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

Abstract

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.

Authors:
 [1];  [1];  [2];  [1];  [3];  [2];  [1]
  1. Iowa State Univ., Ames, IA (United States). Dept. of Chemical and Biological Engineering; Ames Lab., Ames, IA (United States)
  2. 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)
  3. 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)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
1394816
Report Number(s):
IS-J-9446
Journal ID: ISSN 0002-7863; TRN: US1702387
Grant/Contract Number:  
AC02-07CH11358; NSF-CBET 1512126
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 40; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Chadderdon, Xiaotong H., Chadderdon, David J., Matthiesen, John E., Qiu, Yang, Carraher, Jack M., Tessonnier, Jean-Philippe, and Li, Wenzhen. Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates. United States: N. p., 2017. Web. doi:10.1021/jacs.7b06331.
Chadderdon, Xiaotong H., Chadderdon, David J., Matthiesen, John E., Qiu, Yang, Carraher, Jack M., Tessonnier, Jean-Philippe, & Li, Wenzhen. Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates. United States. doi:10.1021/jacs.7b06331.
Chadderdon, Xiaotong H., Chadderdon, David J., Matthiesen, John E., Qiu, Yang, Carraher, Jack M., Tessonnier, Jean-Philippe, and Li, Wenzhen. Wed . "Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates". United States. doi:10.1021/jacs.7b06331. https://www.osti.gov/servlets/purl/1394816.
@article{osti_1394816,
title = {Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates},
author = {Chadderdon, Xiaotong H. and Chadderdon, David J. and Matthiesen, John E. and Qiu, Yang and Carraher, Jack M. and Tessonnier, Jean-Philippe and Li, Wenzhen},
abstractNote = {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.},
doi = {10.1021/jacs.7b06331},
journal = {Journal of the American Chemical Society},
number = 40,
volume = 139,
place = {United States},
year = {Wed Sep 13 00:00:00 EDT 2017},
month = {Wed Sep 13 00:00:00 EDT 2017}
}

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