Abstract
The electrochemical reduction of CO2 in acidic conditions enables high single-pass carbon efficiency. However, the competing hydrogen evolution reaction reduces selectivity in the electrochemical reduction of CO2, a reaction in which the formation of CO, and its ensuing coupling, are each essential to achieving multicarbon (C2+) product formation. These two reactions rely on distinct catalyst properties that are difficult to achieve in a single catalyst. Here we report decoupling the CO2-to-C2+ reaction into two steps, CO2-to-CO and CO-to-C2+, by deploying two distinct catalyst layers operating in tandem to achieve the desired transformation. The first catalyst, atomically dispersed cobalt phthalocyanine, reduces CO2 to CO with high selectivity. This process increases local CO availability to enhance the C–C coupling step implemented on the second catalyst layer, which is a Cu nanocatalyst with a Cu–ionomer interface. The optimized tandem electrodes achieve 61% C2H4 Faradaic efficiency and 82% C2+ Faradaic efficiency at 800 mA cm−2 at 25 °C. When optimized for single-pass utilization, the system reaches a single-pass carbon efficiency of 90 ± 3%, simultaneous with 55 ± 3% C2H4 Faradaic efficiency and a total C2+ Faradaic efficiency of 76 ± 2%, at 800 mA cm−2 with a CO2 flow rate of 2 ml min−1.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
The authors declare that all data supporting the findings of this study are available within the paper and Supplementary Information files. Source data are provided with this paper.
References
Dinh, C. T. et al. CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface. Science 360, 783–787 (2018).
Birdja, Y. Y. et al. Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels. Nat. Energy 4, 732–745 (2019).
Gao, D., Arán-Ais, R. M., Jeon, H. S. & Roldan Cuenya, B. Rational catalyst and electrolyte design for CO2 electroreduction towards multicarbon products. Nat. Catal. 2, 198–210 (2019).
Ren, S. et al. Molecular electrocatalysts can mediate fast, selective CO2 reduction in a flow cell. Science 365, 367–369 (2019).
Wu, Y., Jiang, Z., Lu, X., Liang, Y. & Wang, H. Domino electroreduction of CO2 to methanol on a molecular catalyst. Nature 575, 639–642 (2019).
Choi, C. et al. Highly active and stable stepped Cu surface for enhanced electrochemical CO2 reduction to C2H4. Nat. Catal. 3, 804–812 (2020).
Chen, C. et al. Boosting the productivity of electrochemical CO2 reduction to multi-carbon products by enhancing CO2 diffusion through a porous organic cage. Angew. Chem. Int. Ed. 61, e202202607 (2022).
Weng, L.-C., Bell, A. T. & Weber, A. Z. Towards membrane-electrode assembly systems for CO2 reduction: a modeling study. Energy Environ. Sci. 12, 1950–1968 (2019).
Jeng, E. & Jiao, F. Investigation of CO2 single-pass conversion in a flow electrolyzer. React. Chem. Eng. 5, 1768–1775 (2020).
Ma, M. et al. Insights into the carbon balance for CO2 electroreduction on Cu using gas diffusion electrode reactor designs. Energy Environ. Sci. 13, 977–985 (2020).
Ma, M., Kim, S., Chorkendorff, I. & Seger, B. Role of ion-selective membranes in the carbon balance for CO2 electroreduction via gas diffusion electrode reactor designs. Chem. Sci. 11, 8854–8861 (2020).
Cofell, E. R., Nwabara, U. O., Bhargava, S. S., Henckel, D. E. & Kenis, P. J. A. Investigation of electrolyte-dependent carbonate formation on gas diffusion electrodes for CO2 electrolysis. ACS Appl. Mater. Inter. 13, 15132–15142 (2021).
Iizuka, A. et al. Carbon dioxide recovery from carbonate solutions using bipolar membrane electrodialysis. Sep. Purif. Technol. 101, 49–59 (2012).
Al-Mamoori, A., Krishnamurthy, A., Rownaghi, A. A. & Rezaei, F. Carbon capture and utilization update. Energy Technol. 5, 834–849 (2017).
