Manipulating the Hydrocarbon Selectivity of Copper Nanoparticles in CO 2 Electroreduction by Process Conditions
Open accessAbstract
The formation of ethylene in CO 2 electroreduction over rough copper electrodes is often explained by the presence of specific surface crystal steps, edges and defects. We demonstrate that an identical electrode covered with copper nanoparticles can yield either predominantly ethylene or methane, depending on the electrolyte concentration and applied CO 2 pressure. Calculations of the pH near the electrode surface suggest that ethylene formation is favored by a relatively high (local) pH. Furthermore, the conditions leading to the formation of significant amounts of methane result in rapid deterioration of hydrocarbon production rates, whereas electrode performance in conditions favoring ethylene production can be sustained for hours. This study substantially alters the mechanistic interpretation of formation of ethylene over rough copper surfaces and implies that applied process conditions inducing pH variations near the electrode surface need to be taken into consideration.
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Dufek et al. found a four-fold improvement in FECO and a corresponding decrease in HER when operating at elevated pressures of 20 atm in flow cells.
“On the other hand, even with the mass transport benefits afforded by gas diffusion electrodes in flow cells, Dufek et al. found a four-fold improvement in FECO and a corresponding decrease in HER when operating at elevated pressures of 20 atm.[139,220]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [220]
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Cites
How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels
Peterson, A. A., Abild-Pedersen, F., Studt, F., Rossmeisl, J., & Nørskov, J. K. (2010) · Energy & Environmental Science · doi:10.1039/c0ee00071j · Cited by 3,784 · 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
Li, C. W., & Kanan, M. W. (2012) · Journal of the American Chemical Society · doi:10.1021/ja3010978 · Cited by 2,000 · see citing works
Electrochemical CO2 Reduction on Metal Electrodes
Hori, Y. (2008) · Springer eBooks · doi:10.1007/978-0-387-49489-0_3 · Cited by 1,904 · see citing works
Kondratenko, E. V., Mul, G., Baltrusaitis, J., Larrazábal, G. O., & Pérez-Ramírez, J. (2013) · Energy & Environmental Science · doi:10.1039/c3ee41272e · Cited by 1,802 · see citing works
Self-citationElectroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper
Li, C. W., Ciston, J., & Kanan, M. W. (2014) · Nature · doi:10.1038/nature13249 · Cited by 1,728 · see citing works
Hori, Y., Murata, A., & Takahashi, R. (1989) · Journal of the Chemical Society Faraday Transactions 1 Physical Chemistry in Condensed Phases · doi:10.1039/f19898502309 · Cited by 1,644 · see citing works
Ionic Liquid–Mediated Selective Conversion of CO <sub>2</sub> to CO at Low Overpotentials
Rosen, B. A., Salehi-Khojin, A., Thorson, M. R., Zhu, W., Whipple, D. T., Kenis, P. J. A., & Masel, R. I. (2011) · Science · doi:10.1126/science.1209786 · Cited by 1,558 · see citing works
A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper
Gattrell, M., Gupta, N., & Co, A. C. (2006) · Journal of Electroanalytical Chemistry · doi:10.1016/j.jelechem.2006.05.013 · Cited by 1,499 · 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
Hori, Y., Kikuchi, K., & Suzuki, S. (1985) · Chemistry Letters · doi:10.1246/cl.1985.1695 · Cited by 1,401 · see citing works
Nanostructured Tin Catalysts for Selective Electrochemical Reduction of Carbon Dioxide to Formate
Zhang, S., Kang, P., & Meyer, T. J. (2014) · Journal of the American Chemical Society · doi:10.1021/ja4113885 · Cited by 1,150 · see citing works
