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Title: Trends in the Catalytic Activity of Hydrogen Evolution during CO2 Electroreduction on Transition Metals

Abstract

During CO2 electroreduction (CO2R), the hydrogen evolution reaction (HER) is a competing reaction. We present a combined experimental and theoretical investigation of the HER activity of transition metals under CO2R conditions. Experimental HER polarization curves were measured for six polycrystalline metal surfaces (Au, Ag, Cu, Ni, Pt, and Fe) in the presence of CO2 gas. We found that the HER activity of the transition metals is significantly shifted, relative to the CO2-free case. Density functional theory (DFT) calculations suggest that this shift arises from adsorbate–adsorbate interactions between *CO and *H on intermediate and strong binding metals, which weakens the *H binding energy. Using a simple model for the effect of *CO on the *H binding energy, we construct an activity volcano for HER in the presence of CO2 gas that is consistent with experimental trends. In conclusion, the significant changes in HER activity in the presence of CO2 gas is an important consideration in catalyst design and could help develop catalysts that are more selective for CO2R than the HER.

Authors:
 [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1469212
Grant/Contract Number:  
SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 4; Related Information: The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.7b03807.; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; adsorbate−adsorbate interactions; CO2 electroreduction; electrocatalysis; hydrogen evolution reaction; volcano plot

Citation Formats

Cave, Etosha R., Shi, Chuan, Kuhl, Kendra P., Hatsukade, Toru, Abram, David N., Hahn, Christopher, Chan, Karen, and Jaramillo, Thomas F. Trends in the Catalytic Activity of Hydrogen Evolution during CO2 Electroreduction on Transition Metals. United States: N. p., 2018. Web. doi:10.1021/acscatal.7b03807.
Cave, Etosha R., Shi, Chuan, Kuhl, Kendra P., Hatsukade, Toru, Abram, David N., Hahn, Christopher, Chan, Karen, & Jaramillo, Thomas F. Trends in the Catalytic Activity of Hydrogen Evolution during CO2 Electroreduction on Transition Metals. United States. https://doi.org/10.1021/acscatal.7b03807
Cave, Etosha R., Shi, Chuan, Kuhl, Kendra P., Hatsukade, Toru, Abram, David N., Hahn, Christopher, Chan, Karen, and Jaramillo, Thomas F. Fri . "Trends in the Catalytic Activity of Hydrogen Evolution during CO2 Electroreduction on Transition Metals". United States. https://doi.org/10.1021/acscatal.7b03807. https://www.osti.gov/servlets/purl/1469212.
@article{osti_1469212,
title = {Trends in the Catalytic Activity of Hydrogen Evolution during CO2 Electroreduction on Transition Metals},
author = {Cave, Etosha R. and Shi, Chuan and Kuhl, Kendra P. and Hatsukade, Toru and Abram, David N. and Hahn, Christopher and Chan, Karen and Jaramillo, Thomas F.},
abstractNote = {During CO2 electroreduction (CO2R), the hydrogen evolution reaction (HER) is a competing reaction. We present a combined experimental and theoretical investigation of the HER activity of transition metals under CO2R conditions. Experimental HER polarization curves were measured for six polycrystalline metal surfaces (Au, Ag, Cu, Ni, Pt, and Fe) in the presence of CO2 gas. We found that the HER activity of the transition metals is significantly shifted, relative to the CO2-free case. Density functional theory (DFT) calculations suggest that this shift arises from adsorbate–adsorbate interactions between *CO and *H on intermediate and strong binding metals, which weakens the *H binding energy. Using a simple model for the effect of *CO on the *H binding energy, we construct an activity volcano for HER in the presence of CO2 gas that is consistent with experimental trends. In conclusion, the significant changes in HER activity in the presence of CO2 gas is an important consideration in catalyst design and could help develop catalysts that are more selective for CO2R than the HER.},
doi = {10.1021/acscatal.7b03807},
journal = {ACS Catalysis},
number = 4,
volume = 8,
place = {United States},
year = {2018},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 11 works
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Figures / Tables:

Figure 1 Figure 1: Hydrogen partial current densities under CO2R conditions for six polycrystalline transition metals. The potential at 1 mA/cm2 was used as an activity metric for the metals.

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