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Title: Surface Ligand Promotion of Carbon Dioxide Reduction through Stabilizing Chemisorbed Reactive Intermediates

Abstract

We have explored functionalizing metal catalysts with surface ligands as an approach to facilitate electrochemical carbon dioxide reduction reaction (CO2RR). To provide a molecular level understanding of the mechanism by which this enhancement occurs, we combine in situ spectroscopy analysis with an interpretation based on quantum mechanics (QM) calculations. We find that a surface ligand can play a critical role in stabilizing the chemisorbed CO2, which facilitates CO2 activation and leads to a 0.3 V decrease in the overpotential for carbon monoxide (CO) formation. Moreover, the presence of the surface ligand leads to nearly exclusive CO production. At -0.6 V (versus reversible hydrogen electrode, RHE), CO is the only significant product with a faradic efficiency of 93% and a current density of 1.9 mA cm–2. This improvement corresponds to 53-fold enhancement in turnover frequency compared with the Ag nanoparticles (NPs) without surface ligands.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1];  [3];  [1]; ORCiD logo [4]; ORCiD logo [4]
  1. Harbin Inst. of Technology (China)
  2. Harbin Medical Univ. (China)
  3. Univ. of Oxford (United Kingdom)
  4. California Inst. of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Research Org.:
California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1467603
Grant/Contract Number:  
SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 11; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Zhijiang, Wu, Lina, Sun, Kun, Chen, Ting, Jiang, Zhaohua, Cheng, Tao, and Goddard, III, William A. Surface Ligand Promotion of Carbon Dioxide Reduction through Stabilizing Chemisorbed Reactive Intermediates. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.jpclett.8b00959.
Wang, Zhijiang, Wu, Lina, Sun, Kun, Chen, Ting, Jiang, Zhaohua, Cheng, Tao, & Goddard, III, William A. Surface Ligand Promotion of Carbon Dioxide Reduction through Stabilizing Chemisorbed Reactive Intermediates. United States. https://doi.org/10.1021/acs.jpclett.8b00959
Wang, Zhijiang, Wu, Lina, Sun, Kun, Chen, Ting, Jiang, Zhaohua, Cheng, Tao, and Goddard, III, William A. Tue . "Surface Ligand Promotion of Carbon Dioxide Reduction through Stabilizing Chemisorbed Reactive Intermediates". United States. https://doi.org/10.1021/acs.jpclett.8b00959. https://www.osti.gov/servlets/purl/1467603.
@article{osti_1467603,
title = {Surface Ligand Promotion of Carbon Dioxide Reduction through Stabilizing Chemisorbed Reactive Intermediates},
author = {Wang, Zhijiang and Wu, Lina and Sun, Kun and Chen, Ting and Jiang, Zhaohua and Cheng, Tao and Goddard, III, William A.},
abstractNote = {We have explored functionalizing metal catalysts with surface ligands as an approach to facilitate electrochemical carbon dioxide reduction reaction (CO2RR). To provide a molecular level understanding of the mechanism by which this enhancement occurs, we combine in situ spectroscopy analysis with an interpretation based on quantum mechanics (QM) calculations. We find that a surface ligand can play a critical role in stabilizing the chemisorbed CO2, which facilitates CO2 activation and leads to a 0.3 V decrease in the overpotential for carbon monoxide (CO) formation. Moreover, the presence of the surface ligand leads to nearly exclusive CO production. At -0.6 V (versus reversible hydrogen electrode, RHE), CO is the only significant product with a faradic efficiency of 93% and a current density of 1.9 mA cm–2. This improvement corresponds to 53-fold enhancement in turnover frequency compared with the Ag nanoparticles (NPs) without surface ligands.},
doi = {10.1021/acs.jpclett.8b00959},
journal = {Journal of Physical Chemistry Letters},
number = 11,
volume = 9,
place = {United States},
year = {2018},
month = {5}
}

Journal Article:
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Cited by: 5 works
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Figures / Tables:

Figure 1 Figure 1: (A) chemisorbed CO2 on cysteamine functionalized Ag(111) surface. (B) Chemisorbed CO2 on Ag(111) surface. (C) The free energy profile of the CO2 approaching surface. Only the water molecules directly forming hydrogen bond are shown (the remaining 31 or 30 solvent water molecules are removed for clarity). The hydrogenmore » bonds are shown as a slashed line. The colors are Ag in silver, C in gray, O in red, N in blue, S in yellow and H in white.« less

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