Immobilised Ruthenium Complexes for the Electrooxidation of 5-Hydroxymethylfurfural.

Abundantly available biomass-based platform chemicals, including 5-hydroxymethylfurfural (HMF), are essential stepping stones in steering the chemical industry away from fossil fuels. The efficient catalytic oxidation of HMF to its diacid derivative, 2,5-furandicarboxylic acid (FDCA), is a promising research area with potential applications in the polymer industry. Currently, the most encouraging approaches are based on solid-state catalysts and are often conducted in basic aqueous media, conditions where HMF oxidation competes with its decomposition. Efficient molecular catalysts are practically unknown for this reaction. In this study, we report on the synthesis and electrocatalysis of surface-bound molecular ruthenium complexes for the transformation of HMF to FDCA under acidic conditions. Catalyst immobilisation on mesoporous indium tin oxide electrodes is achieved through the incorporation of phosphonic acid anchoring groups. Screening experiments with HMF and further reaction intermediates revealed the catalytic route and bottlenecks in the catalytic synthesis of FDCA. Utilising these immobilised electrocatalysts, FDCA yields of up to 85 % and faradaic efficiencies of 91 % were achieved, without any indication of substrate decomposition. Surface analysis by X-ray photoelectron spectroscopy (XPS) post-electrocatalysis unveiled the desorption of the catalyst from the electrode surface as a limiting factor in terms of catalytic performance.