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Title: Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold

Abstract

Electrochemical CO 2 reduction is a potential route to the sustainable production of valuable fuels and chemicals. Here, we perform CO 2 reduction experiments on Gold at neutral to acidic pH values to elucidate the long-standing controversy surrounding the rate-limiting step. We find the CO production rate to be invariant with pH on a Standard Hydrogen Electrode scale and conclude that it is limited by the CO 2 adsorption step. We present a new multi-scale modeling scheme that integrates ab initio reaction kinetics with mass transport simulations, explicitly considering the charged electric double layer. The model reproduces the experimental CO polarization curve and reveals the rate-limiting step to be *COOH to *CO at low overpotentials, CO 2 adsorption at intermediate ones, and CO 2 mass transport at high overpotentials. Finally, we show the Tafel slope to arise from the electrostatic interaction between the dipole of *CO 2 and the interfacial field. This work highlights the importance of surface charging for electrochemical kinetics and mass transport.

Authors:
 [1];  [2];  [3];  [1];  [1];  [1];  [4]
  1. Stanford Univ., Stanford, CA (United States). SUNCAT Center for Interface Science and Catalysis, Dept. of Chemical Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
  2. Stanford Univ., Stanford, CA (United States). SUNCAT Center for Interface Science and Catalysis, Dept. of Chemical Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Univ. of California, Los Angeles, CA (United States). Dept. of Chemical and Biomolecular Engineering
  3. California Inst. of Technology (CalTech), Pasadena, CA (United States). Div. of Chemistry and Chemical Engineering
  4. Technical Univ. of Denmark, Lyngby (Denmark). CatTheory Center, Dept. of Physics
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); Swiss National Science Foundation (SNSF)
OSTI Identifier:
1575240
Grant/Contract Number:  
AC02-76SF00515; AC02-05CH11231; SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 11; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ringe, Stefan, Morales-Guio, Carlos G., Chen, Leanne D., Fields, Meredith, Jaramillo, Thomas F., Hahn, Christopher, and Chan, Karen. Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold. United States: N. p., 2020. Web. doi:10.1038/s41467-019-13777-z.
Ringe, Stefan, Morales-Guio, Carlos G., Chen, Leanne D., Fields, Meredith, Jaramillo, Thomas F., Hahn, Christopher, & Chan, Karen. Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold. United States. doi:10.1038/s41467-019-13777-z.
Ringe, Stefan, Morales-Guio, Carlos G., Chen, Leanne D., Fields, Meredith, Jaramillo, Thomas F., Hahn, Christopher, and Chan, Karen. Tue . "Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold". United States. doi:10.1038/s41467-019-13777-z. https://www.osti.gov/servlets/purl/1575240.
@article{osti_1575240,
title = {Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold},
author = {Ringe, Stefan and Morales-Guio, Carlos G. and Chen, Leanne D. and Fields, Meredith and Jaramillo, Thomas F. and Hahn, Christopher and Chan, Karen},
abstractNote = {Electrochemical CO2 reduction is a potential route to the sustainable production of valuable fuels and chemicals. Here, we perform CO2 reduction experiments on Gold at neutral to acidic pH values to elucidate the long-standing controversy surrounding the rate-limiting step. We find the CO production rate to be invariant with pH on a Standard Hydrogen Electrode scale and conclude that it is limited by the CO2 adsorption step. We present a new multi-scale modeling scheme that integrates ab initio reaction kinetics with mass transport simulations, explicitly considering the charged electric double layer. The model reproduces the experimental CO polarization curve and reveals the rate-limiting step to be *COOH to *CO at low overpotentials, CO2 adsorption at intermediate ones, and CO2 mass transport at high overpotentials. Finally, we show the Tafel slope to arise from the electrostatic interaction between the dipole of *CO2 and the interfacial field. This work highlights the importance of surface charging for electrochemical kinetics and mass transport.},
doi = {10.1038/s41467-019-13777-z},
journal = {Nature Communications},
number = 1,
volume = 11,
place = {United States},
year = {2020},
month = {1}
}

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