Electrochemical Oxidation of HMF via Hydrogen Atom Transfer and Hydride Transfer on NiOOH and the Impact of NiOOH Composition

A great deal of attention has been directed toward studying the electrochemical oxidation of 5-hydroxymethylfurfural (HMF), a molecule that can be obtained from biomass-derived cellulose and hemicellulose, to 2,5-furandicarboxylic acid (FDCA), a molecule that can replace the petroleum-derived terephthalic acid in the production of widely used polymers such as polyethylene terephthalate. NiOOH is one of the best and most well studied electrocatalysts for achieving this transformation; however, the mechanism by which it does so is still poorly understood. This study quantitatively examines how two different dehydrogenation mechanisms on NiOOH impact the oxidation of HMF and its oxidation intermediates on the way to FDCA. The first mechanism is a well-established indirect oxidation mechanism featuring chemical hydrogen atom transfer to Ni