Nanoporous Copper–Silver Alloys by Additive-Controlled Electrodeposition for the Selective Electroreduction of CO2 to Ethylene and Ethanol
Abstract
Electrodeposition of CuAg alloy films from plating baths containing 3,5-diamino-1,2,4-triazole (DAT) as an inhibitor yields high surface area catalysts for the active and selective electroreduction of CO 2 to multicarbon hydrocarbons and oxygenates. EXAFS shows the co-deposited alloy film to be homogeneously mixed. The alloy film containing 6% Ag exhibits the best CO 2 electroreduction performance, with the Faradaic efficiency for C 2 H 4 and C 2 H 5 OH production reaching nearly 60 and 25%, respectively, at a cathode potential of just −0.7 V vs RHE and a total current density of ∼ – 300 mA/cm 2 . Such high levels of selectivity at high activity and low applied potential are the highest reported to date. In situ Raman and electroanalysis studies suggest the origin of the high selectivity toward C 2 products to be a combined effect of the enhanced stabilization of the Cu 2 O overlayer and the optimal availability of the CO intermediate due to the Ag incorporated in the alloy.
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Removing the membrane decreases capital costs.
“Removing the membrane reduces ohmic loss, simplifies the system requirements, decreases capital costs, and alleviates salting out issues.[126,127]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [126]
Removing the membrane simplifies the system requirements.
“Removing the membrane reduces ohmic loss, simplifies the system requirements, decreases capital costs, and alleviates salting out issues.[126,127]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [126]
Removing the membrane alleviates salting out issues.
“Removing the membrane reduces ohmic loss, simplifies the system requirements, decreases capital costs, and alleviates salting out issues.[126,127]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [126]
Removing the membrane reduces ohmic loss.
“Removing the membrane reduces ohmic loss, simplifies the system requirements, decreases capital costs, and alleviates salting out issues.[126,127]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [126]
Cites
Modern Aspects of Electrochemistry
Bockris, J. O., White, R. E., & Conway, B. E. (2002) · Kluwer Academic Publishers eBooks · doi:10.1007/b114168 · Cited by 5,954 · see citing works
Biesinger, M. C., Lau, L. W. M., Gerson, A. R., & Smart, R. S. C. (2010) · Applied Surface Science · doi:10.1016/j.apsusc.2010.07.086 · Cited by 4,634 · see citing works
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces
Kuhl, K. P., Cave, E. R., Abram, D. N., & Jaramillo, T. F. (2012) · Energy & Environmental Science · doi:10.1039/c2ee21234j · Cited by 3,160 · see citing works
Appel, A. M., Bercaw, J. E., Bocarsly, A. B., Dobbek, H., DuBois, D. L., Dupuis, M., Ferry, J. G., Fujita, E., Hille, R., Kenis, P. J. A., et al. (2013) · Chemical Reviews · doi:10.1021/cr300463y · Cited by 2,193 · see citing works
Self-citationCatalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide
Kortlever, R., Shen, J., Schouten, K. J. P., Calle‐Vallejo, F., & Koper, M. T. M. (2015) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.5b01559 · Cited by 2,183 · see citing works
Progress in carbon dioxide separation and capture: A review
Yang, H., Xu, Z., Fan, M., Gupta, R. P., Slimane, R. B., Bland, A. E., & Wright, I. G. (2008) · Journal of Environmental Sciences · doi:10.1016/s1001-0742(08)60002-9 · Cited by 2,088 · see citing works
Li, C. W., & Kanan, M. W. (2012) · Journal of the American Chemical Society · doi:10.1021/ja3010978 · Cited by 2,000 · see citing works
Activity Descriptors for CO <sub>2</sub> Electroreduction to Methane on Transition-Metal Catalysts
Peterson, A. A., & Nørskov, J. K. (2012) · The Journal of Physical Chemistry Letters · doi:10.1021/jz201461p · Cited by 1,667 · see citing works