Calle‐Vallejo, F., & Koper, M. T. M. (2013) · Angewandte Chemie International Edition · doi:10.1002/anie.201301470 · Cited by 941 · see citing works
Self-citationSelectivity of CO 2 Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps
Nie, X., Esopi, M. R., Janik, M. J., & Asthagiri, A. (2013) · Angewandte Chemie International Edition · doi:10.1002/anie.201208320 · Cited by 927 · see citing works
Theory of multiple proton–electron transfer reactions and its implications for electrocatalysis
Koper, M. T. M. (2013) · Chemical Science · doi:10.1039/c3sc50205h · Cited by 908 · see citing works
Self-citationTwo 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
Self-citationElectrochemical Reduction of CO at a Copper Electrode
Hori, Y., Takahashi, R., Yoshinami, Y., & Murata, A. (1997) · The Journal of Physical Chemistry B · doi:10.1021/jp970284i · Cited by 818 · see citing works
Electrochemical 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
Renewable and metal-free carbon nanofibre catalysts for carbon dioxide reduction
Kumar, B., Asadi, M., Pisasale, D., Sinha‐Ray, S., Rosen, B. A., Haasch, R. T., Abiade, J. T., Yarin, A. L., & Salehi‐Khojin, A. (2013) · Nature Communications · doi:10.1038/ncomms3819 · Cited by 698 · 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
Gupta, N., Gattrell, M., & MacDougall, B. (2006) · Journal of Applied Electrochemistry · doi:10.1007/s10800-005-9058-y · Cited by 558 · 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
Self-citationElectrochemical Reduction of CO2 at Copper Nanofoams
Sen, S., Liu, D., & Palmore, G. T. R. (2014) · ACS Catalysis · doi:10.1021/cs500522g · Cited by 528 · see citing works
Insights into CC Coupling in CO 2 Electroreduction on Copper Electrodes
Montoya, J. H., Peterson, A. A., & Nørskov, J. K. (2013) · ChemCatChem · doi:10.1002/cctc.201200564 · Cited by 435 · see citing works
“Deactivation of copper electrode” in electrochemical reduction of CO2
Hori, Y., Konishi, H., Futamura, T., Murata, A., Koga, O., Sakurai, H., & Oguma, K. (2005) · Electrochimica Acta · doi:10.1016/j.electacta.2005.03.015 · Cited by 432 · see citing works
The influence of pH on the reduction of CO and CO2 to hydrocarbons on copper electrodes
Schouten, K. J. P., Pérez‐Gallent, E., & Koper, M. T. M. (2013) · Journal of Electroanalytical Chemistry · doi:10.1016/j.jelechem.2013.08.033 · Cited by 402 · see citing works
Self-citationElectrochemistry of Nanoparticles
Kleijn, S. E. F., Lai, S. C. S., Koper, M. T. M., & Unwin, P. R. (2014) · Angewandte Chemie International Edition · doi:10.1002/anie.201306828 · Cited by 399 · see citing works
Self-citationDiMeglio, J. L., & Rosenthal, J. (2013) · Journal of the American Chemical Society · doi:10.1021/ja4033549 · Cited by 386 · see citing works
DeWulf, D. W., Jin, T., & Bard, A. J. (1989) · Journal of The Electrochemical Society · doi:10.1149/1.2096993 · Cited by 372 · see citing works
Structure Sensitivity of the Electrochemical Reduction of Carbon Monoxide on Copper Single Crystals
Schouten, K. J. P., Gallent, E. P., & Koper, M. T. M. (2013) · ACS Catalysis · doi:10.1021/cs4002404 · Cited by 367 · see citing works
Self-citationStable and selective electrochemical reduction of carbon dioxide to ethylene on copper mesocrystals
Chen, C. S., Handoko, A. D., Wan, J. H., Ma, L., Ren, D., & Yeo, B. S. (2014) · Catalysis Science & Technology · doi:10.1039/c4cy00906a · Cited by 348 · see citing works
CO2 Electroreduction to Hydrocarbons on Carbon-Supported Cu Nanoparticles
Baturina, O. A., Lu, Q., Padilla, M. A., Xin, L., Li, W., Serov, A., Artyushkova, K., Atanassov, P. B., Xu, F., Epshteyn, A., et al. (2014) · ACS Catalysis · doi:10.1021/cs500537y · Cited by 320 · see citing works
