Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates

Chadderdon, Xiaotong H.; Chadderdon, David J.; Matthiesen, John E.; Qiu, Yang; Carraher, Jack M.; Tessonnier, Jean-Philippe; Li, Wenzhen

doi:10.1021/jacs.7b06331

Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates

Journal Article · Wed Sep 13 00:00:00 EDT 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b06331· OSTI ID:1394816

Chadderdon, Xiaotong H. ^[1]; Chadderdon, David J. ^[1]; Matthiesen, John E. ^[2]; Qiu, Yang ^[1]; Carraher, Jack M. ^[3]; Tessonnier, Jean-Philippe ^[2]; Li, Wenzhen ^[1]

Iowa State Univ., Ames, IA (United States). Dept. of Chemical and Biological Engineering; Ames Lab., Ames, IA (United States)
Iowa State Univ., Ames, IA (United States). Dept. of Chemical and Biological Engineering; Ames Lab., Ames, IA (United States); NSF Engineering Research Center for Biorenewable Chemicals (CBiRC), Ames, IA (United States)
Iowa State Univ., Ames, IA (United States). Dept. of Chemical and Biological Engineering; NSF Engineering Research Center for Biorenewable Chemicals (CBiRC), Ames, IA (United States)

Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. Understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. Here, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions of each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. By understanding the underlying mechanisms it enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1394816

Report Number(s):: IS-J--9446

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 40 Vol. 139; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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