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Energy- and carbon-efficient CO2/CO electrolysis to multicarbon products via asymmetric ion migration–adsorption

Nature Energy volume 8, pages 179–190 (2023)Cite this article

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Abstract

Carbon dioxide/monoxide (CO2/CO) electrolysis provides a means to convert emissions into multicarbon products. However, impractical energy and carbon efficiencies limit current systems. Here we show that these inefficiencies originate from uncontrolled gas/ion distributions in the local reaction environment. Understanding of the flows of cations and anions motivated us to seek a route to block cation migration to the catalyst surface—a strategy we instantiate using a covalent organic framework (COF) in bulk heterojunction with a catalyst. The π-conjugated hydrophobic COFs constrain cation (potassium) diffusion via cation–π interactions, while promoting anion (hydroxide) and gaseous feedstock adsorption on the catalyst surface. As a result, a COF-mediated catalyst enables electrosynthesis of multicarbon products from CO for 200 h at a single-pass carbon efficiency of 95%, an energy efficiency of 40% and a current density of 240 mA cm−2.

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Fig. 1: Energy and carbon efficiency limitations in CO2/CO electrolysis.
Fig. 2: Local cation and anion transport in a zero-gap, catholyte-free MEA electrolyser.
Fig. 3: The CCBH catalyst.
Fig. 4: The CCBH catalyst for energy- and carbon-efficient CO2RR/CORR.

Data availability

All of the data supporting the findings of this study are available within the published article and its Supplementary Information files. Source data are provided with this paper.

References

  1. 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).

    Article  Google Scholar 

  2. Huang, J. E. et al. CO2 electrolysis to multicarbon products in strong acid. Science 372, 1074–1078 (2021).

    Article  Google Scholar 

  3. Nitopi, S. et al. Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte. Chem. Rev. 119, 7610–7672 (2019).

    Article  Google Scholar 

  4. Jouny, M., Hutchings, G. S. & Jiao, F. Carbon monoxide electroreduction as an emerging platform for carbon utilization. Nat. Catal. 2, 1062–1070 (2019).

    Article  Google Scholar 

  5. De Luna, P. et al. What would it take for renewably powered electrosynthesis to displace petrochemical processes? Science 364, eaav3506 (2019).

    Article  Google Scholar 

  6. Li, J. et al. Enhanced multi-carbon alcohol electroproduction from CO via modulated hydrogen adsorption. Nat. Commun. 11, 3685 (2020).

    Article  Google Scholar 

  7. Wang, X. et al. Efficient electrically powered CO2-to-ethanol via suppression of deoxygenation. Nat. Energy 5, 478–486 (2020).

    Article  Google Scholar 

  8. Ozden, A. et al. High-rate and efficient ethylene electrosynthesis using a catalyst/promoter/transport layer. ACS Energy Lett. 5, 2811–2818 (2020).

    Article  Google Scholar 

  9. Shin, H., Hansen, K. U. & Jiao, F. Techno-economic assessment of low-temperature carbon dioxide electrolysis. Nat. Sustain. 4, 911–919 (2021).

    Article  Google Scholar 

  10. Chen, C., Li, Y. & Yang, P. Address the “alkalinity problem” in CO2 electrolysis with catalyst design and translation. Joule 5, 737–742 (2021).

    Article  Google Scholar 

  11. Rabinowitz, J. A. & Kanan, M. W. The future of low-temperature carbon dioxide electrolysis depends on solving one basic problem. Nat. Commun. 11, 5231 (2020).

    Article  Google Scholar 

  12. Ren, S. et al. Molecular electrocatalysts can mediate fast, selective CO2 reduction in a flow cell. Science 365, 367–369 (2019).

    Article  Google Scholar 

  13. Kim, D. et al. Selective CO2 electrocatalysis at the pseudocapacitive nanoparticle/ordered-ligand interlayer. Nat. Energy 5, 1032–1042 (2020).

    Article  Google Scholar 

  14. Li, J. et al. Efficient electrocatalytic CO2 reduction on a three-phase interface. Nat. Catal. 1, 592–600 (2018).

    Article  Google Scholar 

  15. Ripatti, D. S., Veltman, T. R. & Kanan, M. W. Carbon monoxide gas diffusion electrolysis that produces concentrated C2 products with high single-pass conversion. Joule 3, 240–256 (2019).

    Article  Google Scholar 

  16. De Arquer, P. F. et al. CO2 electrolysis to multicarbon products at activities greater than 1 A cm−2. Science 367, 661–666 (2020).

    Article  Google Scholar 

  17. Dinh, C. T. et al. CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface. Science 360, 783–787 (2018).

    Article  Google Scholar 

  18. Jouny, M., Luc, W. & Jiao, F. High-rate electroreduction of carbon monoxide to multi-carbon products. Nat. Catal. 1, 748–755 (2018).