Theoretical Considerations on the Electroreduction of CO to C2 Species on Cu(100) Electrodes
Calle‐Vallejo, F., & Koper, M. T. M. (2013) · Angewandte Chemie · doi:10.1002/ange.201301470 · Cited by 239 · see citing works
Self-citationHori, Y., Murata, A., Takahashi, R., & Suzuki, S. (1988) · Journal of the Chemical Society Chemical Communications · doi:10.1039/c39880000017 · Cited by 214 · see citing works
Selectivity of CO2 Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps
Nie, X., Esopi, M. R., Janik, M. J., & Asthagiri, A. (2013) · Angewandte Chemie · doi:10.1002/ange.201208320 · Cited by 210 · see citing works
Xie, J., Huang, Y., Li, W., Song, X., Xiong, L., & Yu, H. (2014) · Electrochimica Acta · doi:10.1016/j.electacta.2014.06.034 · Cited by 141 · see citing works
Electrochemical carbon dioxide and bicarbonate reduction on copper in weakly alkaline media
Kortlever, R., Tan, K., Kwon, Y., & Koper, M. T. M. (2013) · Journal of Solid State Electrochemistry · doi:10.1007/s10008-013-2100-9 · Cited by 141 · see citing works
Self-citationElectroreduction of CO2 on differently prepared copper electrodes
Kyriacou, G., & Anagnostopoulos, A. N. (1992) · Journal of Electroanalytical Chemistry · doi:10.1016/0022-0728(92)80079-j · Cited by 114 · see citing works
Electrochemical conversion of CO2 to C2 hydrocarbons using different ex situ copper electrodeposits
Gonçalves, M., Gomes, A., Condeço, J. A. D., Fernandes, T. R. C., Pardal, T. C., Sequeira, C. A. C., & Branco, J. B. (2013) · Electrochimica Acta · doi:10.1016/j.electacta.2013.04.015 · Cited by 97 · see citing works
Enabling Electrocatalytic Fischer–Tropsch Synthesis from Carbon Dioxide Over Copper-based Electrodes
Shibata, H., Moulijn, J. A., & Mul, G. (2008) · Catalysis Letters · doi:10.1007/s10562-008-9488-3 · Cited by 93 · see citing works
Self-citationSelective electrochemical conversion of CO2 to C2 hydrocarbons
Gonçalves, M., Gomes, A., Condeço, J. A. D., Fernandes, R., Pardal, T. C., Sequeira, C. A. C., & Branco, J. B. (2009) · Energy Conversion and Management · doi:10.1016/j.enconman.2009.08.002 · Cited by 84 · see citing works
A Step Closer to the Electrochemical Production of Liquid Fuels
Schouten, K. J. P., Calle‐Vallejo, F., & Koper, M. T. M. (2014) · Angewandte Chemie International Edition · doi:10.1002/anie.201406174 · Cited by 66 · see citing works
Self-citationWickman, B., Seidel, Y. E., Jusys, Z., Kasemo, B., & Behm, R. J. (2011) · ACS Nano · doi:10.1021/nn1021692 · Cited by 33 · 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
Griffin, G. L., & Bugayong, J. (2014) · MRS Proceedings · doi:10.1557/opl.2014.557 · Cited by 5 · see citing works
Ein wichtiger Schritt hin zur elektrochemischen Herstellung von Flüssigbrennstoffen
Schouten, K. J. P., Calle‐Vallejo, F., & Koper, M. T. M. (2014) · Angewandte Chemie · doi:10.1002/ange.201406174 · Cited by 4 · see citing works
Self-citation
Flagged first, then by citations
Research works printed but not linked: 6
- B. Kumar, M. Asadi, D. Pisasale, S. Sinha-Ray, B. A. Rosen, R. Haasch, J. Abiade, A. L. Yarin, A. Salehi-Khojin, Nat. Commun. 2013, 4, 2819.
- F. Calle-Vallejo, M. T. M. Koper, Angew. Chem. Int. Ed. 2013, 52, 7282 - 7285; Angew. Chem. 2013, 125, 7423 -7426.
- M. R. GonÅalves, A. Gomes, J. Condeco, R. Fernandes, T. Pardal, C. Se- queira, J. Branco, Energy Convers. Manage. 2010, 51, 30 -32.
- M. R. GonÅalves, A. Gomes, J. CondeÅo, T. Fernandes, T. Pardal, C. Se- queira, J. Branco, Electrochim. Acta 2013, 102, 388 -392.
- Y. Hori, Mod. Aspects Electrochem. 2008, 42, 89 -189.
- G. L. Griffin, J. Bugayong, MRS Online Proc. Libr. 2014, 1677, 2014.
