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Title: Mechanistic Insights Evaluating Ag, Pb, and Ni as Electrocatalysts for Furfural Reduction from First-Principles Methods

Abstract

Electrochemical reduction of furfural (ECRFF) emerges as an efficient and sustainable means to obtain high-value chemicals and biofuels with the activity and product selectivity being sensitive to cathode materials. In this work, elementary steps describing furfuryl alcohol (FA) and 2-methylfuran (MF) production routes in ECRFF are studied by using periodic density functional theory on Ag, Pb, and Ni, as alternative cathode materials. The established Brønsted–Evans–Polanyi (BEP) relationship has been proven to be reliable to estimate energy barriers of C–O bond cleavage. The intrinsic characters of Ag, Pb, and Ni are then summarized in free energy diagrams to reflect the FA and MF production trends as future guidelines to evaluate ECRFF activity and selectivity on these metals. On all metal surfaces, at both terrace and stepped sites, the first C–H or O–H hydrogenation step, producing respective mh6 or mh7 intermediates, influences overall FA production. On Ag and Pb, pathways involving the mh6 intermediate are thermodynamically and kinetically favored, whereas on Ni, both mh6 and mh7 routes are competitive due to strong interactions between the furan ring and the substrate. In addition, these partially hydrogenated intermediates can also undergo C–O bond cleavage with reduced energy barriers (compared to direct C–O bond cleavagemore » in furfural), which opens potential paths for parallel MF production. Conversion of FA into MF catalyzed by these metallic cathodes was considered as well, although the high C–O bond cleavage energy barrier is likely to hinder this process.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Kansas State Univ., Manhattan, KS (United States). Dept. of Chemical Engineering
  2. Univ. of Rochester, NY (United States). Dept. of Chemical Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1482388
Grant/Contract Number:  
[AC02-05CH11231; AC02-06CH11357]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
[ Journal Volume: 121; Journal Issue: 46]; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Shan, Nannan, Hanchett, Mary K., and Liu, Bin. Mechanistic Insights Evaluating Ag, Pb, and Ni as Electrocatalysts for Furfural Reduction from First-Principles Methods. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b06778.
Shan, Nannan, Hanchett, Mary K., & Liu, Bin. Mechanistic Insights Evaluating Ag, Pb, and Ni as Electrocatalysts for Furfural Reduction from First-Principles Methods. United States. doi:10.1021/acs.jpcc.7b06778.
Shan, Nannan, Hanchett, Mary K., and Liu, Bin. Tue . "Mechanistic Insights Evaluating Ag, Pb, and Ni as Electrocatalysts for Furfural Reduction from First-Principles Methods". United States. doi:10.1021/acs.jpcc.7b06778. https://www.osti.gov/servlets/purl/1482388.
@article{osti_1482388,
title = {Mechanistic Insights Evaluating Ag, Pb, and Ni as Electrocatalysts for Furfural Reduction from First-Principles Methods},
author = {Shan, Nannan and Hanchett, Mary K. and Liu, Bin},
abstractNote = {Electrochemical reduction of furfural (ECRFF) emerges as an efficient and sustainable means to obtain high-value chemicals and biofuels with the activity and product selectivity being sensitive to cathode materials. In this work, elementary steps describing furfuryl alcohol (FA) and 2-methylfuran (MF) production routes in ECRFF are studied by using periodic density functional theory on Ag, Pb, and Ni, as alternative cathode materials. The established Brønsted–Evans–Polanyi (BEP) relationship has been proven to be reliable to estimate energy barriers of C–O bond cleavage. The intrinsic characters of Ag, Pb, and Ni are then summarized in free energy diagrams to reflect the FA and MF production trends as future guidelines to evaluate ECRFF activity and selectivity on these metals. On all metal surfaces, at both terrace and stepped sites, the first C–H or O–H hydrogenation step, producing respective mh6 or mh7 intermediates, influences overall FA production. On Ag and Pb, pathways involving the mh6 intermediate are thermodynamically and kinetically favored, whereas on Ni, both mh6 and mh7 routes are competitive due to strong interactions between the furan ring and the substrate. In addition, these partially hydrogenated intermediates can also undergo C–O bond cleavage with reduced energy barriers (compared to direct C–O bond cleavage in furfural), which opens potential paths for parallel MF production. Conversion of FA into MF catalyzed by these metallic cathodes was considered as well, although the high C–O bond cleavage energy barrier is likely to hinder this process.},
doi = {10.1021/acs.jpcc.7b06778},
journal = {Journal of Physical Chemistry. C},
number = [46],
volume = [121],
place = {United States},
year = {2017},
month = {10}
}

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Cited by: 6 works
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Figures / Tables:

Scheme 1 Scheme 1: Routes for Electrochemical Reduction of Furfural (ECRFF) to Furfuryl Alcohol (FA) and 2-methylfuran (MF).

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.