    Article  Google Scholar 

  19. Ma, W. et al. Electrocatalytic reduction of CO2 to ethylene and ethanol through hydrogen-assisted C–C coupling over fluorine-modified copper. Nat. Catal. 3, 478–487 (2020).

    Article  Google Scholar 

  20. Gabardo, C. M. et al. Continuous carbon dioxide electroreduction to concentrated multi-carbon products using a membrane electrode assembly. Joule 3, 2777–2791 (2019).

    Article  Google Scholar 

  21. O’Brien, C. P. et al. Single pass CO2 conversion exceeding 85% in the electrosynthesis of multicarbon products via local CO2 regeneration. ACS Energy Lett. 6, 2952–2959 (2021).

    Article  Google Scholar 

  22. Ozden, A. et al. Cascade CO2 electroreduction enables efficient carbonate-free production of ethylene. Joule 5, 706–719 (2021).

    Article  Google Scholar 

  23. Ozden, A. et al. Carbon-efficient carbon dioxide electrolysers. Nat. Sustain. 5, 563–573 (2022).

    Article  Google Scholar 

  24. 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).

    Article  Google Scholar 

  25. Xu, Y. et al. Self-cleaning CO2 reduction systems: unsteady electrochemical forcing enables stability. ACS Energy Lett. 6, 809–815 (2021).

    Article  Google Scholar 

  26. Endrődi, B. et al. Operando cathode activation with alkali metal cations for high current density operation of water-fed zero-gap carbon dioxide electrolysers. Nat. Energy 6, 439–448 (2021).

    Article  Google Scholar 

  27. Bohra, D., Chaudhry, J. H., Burdyny, T., Pidko, E. A. & Smith, W. A. Modeling the electrical double layer to understand the reaction environment in a CO2 electrocatalytic system. Energy Environ. Sci. 12, 3380–3389 (2019).

    Article  Google Scholar 

  28. Lin, S. et al. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. Science 349, 1208–1213 (2015).

    Article  Google Scholar 

  29. Kandambeth, S., Kale, V. S., Shekhah, O., Alshareef, H. N. & Eddaoudi, M. 2D covalent-organic framework electrodes for supercapacitors and rechargeable metal-ion batteries. Adv. Energy Mater. 12, 2100177 (2022).

    Article  Google Scholar 

  30. Chen, X., Zhang, H., Ci, C., Sun, W. & Wang, Y. Few-layered boronic ester based covalent organic frameworks/carbon nanotube composites for high-performance K-organic batteries. ACS Nano 13, 3600–3607 (2019).

    Article  Google Scholar 

  31. Kandambeth, S. et al. Covalent organic frameworks as negative electrodes for high-performance asymmetric supercapacitors. Adv. Energy Mater. 10, 2001673 (2020).

    Article  Google Scholar 

  32. Ma, J. C. & Dougherty, D. A. The cation–π interaction. Chem. Rev. 97, 1303–1324 (1997).

    Article  Google Scholar 

  33. Liu, M. et al. Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration. Nature 537, 382–386 (2016).

    Article  Google Scholar 

  34. Zhan, C. et al. Revealing the CO coverage-driven C–C coupling mechanism for electrochemical CO2 reduction on Cu2O nanocubes via operando Raman spectroscopy. ACS Catal. 11, 7694–7701 (2021).

    Article  Google Scholar 

  35. 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).

    Article  Google Scholar 

  36. Niaura, G. Surface-enhanced Raman spectroscopic observation of two kinds of adsorbed OH− ions at copper electrode. Electrochim. Acta 45, 3507–3519 (2000).

    Article  Google Scholar 

  37. Zhao, Y. et al. Speciation of Cu surfaces during the electrochemical CO reduction reaction. J. Am. Chem. Soc. 142, 9735–9743 (2020).

    Google Scholar 

  38. Verdaguer-Casadevall, A. et al. Probing the active surface sites for CO reduction on oxide-derived copper electrocatalysts. J. Am. Chem. Soc. 137, 9808–9811 (2015).

    Article  Google Scholar 

  39. Wakerley, D. et al. Bio-inspired hydrophobicity promotes CO2 reduction on a Cu surface. Nat. Mater. 18, 1222–1227 (2019).

    Article  Google Scholar 

  40. Xing, Z., Hu, L., Ripatti, D. S., Hu, X. & Feng, X. Enhancing carbon dioxide gas-diffusion electrolysis by creating a hydrophobic catalyst microenvironment. Nat. Commun. 12, 136 (2021).

    Article  Google Scholar 

  41. Kim, C. et al. Tailored catalyst microenvironments for CO2 electroreduction to multicarbon products on copper using bilayer ionomer coatings. Nat. Energy 6, 1026–1034 (2021).

    Article  Google Scholar 

  42. 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).

    Article  Google Scholar 

  43. 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).