Cited by
Sorted by citations
Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte
Nitopi, S., Bertheussen, E., Scott, S. B., Liu, X., Engstfeld, A. K., Horch, S., Seger, B., Stephens, I. E. L., Chan, K., Hahn, C., et al. (2019) · Chemical Reviews · doi:10.1021/acs.chemrev.8b00705 · Cited by 5,223 · see citing works
Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels
Birdja, Y. Y., Pérez-Gallent, E., Figueiredo, M. C., Göttle, A. J., Calle-Vallejo, F., & Koper, M. T. M. (2019) · Nature Energy · doi:10.1038/s41560-019-0450-y · Cited by 2,747 · see citing works
Self-citationDinh, C.-T., Burdyny, T., Kibria, M. G., Seifitokaldani, A., Gabardo, C. M., García de Arquer, F. P., Kiani, A., Edwards, J. P., De Luna, P., Bushuyev, O. S., et al. (2018) · Science · doi:10.1126/science.aas9100 · Cited by 2,515 · see citing works
Recent Advances in Inorganic Heterogeneous Electrocatalysts for Reduction of Carbon Dioxide
Zhu, D. D., Liu, J. L., & Qiao, S. Z. (2016) · Advanced Materials · doi:10.1002/adma.201504766 · Cited by 1,594 · see citing works
Kibria, M. G., Edwards, J. P., Gabardo, C. M., Dinh, C., Seifitokaldani, A., Sinton, D., & Sargent, E. H. (2019) · Advanced Materials · doi:10.1002/adma.201807166 · Cited by 1,331 · see citing works
Designing materials for electrochemical carbon dioxide recycling
Ross, M. B., De Luna, P., Li, Y., Dinh, C.-T., Kim, D., Yang, P., & Sargent, E. H. (2019) · Nature Catalysis · doi:10.1038/s41929-019-0306-7 · Cited by 1,302 · see citing works
Electrocatalysis for CO <sub>2</sub> conversion: from fundamentals to value-added products
Wang, G., Chen, J., Ding, Y., Cai, P., Yi, L., Li, Y., Tu, C., Hou, Y., Wen, Z., & Dai, L. (2021) · Chemical Society Reviews · doi:10.1039/d0cs00071j · Cited by 1,295 · 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
Zhang, L., Zhao, Z., & Gong, J. (2017) · Angewandte Chemie International Edition · doi:10.1002/anie.201612214 · Cited by 1,048 · 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
Varela, A. S., Kroschel, M., Reier, T., & Strasser, P. (2016) · Catalysis Today · doi:10.1016/j.cattod.2015.06.009 · Cited by 542 · 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
Lee, S., Kim, D., & Lee, J. (2015) · Angewandte Chemie International Edition · doi:10.1002/anie.201505730 · Cited by 320 · see citing works
Lum, Y., & Ager, J. W. (2018) · Nature Catalysis · doi:10.1038/s41929-018-0201-7 · Cited by 322 · see citing works
Investigating the Role of Copper Oxide in Electrochemical CO <sub>2</sub> Reduction in Real Time
Mandal, L., Yang, K. R., Motapothula, M. R., Ren, D., Lobaccaro, P., Patra, A., Sherburne, M., Batista, V. S., Yeo, B. S., Ager, J. W., et al. (2018) · ACS Applied Materials & Interfaces · doi:10.1021/acsami.7b15418 · Cited by 269 · see citing works
Effects of Anion Identity and Concentration on Electrochemical Reduction of CO <sub>2</sub>
Resasco, J., Lum, Y., Clark, E., Zeledon, J. Z., & Bell, A. T. (2018) · ChemElectroChem · doi:10.1002/celc.201701316 · Cited by 250 · see citing works
Tailoring gas-phase CO <sub>2</sub> electroreduction selectivity to hydrocarbons at Cu nanoparticles
Merino-Garcia, I., Albo, J., & Irabien, A. (2018) · Nanotechnology · doi:10.1088/1361-6528/aa994e · Cited by 129 · see citing works
Cavalca, F., Ferragut, R., Aghion, S., Eilert, A., Diaz-Morales, O., Liu, C., Koh, A. L., Hansen, T. W., Pettersson, L. G. M., & Nilsson, A. (2017) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.7b08278 · Cited by 123 · see citing works
Cao, L., Raciti, D., Li, C., Livi, K. J. T., Rottmann, P. F., Hemker, K. J., Mueller, T., & Wang, C. (2017) · ACS Catalysis · doi:10.1021/acscatal.7b03107 · Cited by 122 · see citing works
- Authors
- Kas, R., Kortlever, R., Yılmaz, H., Koper, M. T. M., & Mul, G.
- Affiliations
- Leiden University (NL)
- University of Twente (NL)
- Corresponding author
- Mul, Guido
- Venue
- ChemElectroChem
- Publisher
- Wiley
- Published
- 2014-12-09
- Volume
- 2
- Issue
- 3
- Pages
- 354-358
- ISSN
- 2196-0216 (ISSN-L)
- OpenAlex
- W2126497185
- Cited by
- 464
- References
- 46
- Citations by year
- 2026: 17 · 2025: 39 · 2024: 40 · 2023: 32 · 2022: 48 · 2021: 52 · 2020: 49 · 2019: 51 · 2018: 50 · 2017: 44 · 2016: 28 · 2015: 14
- FWCI
- 9.44
- Type
- journal article
- Language
- en
- Open access
- green
- hdl.handle.net
- Locations
- ChemElectroChem (publishedVersion)
- Leiden Repository (Leiden University) (submittedVersion)
- University of Twente Research Information (submittedVersion, other-oa)
- Data Archiving and Networked Services (DANS) (submittedVersion, other-oa)
- 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 › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
- Keywords
- electrochemical CO2 reduction, copper nanoparticles, ethylene production, methane production, hydrocarbon selectivity, surface pH, electrolyte concentration, CO2 pressure, electrode degradation
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