The availability of inexpensive industrial CO gas streams motivates efficient electrocatalytic upgrading of CO to higher-value feedstocks such as ethylene. However, the electrosynthesis of ethylene by the CO reduction reaction (CORR) has suffered from low selectivity and energy efficiency. Here we find that the recent strategy of increasing performance through use of highly alkaline electrolyte—which is very effective in CO2RR—fails in CORR and drives the reaction to acetate. We then observe that ethylene selectivity increases when we constrain (decrease) CO availability. Using density functional theory, we show how CO coverage on copper influences the reaction pathways of ethylene versus oxygenate: lower CO coverage stabilizes the ethylene-relevant intermediates whereas higher CO coverage favours oxygenate formation. We then control local CO availability experimentally by tuning the CO concentration and reaction rate; we achieve ethylene Faradaic efficiencies of 72% and a partial current density of >800 mA cm−2. The overall system provides a half-cell energy efficiency of 44% for ethylene production.
Subscribe to Journal
Get full journal access for 1 year
only $8.25 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
The data that support the findings of this study are available from the corresponding author on reasonable request.
Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science 355, eaad4998 (2017).
Zhang, L., Zhao, Z. J. & Gong, J. L. Nanostructured materials for heterogeneous electrocatalytic CO2 reduction and their related reaction mechanisms. Angew. Chem. Int. Ed. 56, 11326–11353 (2017).
Zheng, X. L. et al. Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials. Nat. Catal. 2, 55–61 (2019).
Dinh, C. T. et al. CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface. Science 360, 783–787 (2018).
De Luna, P. et al. Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction. Nat. Catal. 1, 103–110 (2018).
Zhuang, T. T. et al. Steering post-C–C coupling selectivity enables high efficiency electroreduction of carbon dioxide to multi-carbon alcohols. Nat. Catal. 1, 421–428 (2018).
Zhou, Y. S. et al. Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons. Nat. Chem. 10, 974–980 (2018).
Li, C. W., Ciston, J. & Kanan, M. W. Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper. Nature 508, 504–507 (2014).
Jouny, M., Luc, W. & Jiao, F. High-rate electroreduction of carbon monoxide to multi-carbon products. Nat. Catal. 1, 748–755 (2018).
Liu, M. et al. Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration. Nature 537, 382–386 (2016).
Haas, T., Krause, R., Weber, R., Demler, M. & Schmid, G. Technical photosynthesis involving CO2 electrolysis and fermentation. Nat. Catal. 1, 32–39 (2018).
Schreier, M. et al. Solar conversion of CO2 to CO using earth-abundant electrocatalysts prepared by atomic layer modification of CuO. Nat. Energy 2, 17087 (2017).
Li, J. et al. Efficient electrocatalytic CO2 reduction on a three-phase interface. Nat. Catal. 1, 592–600 (2018).
Spurgeon, J. M. & Kumar, B. A comparative technoeconomic analysis of pathways for commercial electrochemical CO2 reduction to liquid products. Energy Environ. Sci. 11, 1536–1551 (2018).
Jouny, M., Luc, W. & Jiao, F. General techno-economic analysis of CO2 electrolysis systems. Ind. Eng. Chem. Res. 57, 2165–2177 (2018).
Han, L. H., Zhou, W. & Xiang, C. X. High-rate electrochemical reduction of carbon monoxide to ethylene using Cu-nanoparticle-based gas diffusion electrodes. ACS Energy Lett. 3, 855–860 (2018).
Zhuang, T. T. et al. Copper nanocavities confine intermediates for efficient electrosynthesis of C3 alcohol fuels from carbon monoxide. Nat. Catal. 1, 946–951 (2018).
Pang, Y. J. et al. Efficient electrocatalytic conversion of carbon monoxide to propanol using fragmented copper. Nat. Catal. 2, 251–258 (2019).
Li, J. et al. Effectively increased efficiency for electroreduction of carbon monoxide using supported polycrystalline copper powder electrocatalysts. ACS Catal. 9, 4709–4718 (2019).
Gabardo, C. M. et al. Combined high alkalinity and pressurization enable efficient CO2 electroreduction to CO. Energy Environ. Sci. 11, 2531–2539 (2018).
