Efficient electrolysis of 5-hydroxymethylfurfural to the biopolymer-precursor furandicarboxylic acid in a zero-gap MEA-type electrolyzer

Replacement of today’s established chemical production processes by “green” sustainable alternatives has become a scientific priority. The oxidative conversion of 5-hydroxymethylfurfural (5-HMF) to the biopolymer component 2.5-furandicarboxylic acid paired with green electrolytic hydrogen production is a promising emerging green process. Here, we present a family of active selective and stable interlayer anion-tuned NiX (X = Fe, Mn, Co, V) bimetallic-layered, double-hydroxide catalysts for the selective oxidation of 5-HMF to 2.5-furandicarboxylic acid in a zero-gap MEA-type electrolyzer. We report that tuning the structural interlayer distance of the catalyst by anion exchange gives rise to previously unachieved catalytic performance for the anodic production of the biopolymer building block. Operando differential electrochemical mass spectrometry analysis reveals the electrode window for the perfectly selective HMF conversion. The role of the catalyst dopants, their real surface areas, the stability of the catalytic interface, and aspects of its favorable techno-economics are discussed. • Active, selective, and stable interlayer anion-tuned catalyst for biomass oxidation • Operating in a zero-gap MEA-type single electrolyzer cell • Operando analysis revealed the perfectly selective HMF conversion window Strasser et al. present a family of active selective and stable Ni-based catalysts for the selective oxidation of biomass in an electrolyzer. The biomass electrolysis device yields previously unachieved production of a biopolymer precursor and may offer techno-economic cost advantages.