Publication Date

2017

Department

Ames Laboratory; Chemical and Biological Engineering; NSF Engineering Research Center for Biorenewable Chemicals

Campus Units

Chemical and Biological Engineering, Ames Laboratory, NSF Engineering Research Center for Biorenewable Chemicals

Report Number

IS-J 9446

DOI

10.1021/jacs.7b06331

Journal Title

Journal of the American Chemical Society

Volume Number

139

Issue Number

40

First Page

14120

Last Page

14128

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.

Language

en

Department of Energy Subject Categories

09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Publisher

Iowa State University Digital Repository, Ames IA (United States)

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