Keith, D. W., Holmes, G., St. Angelo, D. & Heidel, K. A process for capturing CO2 from the atmosphere. Joule 2, 1573–1594 (2018).
Sisler, J. et al. Ethylene electrosynthesis: a comparative techno-economic analysis of alkaline vs membrane electrode assembly vs CO2–CO–C2H4 tandems. ACS Energy Lett. 6, 997–1002 (2021).
Gu, J. et al. Modulating electric field distribution by alkali cations for CO2 electroreduction in strongly acidic medium. Nat. Catal. 5, 268–276 (2022).
Huang, J. E. et al. CO2 electrolysis to multicarbon products in strong acid. Science 372, 1074–1078 (2021).
Monteiro, M. C. O., Philips, M. F., Schouten, K. J. P. & Koper, M. T. M. Efficiency and selectivity of CO2 reduction to CO on gold gas diffusion electrodes in acidic media. Nat. Commun. 12, 4943 (2021).
Xie, Y. et al. High carbon utilization in CO2 reduction to multi-carbon products in acidic media. Nat. Catal. 5, 564–570 (2022).
Ooka, H., Figueiredo, M. C. & Koper, M. T. M. Competition between hydrogen evolution and carbon dioxide reduction on copper electrodes in mildly acidic media. Langmuir 33, 9307–9313 (2017).
Bondue, C. J., Graf, M., Goyal, A. & Koper, M. T. M. Suppression of hydrogen evolution in acidic electrolytes by electrochemical CO2 reduction. J. Am. Chem. Soc. 143, 279–285 (2021).
Mariano, R. G. et al. Microstructural origin of locally enhanced CO2 electroreduction activity on gold. Nat. Mater. 20, 1000–1006 (2021).
Monteiro, M. C. O. et al. Absence of CO2 electroreduction on copper, gold and silver electrodes without metal cations in solution. Nat. Catal. 4, 654–662 (2021).
Banerjee, S., Gerke, C. S. & Thoi, V. S. Guiding CO2RR selectivity by compositional tuning in the electrochemical double layer. Acc. Chem. Res. 55, 504–515 (2022).
Nitopi, S. et al. Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte. Chem. Rev. 119, 7610–7672 (2019).
Shi, C., Hansen, H. A., Lausche, A. C. & Norskov, J. K. Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces. Phys. Chem. Chem. Phys. 16, 4720–4727 (2014).
Zhong, M. et al. Accelerated discovery of CO2 electrocatalysts using active machine learning. Nature 581, 178–183 (2020).
Zhang, Y.-J., Sethuraman, V., Michalsky, R. & Peterson, A. A. Competition between CO2 reduction and H2 evolution on transition-metal electrocatalysts. ACS Catal. 4, 3742–3748 (2014).
Liu, X. et al. Understanding trends in electrochemical carbon dioxide reduction rates. Nat. Commun. 8, 15438 (2017).
Wang, X. et al. Mechanistic reaction pathways of enhanced ethylene yields during electroreduction of CO2–CO co-feeds on Cu and Cu-tandem electrocatalysts. Nat. Nanotechnol. 14, 1063–1070 (2019).
Chen, C. et al. Cu-Ag tandem catalysts for high-rate CO2 electrolysis toward multicarbons. Joule 4, 1688–1699 (2020).
Wang, H. et al. Synergistic enhancement of electrocatalytic CO2 reduction to C2 oxygenates at nitrogen-doped nanodiamonds/Cu interface. Nat. Nanotechnol. 15, 131–137 (2020).
Wang, Y., Zheng, X. & Wang, D. Design concept for electrocatalysts. Nano Res. 15, 1730–1752 (2022).
Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science 355, eaad4998 (2017).
Li, F. et al. Molecular tuning of CO2-to-ethylene conversion. Nature 577, 509–513 (2020).
Li, F. et al. Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces. Nat. Catal. 3, 75–82 (2019).
Hung, S. F. et al. A metal-supported single-atom catalytic site enables carbon dioxide hydrogenation. Nat. Commun. 13, 819 (2022).
