A Direct Grain-Boundary-Activity Correlation for CO Electroreduction on Cu Nanoparticles
Open accessAbstract
Copper catalyzes the electrochemical reduction of CO to valuable C2+ products including ethanol, acetate, propanol, and ethylene. These reactions could be very useful for converting renewable energy into fuels and chemicals, but conventional Cu electrodes are energetically inefficient and have poor selectivity for CO vs H2O reduction. Efforts to design improved catalysts have been impeded by the lack of experimentally validated, quantitative structure-activity relationships. Here we show that CO reduction activity is directly correlated to the density of grain boundaries (GBs) in Cu nanoparticles (NPs). We prepared electrodes of Cu NPs on carbon nanotubes (Cu/CNT) with different average GB densities quantified by transmission electron microscopy. At potentials ranging from -0.3 V to -0.5 V vs the reversible hydrogen electrode, the specific activity for CO reduction to ethanol and acetate was linearly proportional to the fraction of NP surfaces comprised of GB surface terminations. Our results provide a design principle for CO reduction to ethanol and acetate on Cu. GB-rich Cu/CNT electrodes are the first NP catalysts with significant CO reduction activity at moderate overpotential, reaching a mass activity of up to ∼1.5 A per gram of Cu and a Faradaic efficiency >70% at -0.3 V.
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Hoang et al. created an electrodeposited Cu-Ag alloy, containing 6% Ag, which demonstrated a FE for C2H4 and C2H5OH of nearly 55% and 26%, respectively, at a cathode potential of -0.7 V vs RHE.
“In one report, Hoang et al. created an electrodeposited Cu-Ag alloy, containing 6% Ag, which demonstrated a FE for C2H4 and C2H5OH of nearly 55% and 26%, respectively, at a cathode potential of -0.7 V vs RHE.[111]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [111]
In situ Raman revealed the origin of the high selectivity to be the optimum availability of the *CO intermediate and the enhanced stabilization of the Cu2O overlayer.
“In situ Raman revealed the origin of the high selectivity to be the optimum availability of the *CO intermediate and the enhanced stabilization of the Cu2O overlayer.”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [111]
Liquid phase electrolyzers have achieved high current densities toward CO, formate, and multi-carbon hydrocarbons/oxygenates.
“Liquid phase electrolyzer has achieved high current densities toward CO, [128][129][130][131][132][133] formate, [134][135][136] and multi-carbon hydrocarbons/oxygenates. [93,111,114,137,138]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [111]
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- Authors
- Feng, X., Jiang, K., Fan, S., & Kanan, M. W.
- Affiliations
- Stanford University (US)
- Tsinghua University (CN)
- Corresponding author
- Kanan, Matthew W.
- Venue
- ACS Central Science
- Publisher
- American Chemical Society (ACS)
- Published
- 2016-03-07
- Volume
- 2
- Issue
- 3
- Pages
- 169-174
- ISSN
- 2374-7943 (ISSN-L)
- 2374-7951
- PMC
- PMC4827560
- OpenAlex
- W2300899446
- Cited by
- 460
- References
- 42
- Citations by year
- 2026: 19 · 2025: 32 · 2024: 48 · 2023: 44 · 2022: 59 · 2021: 59 · 2020: 63 · 2019: 56 · 2018: 39 · 2017: 32 · 2016: 9
- FWCI
- 12.31
- Type
- journal article
- Language
- en
- Open access
- diamond
- doi.org
- Licence
- Locations
- ACS Central Science (publishedVersion, other-oa)
- PubMed Central (publishedVersion)
- PubMed (publishedVersion)
- DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
- Funders
- Air Force Office of Scientific Research (FA9550-14-1-0132)
- The Global Climate and Energy Project (106765)
- 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
- CO electroreduction, copper nanoparticles, grain boundaries, structure-activity relationship, ethanol production, acetate production, C2+ products, carbon nanotube electrodes, Faradaic efficiency, mass activity, electrocatalysis
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