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Investigating the Nature of the Active Sites for the CO 2 Reduction Reaction on Carbon-Based Electrocatalysts

35 Pages Posted: 19 Mar 2019 Sneak Peek Status: Review Complete

See all articles by Tristan Asset

Tristan Asset

University of California, Irvine - Department of Chemical and Biomolecular Engineering

Samuel T. Garcia

University of New Mexico - Department of Chemical and Biological Engineering

Sergio Herrera

University of New Mexico - Department of Chemical and Biological Engineering

Nalin Andersen

University of New Mexico - Department of Chemical and Biological Engineering

Yechuan Chen

University of California, Irvine - Department of Chemical and Biomolecular Engineering

Eric J. Peterson

University of New Mexico - Department of Chemical and Biological Engineering

Ivana Matanovic

University of New Mexico - Department of Chemical and Biological Engineering; Los Alamos National Laboratory - Theoretical Division

Kateryna Artyushkova

University of New Mexico - Department of Chemical and Biological Engineering

Jack Lee

University of Utah - Department of Chemistry

Shelley D. Minteer

University of Utah - Department of Chemistry

Sheng Dai

University of California, Irvine - Department of Materials Science and Engineering

Xiaoqing Pan

University of California, Irvine - Department of Materials Science and Engineering; University of California, Irvine - Department of Physics and Astronomy; University of California, Irvine - Irvine Materials Research Institute (IMRI)

Kanchan Chavan

Michigan State University - Department of Chemical and Materials Engineering

Scott Calabrese Barton

Michigan State University - Department of Chemical and Materials Engineering

Plamen Atanassov

University of California, Irvine - Department of Chemical and Biomolecular Engineering; University of New Mexico - Department of Chemical and Biological Engineering

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Abstract

To achieve a better understanding of the CO2 reduction reaction on carbon-based electrocatalysts, we synthesized a library of nitrogen-doped carbonaceous materials with atomically dispersed 3d transition metals and corresponding metal-free electrocatalysts. The sacrificial support method was used yielding catalyst materials of high dispersity and high graphitic content. The resulting electrocatalysts were impurity free, hence allowing a better understanding of the mech-anism of CO2 reduction. By combining the electrochemical results with density functional theo-ry, we were able to separate the electrocatalysts into several categories, based on their CO2 → COOHads free energy and their COads binding strength. The ‘strong-CO binder’ electrocatalysts (e.g. Cr, Mn and Fe – N – C) achieved a Faradaic efficiency up to 50% at – 0.35 V vs. RHE (at pH = 7.5, in 0.1 M phosphate buffer). Such Faradaic efficiency was also achieved for a metal-free electrocatalyst, therefore showing the high activity of the metal-free, N-containing, moieties toward the CO2 reduction reaction. This was confirmed by near ambient pressure X-ray photoe-lectron spectroscopy that confirmed pyridinic and hydrogenated (pyrrolic) nitrogen moieties act as preferential absorption sites for the CO2 on the Fe – N – C catalyst surface.

Keywords: Nitrogen-doped carbonaceous materials; transition metal-nitrogen-carbon catalysts; atomically dispersed transition metal sites; CO2 reduction reaction; near ambient pressure X-ray photoelectron spectroscopy; density functional theory

Suggested Citation

Asset, Tristan and Garcia, Samuel T. and Herrera, Sergio and Andersen, Nalin and Chen, Yechuan and Peterson, Eric J. and Matanovic, Ivana and Artyushkova, Kateryna and Lee, Jack and Minteer, Shelley D. and Dai, Sheng and Pan, Xiaoqing and Chavan, Kanchan and Barton, Scott Calabrese and Atanassov, Plamen, Investigating the Nature of the Active Sites for the CO 2 Reduction Reaction on Carbon-Based Electrocatalysts (March 16, 2019). Available at SSRN: https://ssrn.com/abstract=3353708 or http://dx.doi.org/10.2139/ssrn.3353708
This is a paper under consideration at Cell Press and has not been peer-reviewed.

Tristan Asset

University of California, Irvine - Department of Chemical and Biomolecular Engineering

P.O. Box 19556
Irvine, CA 62697-3125
United States

Samuel T. Garcia

University of New Mexico - Department of Chemical and Biological Engineering

Albuquerque, NM 87131-1221
United States

Sergio Herrera

University of New Mexico - Department of Chemical and Biological Engineering

Albuquerque, NM 87131-1221
United States

Nalin Andersen

University of New Mexico - Department of Chemical and Biological Engineering

Albuquerque, NM 87131-1221
United States

Yechuan Chen

University of California, Irvine - Department of Chemical and Biomolecular Engineering

P.O. Box 19556
Irvine, CA 62697-3125
United States

Eric J. Peterson

University of New Mexico - Department of Chemical and Biological Engineering

Albuquerque, NM 87131-1221
United States

Ivana Matanovic

University of New Mexico - Department of Chemical and Biological Engineering

Albuquerque, NM 87131-1221
United States

Los Alamos National Laboratory - Theoretical Division

Los Alamos, NM 87545
United States

Kateryna Artyushkova

University of New Mexico - Department of Chemical and Biological Engineering

Albuquerque, NM 87131-1221
United States

Jack Lee

University of Utah - Department of Chemistry

1645 E. Campus Center
Salt Lake City, UT 84112
United States

Shelley D. Minteer

University of Utah - Department of Chemistry

1645 E. Campus Center
Salt Lake City, UT 84112
United States

Sheng Dai

University of California, Irvine - Department of Materials Science and Engineering

P.O. Box 19556
Irvine, CA 62697-3125
United States

Xiaoqing Pan

University of California, Irvine - Department of Materials Science and Engineering

P.O. Box 19556
Irvine, CA 62697-3125
United States

University of California, Irvine - Department of Physics and Astronomy

P.O. Box 19556
Irvine, CA 62697-3125
United States

University of California, Irvine - Irvine Materials Research Institute (IMRI)

P.O. Box 19556
Irvine, CA 62697-3125
United States

Kanchan Chavan

Michigan State University - Department of Chemical and Materials Engineering

East Lansing, MI 48824-1122
United States

Scott Calabrese Barton

Michigan State University - Department of Chemical and Materials Engineering

East Lansing, MI 48824-1122
United States

Plamen Atanassov (Contact Author)

University of California, Irvine - Department of Chemical and Biomolecular Engineering ( email )

P.O. Box 19556
Irvine, CA 62697-3125
United States

University of New Mexico - Department of Chemical and Biological Engineering ( email )

Albuquerque, NM 87131-1221
United States

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