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Article
Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates
Ames Laboratory Accepted Manuscripts
  • Xiaotong H. Chadderdon, Iowa State University and Ames Laboratory
  • David J. Chadderdon, Iowa State University and Ames Laboratory
  • John E. Matthiesen, Iowa State University and Ames Laboratory
  • Yang Qiu, Iowa State University and Ames Laboratory
  • Jack M. Carraher, Iowa State University
  • Jean-Philippe Tessonnier, Iowa State University and Ames Laboratory
  • Wenzhen Li, Iowa State University and Ames Laboratory
Publication Date
1-1-2017
Department
Ames Laboratory; Chemical and Biological Engineering; 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
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
Publisher
Iowa State University Digital Repository, Ames IA (United States)
Citation Information
Xiaotong H. Chadderdon, David J. Chadderdon, John E. Matthiesen, Yang Qiu, et al.. "Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates" Vol. 139 Iss. 40 (2017) p. 14120 - 14128
Available at: http://works.bepress.com/jean-philippe_tessonnier/19/