Conductive Metal‐Organic Frameworks Bearing M−O₄ Active Sites as Highly Active Biomass Valorization Electrocatalysts

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The electrochemical oxidation of the biomass platform 5‐hydroxymethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA), is an important reaction in the emerging area of renewable energy‐powered biomass valorization. A key limitation in this field is the ill‐defined nature of the catalytic sites of the highest‐performing materials that limits the fundamental insights that can be extracted. To this end, a conductive metal‐organic framework‐based electrocatalytic model system with well‐defined M−O 4 active sites for electrochemical HMF oxidation was developed. These materials were found to be highly active towards FDCA generation, with product yields of over 95 %. In parallel, infrared spectroscopy was employed to capture a surface‐bound aldehyde group as the key intermediate in the catalytic cycle, which forms once M(II/III) oxidation occurs. This work illustrates the advantage of utilizing molecularly defined active sites coupled with operando spectroscopy to provide fundamental insights into a variety of electrosynthetic reactions and thus paves the way for future catalyst design.