Gas Phase Hydrogenation of Furaldehydes via Coupling with Alcohol Dehydrogenation over Ceria Supported Au-Cu

We have investigated the synthesis and application of Au-Cu/CeO₂ (Cu: Au = 2) in the continuous gas phase (P = 1 atm; T = 498 K) coupled hydrogenation of 5-hydroxymethyl-2-furaldehyde (HMF) with 2-butanol dehydrogenation. STEM-EDX analysis revealed a close surface proximity of both metals in Au-Cu/CeO₂ post-TPR. XPS measurements suggest (support → metal) charge transfer to form Au^- and strong metal-support interactions to generate Cu⁰ and Cu⁺. Au-Cu/CeO₂ promoted the sole formation of 2,5-dihydroxymethylfuran (DHMF) and 2-butanone in the HMF/2-butanol coupling with full hydrogen utilisation. Under the same reaction conditions, Au/CeO₂ was fully selective to DHMF in standard HMF hydrogenation (using an external hydrogen supply), but delivered a lower production rate and utilised less than 0.2% of the hydrogen supplied. Exclusive -C=O hydrogenation and -OH dehydrogenation is also demonstrated for the coupling of a series of m-substituted (-CH₃, -CH₂CH₃, -CH₂OH, -CF₃, -N(CH₃)₂, -H) furaldehydes with alcohol (1-propanol, 1-butanol, 2-propanol, 2-butanol, cyclohexanol) dehydrogenation over Au-Cu/CeO₂, consistent with a nucleophilic mechanism. In each case, we observed a greater hydrogenation rate and hydrogen utilisation efficiency with a 3⁻15 times lower E-factor in the coupling process relative to standard hydrogenation. Our results demonstrate the feasibility of using hydrogen generated in situ through alcohol dehydrogenation for the selective hydrogenation of m-furaldehydes with important industrial applications.