Catalysis of the electrochemical reduction of carbon dioxide
Costentin, C., Robert, M., & Savéant, J. (2012) · Chemical Society Reviews · doi:10.1039/c2cs35360a · Cited by 1,664 · see citing works
Prospects of CO 2 Utilization via Direct Heterogeneous Electrochemical Reduction
Whipple, D. T., & Kenis, P. J. A. (2010) · The Journal of Physical Chemistry Letters · doi:10.1021/jz1012627 · Cited by 1,419 · see citing works
Self-citationAnthropogenic Chemical Carbon Cycle for a Sustainable Future
Olah, G. A., Prakash, G. K. S., & Goeppert, A. (2011) · Journal of the American Chemical Society · doi:10.1021/ja202642y · Cited by 1,378 · see citing works
Kim, D., Resasco, J., Yu, Y., Asiri, A. M., & Yang, P. (2014) · Nature Communications · doi:10.1038/ncomms5948 · Cited by 1,374 · see citing works
Schlesinger, M. 1.-2., & Paunovic, M. 1.-2. (2010) · Wiley eBooks · doi:10.1002/9780470602638 · Cited by 1,223 · see citing works
Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene
Mistry, H., Varela, A. S., Bonifacio, C. S., Zegkinoglou, I., Sinev, I., Choi, Y.-W., Kisslinger, K., Stach, E. A., Yang, J. C., Strasser, P., et al. (2016) · Nature Communications · doi:10.1038/ncomms12123 · Cited by 1,214 · see citing works
Yin, M., Wu, C., Lou, Y., Burda, C., Koberstein, J. T., Zhu, Y., & O'Brien, S. P. (2005) · Journal of the American Chemical Society · doi:10.1021/ja050006u · Cited by 989 · see citing works
Schouten, K. J. P., Kwon, Y., van der Ham, C. J. M., Qin, Z., & Koper, M. T. M. (2011) · Chemical Science · doi:10.1039/c1sc00277e · Cited by 960 · see citing works
Ren, D., Deng, Y., Handoko, A. D., Chen, C. S., Malkhandi, S., & Yeo, B. S. (2015) · ACS Catalysis · doi:10.1021/cs502128q · Cited by 930 · see citing works
Two Pathways for the Formation of Ethylene in CO Reduction on Single-Crystal Copper Electrodes
Schouten, K. J. P., Qin, Z., Pérez‐Gallent, E., & Koper, M. T. M. (2012) · Journal of the American Chemical Society · doi:10.1021/ja302668n · Cited by 898 · see citing works
Theoretical Insights into a CO Dimerization Mechanism in CO 2 Electroreduction
Montoya, J. H., Shi, C., Chan, K., & Nørskov, J. K. (2015) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.5b00722 · Cited by 861 · see citing works
Jhong, H. “., Ma, S., & Kenis, P. J. A. (2013) · Current Opinion in Chemical Engineering · doi:10.1016/j.coche.2013.03.005 · Cited by 824 · see citing works
Self-citationElectrochemical reduction of carbon dioxide at various series of copper single crystal electrodes
Hori, Y., Takahashi, I., Koga, O., & Hoshi, N. (2003) · Journal of Molecular Catalysis A Chemical · doi:10.1016/s1381-1169(03)00016-5 · Cited by 762 · see citing works
Ren, D., Ang, B. S.-H., & Yeo, B. S. (2016) · ACS Catalysis · doi:10.1021/acscatal.6b02162 · Cited by 724 · see citing works
Tang, W., Peterson, A. A., Varela, A. S., Jovanov, Z. P., Bech, L., Durand, W. J., Dahl, S., Nørskov, J. K., & Chorkendorff, I. (2011) · Physical Chemistry Chemical Physics · doi:10.1039/c1cp22700a · Cited by 691 · see citing works
Hansen, J. E., Kharecha, P. A., Sato, M., Masson‐Delmotte, V., Ackerman, F., Beerling, D. J., Hearty, P. J., Hoegh‐Guldberg, O., Hsu, S.-L., Parmesan, C., et al. (2013) · PLoS ONE · doi:10.1371/journal.pone.0081648 · Cited by 676 · see citing works
Clark, E. L., Hahn, C., Jaramillo, T. F., & Bell, A. T. (2017) · Journal of the American Chemical Society · doi:10.1021/jacs.7b08607 · Cited by 676 · see citing works
Verma, S., Kim, B., Jhong, H. “., Ma, S., & Kenis, P. J. A. (2016) · ChemSusChem · doi:10.1002/cssc.201600394 · Cited by 655 · see citing works
Self-citationMa, M., Djanashvili, K., & Smith, W. A. (2016) · Angewandte Chemie International Edition · doi:10.1002/anie.201601282 · Cited by 640 · see citing works
Debbichi, L., de Lucas, M. C. M., Pierson, J. F., & Krüger, P. (2012) · The Journal of Physical Chemistry C · doi:10.1021/jp303096m · Cited by 583 · see citing works
Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces
Durand, W. J., Peterson, A. A., Studt, F., Abild‐Pedersen, F., & Nørskov, J. K. (2011) · Surface Science · doi:10.1016/j.susc.2011.04.028 · Cited by 552 · see citing works
Kaş, R., Kortlever, R., Milbrat, A., Koper, M. T. M., Mul, G., & Baltrušaitis, J. (2014) · Physical Chemistry Chemical Physics · doi:10.1039/c4cp01520g · Cited by 550 · see citing works
Enhanced Electrochemical Methanation of Carbon Dioxide with a Dispersible Nanoscale Copper Catalyst
Manthiram, K., Beberwyck, B. J., & Alivisatos, A. P. (2014) · Journal of the American Chemical Society · doi:10.1021/ja5065284 · Cited by 546 · see citing works
Mesostructure-Induced Selectivity in CO2 Reduction Catalysis
Hall, A. S., Yoon, Y., Wuttig, A., & Surendranath, Y. (2015) · Journal of the American Chemical Society · doi:10.1021/jacs.5b08259 · Cited by 505 · see citing works
Electrochemical Reduction of CO2 to CH3OH at Copper Oxide Surfaces
Le, M., Ren, M.-Y., Zhang, Z., Sprunger, P. T., Kurtz, R. L., & Flake, J. C. (2011) · Journal of The Electrochemical Society · doi:10.1149/1.3561636 · Cited by 489 · see citing works
One-step electrosynthesis of ethylene and ethanol from CO2 in an alkaline electrolyzer
Ma, S., Sadakiyo, M., Luo, R., Heima, M., Yamauchi, M., & Kenis, P. J. A. (2016) · Journal of Power Sources · doi:10.1016/j.jpowsour.2015.09.124 · Cited by 488 · see citing works
Self-citationTrends in electrochemical CO2 reduction activity for open and close-packed metal surfaces
Shi, C., Hansen, H. A., Lausche, A. C., & Nørskov, J. K. (2014) · Physical Chemistry Chemical Physics · doi:10.1039/c3cp54822h · Cited by 465 · see citing works
Lim, R. J., Xie, M., Sk, M. A., Lee, J.-M., Fisher, A., Wang, X., & Lim, K. H. (2014) · Catalysis Today · doi:10.1016/j.cattod.2013.11.037 · Cited by 460 · see citing works
Kaş, R., Hummadi, K. K., Kortlever, R., de Wit, P., Milbrat, A., Luiten-Olieman, M. W. J., Benes, N. E., Koper, M. T. M., & Mul, G. (2016) · Nature Communications · doi:10.1038/ncomms10748 · Cited by 366 · see citing works
Martín, A. J., Larrazábal, G. O., & Pérez‐Ramírez, J. (2015) · Green Chemistry · doi:10.1039/c5gc01893e · Cited by 361 · see citing works
Tuning of Silver Catalyst Mesostructure Promotes Selective Carbon Dioxide Conversion into Fuels
Yoon, Y., Hall, A. S., & Surendranath, Y. (2016) · Angewandte Chemie International Edition · doi:10.1002/anie.201607942 · Cited by 310 · see citing works
Nanoporous Copper Films by Additive-Controlled Electrodeposition: CO<sub>2</sub> Reduction Catalysis
Hoang, T. T. H., Ma, S., Gold, J. I., Kenis, P. J. A., & Gewirth, A. A. (2017) · ACS Catalysis · doi:10.1021/acscatal.6b03613 · Cited by 296 · see citing works
Self-citationSurface chemistry of electrodeposited Cu2O films studied by XPS
Zhu, C., Osherov, A., & Panzer, M. J. (2013) · Electrochimica Acta · doi:10.1016/j.electacta.2013.08.038 · Cited by 280 · see citing works
Reller, C., Krause, R. K., Volkova, E., Schmid, B., Neubauer, S., Rucki, A., Schuster, M. E., & Schmid, G. (2017) · Advanced Energy Materials · doi:10.1002/aenm.201602114 · Cited by 270 · see citing works
Electrochemical Reduction of CO 2 at Intentionally Oxidized Copper Electrodes
Frese, K. W. (1991) · Journal of The Electrochemical Society · doi:10.1149/1.2085411 · Cited by 213 · see citing works
Watanabe, M., Shibata, M., Kato, A., Azuma, M., & Sakata, T. (1991) · Journal of The Electrochemical Society · doi:10.1149/1.2085417 · Cited by 194 · see citing works
Christophe, J., Doneux, T., & Buess‐Herman, C. (2012) · Electrocatalysis · doi:10.1007/s12678-012-0095-0 · Cited by 193 · see citing works
Choi, J., Kim, M. J., Ahn, . H., Choi, I., Jang, J. H., Ham, Y. S., Kim, J. J., & Kim, S. (2016) · Chemical Engineering Journal · doi:10.1016/j.cej.2016.04.037 · Cited by 178 · see citing works
