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]
- 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 = {Fri Mar 09 00:00:00 EST 2018},
month = {Fri Mar 09 00:00:00 EST 2018}
}
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Figures / Tables:
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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