    Article  Google Scholar 

  44. Rubcumintara, T. & Han, K. N. Metal ionic diffusivity: measurement and application. Miner. Process. Extr. Metall. Rev. 7, 23–47 (2007).

    Article  Google Scholar 

  45. Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).

    Article  Google Scholar 

  46. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Article  Google Scholar 

  47. Blöchl, P. E., Jepsen, O. & Andersen, O. K. Improved tetrahedron method for Brillouin-zone integrations. Phys. Rev. B 49, 16223–16233 (1994).

    Article  Google Scholar 

  48. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

    Article  Google Scholar 

  49. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  Google Scholar 

  50. Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).

    Article  MathSciNet  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the Ontario Research Fund – Research Excellence programme, the Natural Sciences and Engineering Research Council (NSERC) of Canada and Natural Resources Canada’s Clean Growth Program. This research used synchrotron resources of the Advanced Photon Source (an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory) and was supported by the US DOE under contract number DE-AC02-06CH11357, as well as the Canadian Light Source and its funding partners. Support from the Canada Research Chairs Program is gratefully acknowledged, as is support from an NSERC E.W.R. Steacie Fellowship to D.S. J.L. thanks the National Natural Science Foundation of China (grant number BE3250011), the National Key Research and Development Program of China (grant number 2022YFA1505100), and Shanghai Jiao Tong University (grant number WH220432516) for support. F.P.G.d.A. acknowledges funding from CEX2019-000910-S (MCIN/AEI/10.13039/501100011033), Fundación Cellex, Fundació Mir-Puig, Generalitat de Catalunya through CERCA and the La Caixa Foundation (100010434; EU Horizon 2020 Marie Skłodowska-Curie grant agreement 847648).

Author information

Author notes

  1. These authors contributed equally: Adnan Ozden, Jun Li, Sharath Kandambeth, Xiao-Yan Li.

Authors and Affiliations

  1. Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario, Canada

    Adnan Ozden, Jun Li, Shijie Liu, Tartela Alkayyali & David Sinton

  2. Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario, Canada

    Jun Li, Xiao-Yan Li, Pengfei Ou, Ya-Kun Wang, Alexander H. Ip & Edward H. Sargent

  3. Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai, China

    Jun Li

  4. Division of Physical Sciences and Engineering, Advanced Membranes and Porous Materials Center, Functional Materials Design, Discovery and Development Research Group, King Abdullah University of Science and Technology, Thuwal, Kingdom of Saudi Arabia

    Sharath Kandambeth, Osama Shekhah, Vinayak S. Kale, Prashant M. Bhatt & Mohamed Eddaoudi

  5. Structural Biology Center, X-Ray Science Division, Argonne National Laboratory, Lemont, IL, USA

    Y. Zou Finfrock

  6. ICFO – Institut de Ciències Fotòniques, The Barcelona Institute of Science and Technology, Barcelona, Spain

    F. Pelayo García de Arquer

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Contributions

D.S., E.H.S., M.E. and J.L. supervised the project. A.O., J.L. and S.K. conceived of the idea. A.O. and J.L. designed and carried out all of the electrochemical experiments. A.O. synthesized the catalysts and fabricated the electrodes and slim flow-cell electrolyser. A.O. performed the SEM, TEM and XPS measurements. S.L. performed the COMSOL simulations. S.K., V.S.K. and P.M.B. synthesized and characterized the Hex–Aza–COF nanosheets. Y.Z.F. performed the XAS measurements. Y.-K.W. performed the XRD measurements. X.-Y.L. performed the DFT calculations with the assistance of P.O. T.A., F.P.G.d.A. and A.H.I. contributed to data analysis. A.O. and J.L. cowrote the manuscript. D.S., E.H.S. and O.S. contributed to manuscript editing. All authors discussed the results and assisted during manuscript preparation.

Corresponding authors

Correspondence to Jun Li, Mohamed Eddaoudi, Edward H. Sargent or David Sinton.

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Nature Energy thanks Ezra Clark and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs., 1–57, notes 1–7, Tables 1–50 and references 1–15.

Supplementary Data

Source data for Supplementary Figs. 2a–f, 3a–f, 18a,b, 19a–f, 20, 24a–c, 26a,b, 27a,b, 29b,c, 32, 33, 35, 36a–f, 37, 38a–c, 39, 40a–c, 41, 42a–c, 43a–d, 51–54, 56 and 57.

Source data

Source Data Fig. 1

Source data for Fig. 1b.

Source Data Fig. 3

Source data for Fig. 3f–h.

Source Data Fig. 4

Source data for Fig. 4a.

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Ozden, A., Li, J., Kandambeth, S. et al. Energy- and carbon-efficient CO2/CO electrolysis to multicarbon products via asymmetric ion migration–adsorption. Nat Energy 8, 179–190 (2023). https://doi.org/10.1038/s41560-022-01188-2

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