Mechanistic Insights into the Electrochemical Oxidation of 5-Hydroxymethylfurfural on a Thin-Film Ni Anode

• DOI: 10.1021/acscatal.4c01448
• Publication Date: 2024-06-20T15:04:41Z
• Authors: Aditya Prajapati; Nitish Govindarajan; Wenyu Sun; Jiayi Huang; Hossein Bemana; Jeremy T. Feaster; Sneha A. Akhade; Nikolay Kornienko; Christopher Hahn
• Keywords: Alcohol Oxidation; Partial oxidation; Oxidation state

The electrochemical oxidation of alcohols is being explored as a favorable substitute for the oxygen evolution reaction owing to its capability generate high-value products and lower overpotentials. Herein, we present systematic investigation into 5-hydroxymethylfurfural (HMF), model biomass platform chemical, on thin-film nickel catalyst, aiming investigate underlying mechanism shed light role catalyst's microenvironment phase activity product selectivity. Utilizing combined experimental computational approach, demonstrate that NiOOH active HMF oxidation. Additionally, find substantial impact environment, particularly electrolyte pH, reaction. Under highly alkaline conditions (pH = 13), higher observed, accompanied by an increased selectivity toward 2,5-furandicarboxylic acid (FDCA) production. Conversely, less environment 11) results in diminished preference partial 2,5-diformylfuran (DFF). Mechanistic insights from DFT studies reveal geminal diols are under undergo hydride transfer via HMFCA, while shift alkoxide route occurs at favoring DFF pathway. Hydride energetics also strongly affected surface Ni state. This integrated bridging insights, provides general framework investigating aldehydes alcohols, thereby advancing rational design strategies electrocatalysts alcohol electro-oxidation reactions.