Larrazábal, G. O., Martín, A. J., & Pérez-Ramírez, J. (2017) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.7b01380 · Cited by 176 · see citing works
Hoang, T. T. H., & Gewirth, A. A. (2015) · ACS Catalysis · doi:10.1021/acscatal.5b02365 · Cited by 172 · see citing works
Self-citationKim, N. R., Shin, K., Jung, I., et al. (2014) · The Journal of Physical Chemistry C · doi:10.1021/jp506069c · Cited by 149 · see citing works
In Situ Scanning Tunneling Microscopy Study of the Anodic Oxidation of Cu(111) in 0.1 M NaOH
Kunze‐Liebhäuser, J., Maurice, V., Klein, L. H., et al. (2001) · The Journal of Physical Chemistry B · doi:10.1021/jp004012i · Cited by 148 · see citing works
XANES, EXAFS and photocatalytic investigations on copper oxide nanoparticles and nanocomposites
Sharma, A., Varshney, M., Park, J., et al. (2015) · RSC Advances · doi:10.1039/c4ra16217j · Cited by 128 · see citing works
Electrochemical CO 2 Conversion Using Skeleton (Sponge) Type of Cu Catalysts
Dutta, A., Rahaman, M., Mohos, M., Zanetti, A., & Broekmann, P. (2017) · ACS Catalysis · doi:10.1021/acscatal.7b01548 · Cited by 128 · see citing works
Schultz, Z. D., Feng, Z. V., Biggin, M. E., et al. (2006) · Journal of The Electrochemical Society · doi:10.1149/1.2139952 · Cited by 97 · see citing works
Voltammetric and Force Spectroscopic Examination of Oxide Formation on Cu(111) in Basic Solution
Kang, M., & Gewirth, A. A. (2002) · The Journal of Physical Chemistry B · doi:10.1021/jp025882y · Cited by 62 · see citing works
Self-citationHirsimäki, M., Lampimäki, M., Lahtonen, K., et al. (2005) · Surface Science · doi:10.1016/j.susc.2005.03.035 · Cited by 53 · see citing works
Akemann, W., & Otto, A. (1993) · Surface Science · doi:10.1016/0039-6028(93)90751-5 · Cited by 37 · see citing works
Wu, G. Y., Bae, S.-E., Gewirth, A. A., et al. (2007) · Surface Science · doi:10.1016/j.susc.2007.02.016 · Cited by 34 · see citing works
Self-citationYu, L., & Akolkar, R. N. (2016) · Journal of The Electrochemical Society · doi:10.1149/2.0701606jes · Cited by 18 · see citing works
Selection of Phase Formation in Electroplated Ag-Cu Alloys
Liang, D., Shao, W., & Zangari, G. (2015) · Journal of The Electrochemical Society · doi:10.1149/2.0651602jes · Cited by 15 · see citing works
Introduction to Global Carbon Cycling: An Overview of the Global Carbon Cycle
Ussiri, D. A. N., & Lal, R. (2017) · Springer eBooks · doi:10.1007/978-3-319-53845-7_3 · Cited by 15 · see citing works
Electrochemical Reduction of CO2 Using Supported Cu2O Nanoparticles
Bugayong, J., & Griffin, G. L. (2013) · ECS Transactions · doi:10.1149/05802.0081ecst · Cited by 14 · see citing works
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- Authors
- Hoang, T. T. H., Verma, S., Ma, S., Fister, T. T., Timoshenko, J., Frenkel, A. I., Kenis, P. J. A., & Gewirth, A. A.
- Affiliations
- University of Illinois Urbana-Champaign (US)
- Kyushu University (JP)
- Argonne National Laboratory (US)
- Stony Brook University (US)
- Corresponding author
- Gewirth, Andrew A.
- ORCID
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2018-04-05
- Volume
- 140
- Issue
- 17
- Pages
- 5791-5797
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2795676722
- Cited by
- 852
- References
- 61
- Citations by year
- 2026: 57 · 2025: 99 · 2024: 121 · 2023: 100 · 2022: 128 · 2021: 125 · 2020: 117 · 2019: 78 · 2018: 27
- FWCI
- 20.06
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Division of Chemistry (CHE-1309731)
- Ministry of Education, Culture, Sports, Science and Technology
- 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
- silver-copper alloys, nanoporous films, electrochemical CO2 reduction, ethylene production, ethanol production, 3,5-diamino-1,2,4-triazole, Faradaic efficiency, CO intermediate, alloy catalysts, EXAFS, in situ Raman spectroscopy
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