Skafte, T. L. et al. Selective high-temperature CO2 electrolysis enabled by oxidized carbon intermediates. Nat. Energy 4, 846–855 (2019).
Yan, J. et al. High-efficiency intermediate temperature solid oxide electrolyzer cells for the conversion of carbon dioxide to fuels. J. Power Sources 252, 79–84 (2014).
Ozden, A. et al. Carbon-efficient carbon dioxide electrolysers. Nat. Sustain. 5, 563–573 (2022).
Luc, W., Rosen, J. & Jiao, F. An Ir-based anode for a practical CO2 electrolyzer. Catal. Today 288, 79–84 (2017).
Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).
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).
Blochl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).
Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).
Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).
Fan, Q. et al. Electrochemical CO2 reduction to C2+ species: heterogeneous electrocatalysts, reaction pathways, and optimization strategies. Mater. Today Energy 10, 280–301 (2018).
Acknowledgements
This work was financially supported by the Ontario Research Foundation’s Research Excellence programme, the Natural Sciences and Engineering Research Council (NSERC) of Canada and TotalEnergies SE. This research used synchrotron resources of the Advanced Photon Source, an Office of Science User Facility 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 by the Canadian Light Source and its funding partners. All DFT computations were performed on the IBM BlueGene/Q supercomputer with support from the Southern Ontario Smart Computing Innovation Platform (SOSCIP) and the Niagara supercomputer at the SciNet HPC Consortium. SOSCIP 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, the Ontario Research Fund—Research Excellence and the University of Toronto. We acknowledge the Ontario Centre for the Characterization of Advanced Materials (OCCAM) for characterization facilities. J.D. acknowledges financial support from the Youth Innovation Promotion Association of the Chinese Academy of Sciences (Y2022006).
Author information
Authors and Affiliations
Contributions
E.H.S. supervised the project. Y.C. and E.H.S. conceived the idea. Y.C. designed the synthesis of the catalysts and carried out all the electrochemical experiments. X.-Y.L. with the help of P.O. carried out the DFT calculation. Z.C. performed the in situ Raman measurements. A.O. contributed to the preparation of IrOx-coated Ti mesh electrodes and the energy assessment. J.D. and J.A. performed the X-ray absorption spectroscopy measurements. J.D. helped to analyse the X-ray absorption spectroscopy data. J.Z., Q.Q., X.W., S.W. and C.Q. helped to characterize the materials. S.L. performed the COMSOL simulation. J.E.H. contributed to manuscript editing. A.O., J.Z., B.-H.L., C.T., Y.X., R.K.M., Y.Z., Y. Liu, H.L., H.S. and D.S. assisted with the data analysis and discussions. D.W. and Y. Li contributed to the design of catalysts and assisted in conceiving the idea. Y.C., X.-Y.L., Z.C. and E.H.S. wrote the manuscript. All authors discussed the results and assisted during manuscript preparation.
Corresponding author
Ethics declarations
Competing interests
There is a US provisional patent application (63/482.861) titled ‘Electroreduction of CO2 in acidic conditions using a catalyst having a dual CO generation and C-C coupling function’ filed by the authors Y.C., X.-Y.L., Z.C. and E.H.S. and their institutions. The remaining authors declare no competing interests.
Peer review
Peer review information
Nature Nanotechnology thanks Joel Ager III, Kazuhiro Takanabe and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Supplementary Information
Supplementary Figs. 1–68, Notes 1–12 and Tables 1–6.
Supplementary Data 1
The atomic coordination of the optimized models and related reaction transition states.
Source data
Source Data Figs. 1–4
Numerical data.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Chen, Y., Li, XY., Chen, Z. et al. Efficient multicarbon formation in acidic CO2 reduction via tandem electrocatalysis. Nat. Nanotechnol. 19, 311–318 (2024). https://doi.org/10.1038/s41565-023-01543-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41565-023-01543-8
This article is cited by
-
Electrochemical CO2 reduction passes the acid test
Nature Nanotechnology (2024)
