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

TitleMechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates
Publication TypeJournal Article
Year of Publication2017
AuthorsChadderdon, XH, Chadderdon, DJ, Matthiesen, JE, Qiu, Y, Carraher, JM, Tessonnier, JP, Li, WZ
JournalJournal of the American Chemical Society
Volume139
Pagination14120-14128
Date Published10
Type of ArticleArticle
ISBN Number0002-7863
Accession NumberWOS:000413057100031
Keywords2,5-bis(hydroxymethyl)furan, 2-mercaptobenzothiazole, chemistry, conversion, copper, electrocatalytic hydrogenation, furanic compounds, junctions, microscopy, molecular, organic-compounds, self-assembled monolayers
Abstract

Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. However, understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. In this work, 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. Understanding the underlying mechanisms 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.

DOI10.1021/jacs.7b06331
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