Selective oxidation of ethanol on a nickel foam electrode followed by aldol condensation with furfural: An electrochemical approach for utilization of biomass-derived molecules

Authors: Manamperi, Hemanthi; Jackson, Michael; Wegener, Evan; Vermillion, Karl

Submitted to: ACS Electrochemistry
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: 11/13/2024
Publication Date: 3/6/2025
Citation: Manamperi, H.D., Jackson, M.A., Wegener, E.C., Vermillion, K.E. 2025. Selective oxidation of ethanol on a nickel foam electrode followed by aldol condensation with furfural: an electrochemical approach for the utilization of biomass-derived molecules. ACS Electrochemistry. 1(3):369-377. https://doi.org/10.1021/acselectrochem.4c00094.
DOI: https://doi.org/10.1021/acselectrochem.4c00094

Interpretive Summary: Ethanol is a renewable fuel made predominantly from corn in the United States. In an effort to further expand the market potential beyond its use as a transportation fuel, researchers at the USDA, Agricultural Research Service in Peoria, Illinois, developed new technologies to convert ethanol to chemicals used in production of numerous consumer goods. This was accomplished by using electrical energy to facilitate an electrochemical conversion reaction in the presences of furfural, a biobased chemical made from corn cobs. Ethanol is first converted to acetaldehyde, which had a global market size of USD 1.63 billion in 2023, and then to 3-(2-furyl)acrolein or F2A for use in foods, cosmetics, medicine, and agriculture. This process is advantageous over current methods because the electrical energy to drive the reaction can be derived from renewable resources. This work will benefit corn growers, operators of biorefineries, and the rural economy.

Technical Abstract: An electrochemical method was developed to achieve the oxidative aldol condensation of ethanol with biomass-derived furfural under ambient conditions. The product distribution was composed of 3-(2-furyl)acrolein (F2A) as the major product and 5-(2-furanyl)-2,4-pentadienal (F24P) as the minor product resulting from the cross aldol condensation of F2A with a second acetaldehyde molecule. The latter reaction step was successfully eliminated to achieve a single product 3-(2-furanyl)-2-methyl-2-propenal (F22P) simply by substituting ethanol with 1-propanol. Over 90% Faradaic efficiency for the electrochemical step was achieved in 0.5 M KOH and 50% aqueous ethanol at a nickel foam anode. In addition, the same anode and cathode electrodes can be used up to four times without compromising the efficiency of the overall process, thus highlighting nickel foam as an inexpensive and robust anode material for ethanol to acetaldehyde oxidation.