Pulcherrimin: a bio-derived iron chelate catalyst for base-free oxidation of 5-hydroxymethylfurfural to furandicarboxylic acid.

Abstract

This study explores the green and sustainable catalytic properties of pulcherrimin, a naturally occurring iron chelate, for the base-free oxidation of 5-hydroxymethylfurfural (5-HMF) to high-value products such as 2,5-furandicarboxylic acid (FDCA), a vital precursor for renewable bioplastics. Pulcherrimin, derived from Metschnikowia pulcherrima, selectively oxidised 5-HMF to 5,5-diformylfuran (DFF) at 100 °C, while at 120 °C, the oxidation proceeded efficiently to FDCA with a conversion of 73.3 ± 1.1%, and FDCA selectivity of 89.0 ± 1.9% under mild, base-free conditions. Adding a mild base enhanced overall conversion but diverted the reaction pathway towards 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), reducing the FDCA yield. The reusability of the pulcherrimin catalyst was tested over five reaction cycles, retaining a conversion activity of 59.1% and FDCA selectivity of 39.8%. These findings establish pulcherrimin as a promising, water-tolerant biocatalyst with potential environmental advantages, such as base-free operation and simplified product recovery, contributing to greener catalytic processes. Eliminating a homogenous base co-catalyst makes the process greener by avoiding the need for subsequent neutralisation steps while reducing environmental and economic costs.