Enhanced Electrochemical Methanation of Carbon Dioxide with a Dispersible Nanoscale Copper Catalyst
Abstract
Although the vast majority of hydrocarbon fuels and products are presently derived from petroleum, there is much interest in the development of routes for synthesizing these same products by hydrogenating CO2. The simplest hydrocarbon target is methane, which can utilize existing infrastructure for natural gas storage, distribution, and consumption. Electrochemical methods for methanizing CO2 currently suffer from a combination of low activities and poor selectivities. We demonstrate that copper nanoparticles supported on glassy carbon (n-Cu/C) achieve up to 4 times greater methanation current densities compared to high-purity copper foil electrodes. The n-Cu/C electrocatalyst also exhibits an average Faradaic efficiency for methanation of 80% during extended electrolysis, the highest Faradaic efficiency for room-temperature methanation reported to date. We find that the level of copper catalyst loading on the glassy carbon support has an enormous impact on the morphology of the copper under catalytic conditions and the resulting Faradaic efficiency for methane. The improved activity and Faradaic efficiency for methanation involves a mechanism that is distinct from what is generally thought to occur on copper foils. Electrochemical data indicate that the early steps of methanation on n-Cu/C involve a pre-equilibrium one-electron transfer to CO2 to form an adsorbed radical, followed by a rate-limiting non-electrochemical step in which the adsorbed CO2 radical reacts with a second CO2 molecule from solution. These nanoscale copper electrocatalysts represent a first step toward the preparation of practical methanation catalysts that can be incorporated into membrane-electrode assemblies in electrolyzers.
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The predicted theoretical limiting potential for CH3OH production using Pt@dv-Gr is significantly less negative than any catalysts that produce CH4 or CH3OH in the literature, whether synthesized (-0.5 to -1.0 V) or predicted (-0.3 to -1.0 V).
“In particular, as in the free energy diagram shown in Fig. 4 in detail, the predicted theoretical limiting potential (U L) for CH3OH production using Pt@dv-Gr is significantly less negative than any catalysts that produce CH4 or CH3OH in the literature, synthesized (–0.5 to –1.0 V)35,37,38 or predicted (–0.3 V to –1.0 V).4,6,39,40”
From Single-atom catalysts for CO <sub>2</sub> electroreduction with significant activity and selectivity improvements (2017) · cites this paper as [37]
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- Authors
- Manthiram, K., Beberwyck, B. J., & Alivisatos, A. P.
- Affiliations
- Lawrence Berkeley National Laboratory (US)
- Corresponding author
- Alivisatos, A. Paul
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2014-09-10
- Volume
- 136
- Issue
- 38
- Pages
- 13319-13325
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2333668949
- Cited by
- 546
- References
- 41
- Citations by year
- 2026: 15 · 2025: 26 · 2024: 43 · 2023: 48 · 2022: 44 · 2021: 54 · 2020: 81 · 2019: 62 · 2018: 53 · 2017: 52 · 2016: 40 · 2015: 27 · 2014: 1
- FWCI
- 13.20
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- CaltechAUTHORS (California Institute of Technology) (submittedVersion)
- eScholarship (California Digital Library) (submittedVersion)
- Funders
- U.S. Department of Energy (DE-AC02-05CH11231)
- Dow Chemical Company (20120984)
- Office of Science
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
- Physical Sciences › Chemical Engineering › Catalysis › Catalysts for Methane Reforming
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Keywords
- copper nanoparticles, glassy carbon support, Faradaic efficiency, catalyst loading, single electron transfer, membrane electrode assembly, CO2 electrolysis
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