Lum, Y. W. & Ager, J. W. Evidence for product-specific active sites on oxide-derived Cu catalysts for electrochemical CO2 reduction. Nat. Catal. 2, 86–93 (2019).
Xiao, H., Cheng, T. & Goddard, W. A. Atomistic mechanisms underlying selectivities in C1 and C2 products from electrochemical reduction of CO on Cu(111). J. Am. Chem. Soc. 139, 130–136 (2017).
Lum, Y. W., Cheng, T., Goddard, W. A. & Ager, J. W. Electrochemical CO reduction builds solvent water into oxygenate products. J. Am. Chem. Soc. 140, 9337–9340 (2018).
Cheng, T., Xiao, H. & Goddard, W. A. Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K. Proc. Natl Acad. Sci. USA 114, 1795–1800 (2017).
Lausche, A. C. et al. On the effect of coverage-dependent adsorbate-adsorbate interactions for CO methanation on transition metal surfaces. J. Catal. 307, 275–282 (2013).
Montoya, J. H., Shi, C., Chan, K. & Nørskov, J. K. Theoretical insights into a CO dimerization mechanism in CO2 electroreduction. J. Phys. Chem. Lett. 6, 2032–2037 (2015).
Liu, X. Y. et al. Understanding trends in electrochemical carbon dioxide reduction rates. Nat. Commun. 8, 15438 (2017).
Sandberg, R. B., Montoya, J. H., Chan, K. & Nørskov, J. K. CO–CO coupling on Cu facets: coverage, strain and field effects. Surf. Sci. 654, 56–62 (2016).
Nørskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004).
Schouten, K. J. P., Qin, Z., Pérez Gallent, E. & Koper, M. T. Two pathways for the formation of ethylene in CO reduction on single-crystal copper electrodes. J. Am. Chem. Soc. 134, 9864–9867 (2012).
Wang, Z., Cao, X. M., Zhu, J. & Hu, P. Activity and coke formation of nickel and nickel carbide in dry reforming: a deactivation scheme from density functional theory. J. Catal. 311, 469–480 (2014).
Wang, Z., Wang, H.-F. & Hu, P. Possibility of designing catalysts beyond the traditional volcano curve: a theoretical framework for multi-phase surfaces. Chem. Sci. 6, 5703–5711 (2015).
Liu, Q. et al. Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping. Nat. Energy 3, 936–943 (2018).
Schreier, M., Yoon, Y., Jackson, M. N. & Surendranath, Y. Competition between H and CO for active sites governs copper‐mediated electrosynthesis of hydrocarbon fuels. Angew. Chem., Int. Ed. 57, 10221–10225 (2018).
Wang, L. et al. Electrochemical carbon monoxide reduction on polycrystalline copper: effects of potential, pressure, and pH on selectivity toward multicarbon and oxygenated products. ACS Catal. 8, 7445–7454 (2018).
Handoko, A. D., Wei, F., Yeo, B. S. & Seh, Z. W. Understanding heterogeneous electrocatalytic carbon dioxide reduction through operando techniques. Nat. Catal. 1, 922–934 (2018).
Razzaq, R., Li, C. & Zhang, S. Coke oven gas: availability, properties, purification, and utilization in China. Fuel 113, 287–299 (2013).
Wang, S., Wang, G., Jiang, F., Luo, M. & Li, H. Chemical looping combustion of coke oven gas by using Fe2O3/CuO with MgAl2O4 as oxygen carrier. Energy Environ. Sci. 3, 1353–1360 (2010).
Hoang, T. T. H., Ma, S. C., Gold, J. I., Kenis, P. J. A. & Gewirth, A. A. Nanoporous copper films by additive-controlled electrodeposition: CO2 reduction catalysis. ACS Catal. 7, 3313–3321 (2017).
Hoang, T. T. H. et al. Nanoporous copper silver alloys by additive-controlled electrodeposition for the selective electroreduction of CO2 to ethylene and ethanol. J. Am. Chem. Soc. 140, 5791–5797 (2018).
Ma, S. C. et al. One-step electrosynthesis of ethylene and ethanol from CO2 in an alkaline electrolyzer. J. Power Sources 301, 219–228 (2016).
Huang, Y., Handoko, A. D., Hirunsit, P. & Yeo, B. S. Electrochemical reduction of CO2 using copper single-crystal surfaces: effects of CO* coverage on the selective formation of ethylene. ACS Catal. 7, 1749–1756 (2017).
