Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces
Abstract
We present a theoretical analysis of trends in overpotentials for electrocatalytic CO2 reduction based on density functional theory calculations. The analysis is based on understanding variations in the free energy of intermediates and mapping out the potential at which different elementary steps are exergonic as a measure of the catalytic activity. We study different surface structures and introduce a simple model for including the effect of adsorbate-adsorbate interactions. We find that high coverages of CO under typical reaction conditions for the more reactive transition metals affect the catalytic activity towards the CO2 reduction reaction, but the ordering of metal activities is not changed. For the hydrogen evolution reaction, a high CO coverage shifts the maximum activity towards more reactive metals than Pt.
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Increasing *CO coverage significantly decreases *CO binding energy due to adsorbate-adsorbate lateral repulsion, and consequently improves *CO dimerization.
“For example, when increasing *CO coverage, it has been shown that *CO binding energy significantly decreases due to the adsorbate-adsorbate lateral repulsion, [58] and consequently, *CO dimerization improves.[33]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [58]
A strong correlation between binding energies of various reaction intermediates on transition metals and a lack of ability to independently control them poses a significant intrinsic limitation in developing suitable catalysts for large-scale commercialization of the CO2 reduction reaction.
“general understanding at present is that a strong correlation between binding energies of various reaction intermediates on transition metals and a lack of ability to independently control them poses a significant intrinsic limitation in developing suitable catalysts for large-scale commercialization of the CO2 reduction reaction.”
From Single-atom catalysts for CO <sub>2</sub> electroreduction with significant activity and selectivity improvements (2017) · cites this paper as [8]
The origin of dominant H2 production during CO2 reduction on strong *CO binding catalysts such as Ni and Pt has been suggested to be that *H binding energies shift toward being weaker as *CO coverage increases due to repulsive interaction between *CO and *H, making Ni and Pt more active for HER.
“The origin of the dominant H2 production during the CO2 reduction reaction has been suggested to be that for strong *CO binding catalysts such as Ni and Pt, the *H binding energies shift toward being weaker as the coverage of *CO increases due to a repulsive interaction between *CO and *H. This then makes Ni and Pt catalysts more active for the HER”
From Single-atom catalysts for CO <sub>2</sub> electroreduction with significant activity and selectivity improvements (2017) · cites this paper as [8]
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- Authors
- Shi, C., Hansen, H. A., Lausche, A. C., & Nørskov, J. K.
- Affiliations
- Stanford University (US)
- SLAC National Accelerator Laboratory (US)
- Corresponding author
- Nørskov, Jens K.
- Venue
- Physical Chemistry Chemical Physics
- Publisher
- Royal Society of Chemistry (RSC)
- Published
- 2014
- Volume
- 16
- Issue
- 10
- Pages
- 4720
- ISSN
- 1463-9076 (ISSN-L)
- 1463-9084
- OpenAlex
- W2111927542
- Cited by
- 465
- References
- 48
- Citations by year
- 2026: 19 · 2025: 36 · 2024: 41 · 2023: 52 · 2022: 56 · 2021: 46 · 2020: 53 · 2019: 44 · 2018: 39 · 2017: 25 · 2016: 25 · 2015: 15 · 2014: 14
- FWCI
- 8.69
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Physical Chemistry Chemical Physics (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Multidisciplinary University Research Initiative
- Air Force Office of Scientific Research
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
- Physical Sciences › Chemical Engineering › Catalysis › Catalysts for Methane Reforming
- Keywords
- electrochemical CO2 reduction, overpotential, transition metal electrocatalysts, surface structure, lateral interactions, hydrogen evolution reaction
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