon nanofibers (CNFs) were functionalized with acid and base sites.
• Au and Pt catalysts supported on CNFs were characterized and used for HMF oxidation.

The reaction mechanism of 5-hydroxymethylfurfural (HMF) oxidation in neutral aqueous solution with O2 to 5-hydroxymethyl-2-furancarboxylic acid (HFCA) and 2,5-furandicarboxylic acid (FDCA) was evaluated over a 3 wt% Pt/activated carbon catalyst in a semibatch reactor and confirmed that the mechanism was the same as that determined at high pH. In addition, the reaction kinetics of intermediate HFCA oxidation to FDCA over supported Pt at high pH were investigated. The combination of reaction kinetics and isotopic labeling studies using 18O-labeled H2O and O2 was used to suggest a reaction mechanism in which H2O inserts oxygen into the product and O2 scavenges electrons from the metal catalyst. Carbon nanofibers (CNF) containing excess acid or base groups were also used as supports for Pt and Au nanoparticles and evaluated as catalysts in HMF oxidation. Although the CNF-supported samples catalyzed HMF oxidation at rates similar to other carbon-supported Pt and Au catalysts, the CNF support with basic groups improved the ability of supported Au to form FDCA from HMF under mild conditions.

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