Eren, B. et al. Activation of Cu(111) surface by decomposition into nanoclusters driven by CO adsorption. Science 351, 475–478 (2016).
Eren, B. et al. One-dimensional nanoclustering of the Cu(100) surface under CO gas in the mbar pressure range. Surf. Sci. 651, 210–214 (2016).
Li, J. et al. Copper adparticle enabled selective electrosynthesis of n-propanol. Nat. Commun. 9, 4614 (2018).
Kresse, G. & Furthmuller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Kresse, G. & Furthmuller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).
Kresse, G. & Hafner, J. Ab-initio molecular-dynamics simulation of the liquid-metal amorphous–semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).
Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).
Blochl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H–Pu. J. Chem. Phys. 132, 154104 (2010).
Alavi, A., Hu, P., Deutsch, T., Silvestrelli, P. L. & Hutter, J. CO oxidation on Pt(111): an ab initio density functional theory study. Phys. Rev. Lett. 80, 3650 (1998).
Michaelides, A. et al. Identification of general linear relationships between activation energies and enthalpy changes for dissociation reactions at surfaces. J. Am. Chem. Soc. 125, 3704–3705 (2003).
Liu, Z. P. & Hu, P. General rules for predicting where a catalytic reaction should occur on metal surfaces: a density functional theory study of C–H and C–O bond breaking/making on flat, stepped, and kinked metal surfaces. J. Am. Chem. Soc. 125, 1958–1967 (2003).
Shang, Y., Zhang, D. F. & Guo, L. CuCl-intermediated construction of short-range-ordered Cu2O mesoporous spheres with excellent adsorption performance. J. Mater. Chem. 22, 856–861 (2012).
Jhong, H. R. M., Brushett, F. R. & Kenis, P. J. The effects of catalyst layer deposition methodology on electrode performance. Adv. Energy Mater. 3, 589–599 (2013).
This work was supported financially by the Ontario Research Fund: Research Excellence programme, the Natural Sciences and Engineering Research Council of Canada, the CIFAR Bio-inspired Solar Energy programme and the University of Toronto Connaught grant. This research used synchrotron resources of the APS, an Office of Science user facility that is operated for the US Department of Energy Office of Science by Argonne National Laboratory and was supported by the US Department of Energy under contract no. DE-AC02-06CH11357, as well as the Canadian Light Source and its funding partners. This research also used infrastructure provided by the Canada Foundation for Innovation and the Ontario Research Fund. The authors thank T.P. Wu, Y.Z. Finfrock and L. Ma for technical support at the 9BM beamline of APS. D.S. acknowledges the Natural Sciences and Engineering Research Council E.W.R Steacie Memorial Fellowship. J.L. acknowledges the Banting Postdoctoral Fellowships programme. C.M.G. acknowledges the Natural Sciences and Engineering Research Council Postdoctoral Fellowships programme. All of the DFT computations were performed on the IBM BlueGene/Q supercomputer with support from the Southern Ontario Smart Computing Innovation Platform and Niagara supercomputer at the SciNet HPC Consortium. The Southern Ontario Smart Computing Innovation Platform is funded by the Federal Economic Development Agency of Southern Ontario, the Province of Ontario, IBM Canada Ltd., Ontario Centres of Excellence, Mitacs and 15 Ontario academic member institutions. SciNet is funded by: the Canada Foundation for Innovation; the Government of Ontario; Ontario Research Fund - Research Excellence; and the University of Toronto.
The authors declare no competing interests.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Li, J., Wang, Z., McCallum, C. et al. Constraining CO coverage on copper promotes high-efficiency ethylene electroproduction. Nat Catal 2, 1124–1131 (2019). https://doi.org/10.1038/s41929-019-0380-x
Synergistic adsorption and activation of nickel phthalocyanine anchored onto ketjenblack for CO2 electrochemical reduction
Applied Surface Science (2021)
Journal of the American Chemical Society (2020)
A reconstructed porous copper surface promotes selectivity and efficiency toward C2 products by electrocatalytic CO2 reduction
Chemical Science (2020)
Covalent Triazine Framework Confined Copper Catalysts for Selective Electrochemical CO2 Reduction: Operando Diagnosis of Active Sites
ACS Catalysis (2020)