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:
-
- 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. doi: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. doi: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}
}
Web of Science
Figures / Tables:

Works referencing / citing this record:
Designing materials for electrochemical carbon dioxide recycling
journal, July 2019
- Ross, Michael B.; De Luna, Phil; Li, Yifan
- Nature Catalysis, Vol. 2, Issue 8
Designing materials for electrochemical carbon dioxide recycling
journal, July 2019
- Ross, Michael B.; De Luna, Phil; Li, Yifan
- Nature Catalysis, Vol. 2, Issue 8
Alloy Nanocatalysts for the Electrochemical Oxygen Reduction (ORR) and the Direct Electrochemical Carbon Dioxide Reduction Reaction (CO 2 RR)
journal, December 2018
- Kim, Cheonghee; Dionigi, Fabio; Beermann, Vera
- Advanced Materials, Vol. 31, Issue 31
Lateral Adsorbate Interactions Inhibit HCOO − while Promoting CO Selectivity for CO 2 Electrocatalysis on Silver
journal, December 2018
- Bohra, Divya; Ledezma-Yanez, Isis; Li, Guanna
- Angewandte Chemie, Vol. 131, Issue 5
Switching of Kinetically Relevant Reactants for the Aqueous Cathodic Process Determined by Mass‐transport Coupled with Protolysis
journal, October 2019
- Shinagawa, Tatsuya; Obata, Keisuke; Takanabe, Kazuhiro
- ChemCatChem, Vol. 11, Issue 24
Catalyst–Electrolyte Interactions in Aqueous Reline Solutions for Highly Selective Electrochemical CO 2 Reduction
journal, November 2019
- Garg, Sahil; Li, Mengran; Rufford, Thomas E.
- ChemSusChem, Vol. 13, Issue 2
Carbon‐Rich Nonprecious Metal Single Atom Electrocatalysts for CO 2 Reduction and Hydrogen Evolution
journal, May 2019
- Wang, Tingting; Zhao, Qidong; Fu, Yuanyuan
- Small Methods, Vol. 3, Issue 10
Theory-guided design of catalytic materials using scaling relationships and reactivity descriptors
journal, November 2019
- Zhao, Zhi-Jian; Liu, Sihang; Zha, Shenjun
- Nature Reviews Materials, Vol. 4, Issue 12
Robust and biocompatible catalysts for efficient hydrogen-driven microbial electrosynthesis
journal, April 2019
- Kracke, Frauke; Wong, Andrew Barnabas; Maegaard, Karen
- Communications Chemistry, Vol. 2, Issue 1
CO 2 reduction on gas-diffusion electrodes and why catalytic performance must be assessed at commercially-relevant conditions
journal, January 2019
- Burdyny, Thomas; Smith, Wilson A.
- Energy & Environmental Science, Vol. 12, Issue 5
Surface structure-dependent electrocatalytic reduction of CO 2 to C1 products on SnO 2 catalysts
journal, January 2020
- Fang, Minling; Zheng, Zhiping; Chen, Jiayu
- Sustainable Energy & Fuels, Vol. 4, Issue 2
Self-supported copper-based gas diffusion electrodes for CO 2 electrochemical reduction
journal, January 2019
- Zhang, Jie; Luo, Wen; Züttel, Andreas
- Journal of Materials Chemistry A, Vol. 7, Issue 46
Figures / Tables found in this record: