Tuned Chemical Bonding Ability of Au at Grain Boundaries for Enhanced Electrochemical CO2 Reduction
Abstract
Electrochemical carbon dioxide (CO 2 ) reduction is an emerging technology for efficiently recycling CO 2 into fuel, and many studies of this reaction are focused on developing advanced catalysts with high activity, selectivity, and durability. Of these catalysts, oxide-derived metal nanoparticles, which are prepared by reducing a metal oxide, have received considerable attention due to their catalytic properties. However, the mechanism of the nanoparticles’ activity enhancement is not well-understood. Recently, it was discovered that the catalytic activity is quantitatively correlated to the surface density of grain boundaries (GBs), implying that GBs are mechanistically important in electrochemical CO 2 reduction. Here, using extensive density functional theory (DFT) calculations modeling the atomistic structure of GBs on the Au (111) surface, we suggest a mechanism of electrochemical CO 2 reduction to CO mediated by GBs; the broken local spatial symmetry near a GB tunes the Au metal-to-adsorbate π-backbonding ability, thereby stabilizing the key COOH intermediate. This stabilization leads to a decrease of ∼200 mV in the overpotential and a change in the rate-determining step to the second reduction step, of which are consistent with previous experimental observations. The atomistic and electronic details of the mechanistic role of GBs during electrochemical CO 2 reduction presented in this work demonstrate the structure–activity relationship of atomically disordered metastable structures in catalytic applications.
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Further studies on NCNTs revealed that catalytic activity is very dependent on the density and type of nitrogen defect.
“Further studies on NCNTs revealed that the catalytic activity is very dependent on the density and type of nitrogen defect.[88]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [88]
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- Authors
- Kim, K.-S., Kim, W. J., Lim, H.-K., Lee, E. K., & Kim, H.
- Affiliations
- Korea Advanced Institute of Science and Technology (KR)
- Corresponding author
- Lee, Eok Kyun
- Kim, Hyungjun
- Venue
- ACS Catalysis
- Publisher
- American Chemical Society (ACS)
- Published
- 2016-06-13
- Volume
- 6
- Issue
- 7
- Pages
- 4443-4448
- ISSN
- 2155-5435 (ISSN-L)
- OpenAlex
- W2416506829
- Cited by
- 123
- References
- 34
- Citations by year
- 2026: 3 · 2025: 9 · 2024: 12 · 2023: 14 · 2022: 10 · 2021: 15 · 2020: 19 · 2019: 15 · 2018: 15 · 2017: 9 · 2016: 2
- FWCI
- 3.71
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- ACS Catalysis (publishedVersion)
- Funders
- Ministry of Trade, Industry and Energy (20153030031720)
- Ministry of Science, ICT and Future Planning (2013M3A6B1078884)
- 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, grain boundaries, gold nanoparticles, Au(111), COOH intermediate, π-backbonding, spatial symmetry breaking, reaction mechanism, overpotential, rate-determining step, structure-activity relationship
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