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Self-pressurizing nanoscale capsule catalysts for CO2 electroreduction to acetate or propanol

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The selective one-step CO2 electroreduction reaction (CO2RR) to acetate and propanol has garnered intense interest. Here we report the design of self-pressurizing nanoscale capsule catalysts for the CO2RR. A high-pressure CO intermediate environment is created around copper catalysts by a permselective enclosure. Microkinetic modelling, 13CO2/12CO co-feed experiments and in situ Raman spectroscopy confirm that a unique CO–CO2 coupling path is involved, which is only initiated at high CO intermediate pressure. This pathway benefits acetate production due to the kinetic and energetic advantages of COCO2*. The acetate Faradaic efficiency is 38.5 ± 2.2% (8 times higher than that achieved without enclosure) and the acetate partial current density is 328 ± 19 mA cm−2, which surpasses the performance of previous CO2RR catalysts. In situ investigation indicates that the CO pressure inside the nanoscale capsule catalysts can reach 8 ± 3 bar. Furthermore, self-pressurizing nanoscale capsule catalysts with a CuI-derived core can reduce CO2 to propanol with a Faradaic efficiency of 25.7 ± 1.2% and a conversion rate of 155 ± 3 mA cm−2.

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Fig. 1
Fig. 2: DFT and microkinetic model calculations.
Fig. 3: Mechanistic studies of the CO–CO2 coupling pathway under 13CO2/12CO reactant co-feeds.
Fig. 4: Structural and compositional analyses of the self-pressurizing nanoscale capsule catalysts.
Fig. 5: CO2RR performance of the Cu@CS-P self-pressurizing nanoscale capsule catalysts.
Fig. 6: Potential-dependent in situ Raman spectra under different feeding conditions.
Fig. 7: Other self-pressurizing nanoscale capsule catalysts and their CO2RR performance.

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Data availability

Data supporting the findings of this study are available in the paper and its Supplementary Information or are available from the corresponding authors upon request. Source data are available via Zenodo at (ref. 44). Source data are provided with this paper.

Change history

  • 28 June 2024

    The left arrow in the graphical abstract was originally labelled C2+ and has now been corrected to CO2.


  1. Chen, C., Khosrowabadi Kotyk, J. F. & Sheehan, S. W. Progress toward commercial application of electrochemical carbon dioxide reduction. Chem 4, 2571–2586 (2018).

    Article  CAS  Google Scholar 

  2. Arán-Ais, R. M., Scholten, F., Kunze, S., Rizo, R. & Roldan Cuenya, B. The role of in situ generated morphological motifs and Cu(I) species in C2+ product selectivity during CO2 pulsed electroreduction. Nat. Energy 5, 317–325 (2020).

    Article  Google Scholar 

  3. Sun, Z., Ma, T., Tao, H., Fan, Q. & Han, B. Fundamentals and challenges of electrochemical CO2 reduction using two-dimensional materials. Chem 3, 560–587 (2017).

    Article  CAS  Google Scholar 

  4. 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).

    Article  CAS  PubMed  Google Scholar 

  5. 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  CAS  Google Scholar 

  6. Gu, J. et al. Modulating electric field distribution by alkali cations for CO2 electroreduction in strongly acidic medium. Nat. Catal. 5, 268–276 (2022).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  8. Jouny, M., Luc, W. & Jiao, F. General techno-economic analysis of CO2 electrolysis systems. Ind. Eng. Chem. Res. 57, 2165–2177 (2018).

    Article  CAS  Google Scholar 

  9. Wang, X. et al. Efficient electrosynthesis of n-propanol from carbon monoxide using a Ag–Ru–Cu catalyst. Nat. Energy 7, 170–176 (2022).

    Article  Google Scholar 

  10. 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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  12. Ji, Y. et al. Selective CO-to-acetate electroreduction via intermediate adsorption tuning on ordered Cu–Pd sites. Nat. Catal. 5, 251–258 (2022).

    Article  CAS  Google Scholar 

  13. Wakerley, D. et al. Gas diffusion electrodes, reactor designs and key metrics of low-temperature CO2 electrolysers. Nat. Energy 7, 130–143 (2022).

    Article  CAS  Google Scholar 

  14. De Luna, P. et al. Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction. Nat. Catal. 1, 103–110 (2018).

    Article  Google Scholar 

  15. Li, J. et al. Constraining CO coverage on copper promotes high-efficiency ethylene electroproduction. Nat. Catal. 2, 1124–1131 (2019).

    Article  CAS  Google Scholar 

  16. Song, H., Song, J. T., Kim, B., Tan, Y. C. & Oh, J. Activation of C2H4 reaction pathways in electrochemical CO2 reduction under low CO2 partial pressure. Appl. Catal. B 272, 119049 (2020).

    Article  CAS  Google Scholar 

  17. Yang, P. P. et al. Protecting copper oxidation state via intermediate confinement for selective CO2 electroreduction to C2+ fuels. J. Am. Chem. Soc. 142, 6400–6408 (2020).

    Article  CAS  PubMed  Google Scholar 

  18. 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).

    Article  CAS  Google Scholar 

  19. Li, F. et al. Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces. Nat. Catal. 3, 75–82 (2019).

    Article  Google Scholar 

  20. Zhang, T. et al. Highly selective and productive reduction of carbon dioxide to multicarbon products via in situ CO management using segmented tandem electrodes. Nat. Catal. 5, 202–211 (2022).

    Article  CAS  Google Scholar 

  21. Chen, C. et al. Cu–Ag tandem catalysts for high-rate CO2 electrolysis toward multicarbons. Joule 4, 1688–1699 (2020).

    Article  CAS  Google Scholar 

  22. Peng, H. et al. The role of atomic carbon in directing electrochemical CO2 reduction to multicarbon products. Energy Environ. Sci. 14, 473–482 (2021).

    Article  CAS  Google Scholar 

  23. Li, J. et al. Electroreduction of CO2 to formate on a copper-based electrocatalyst at high pressures with high energy conversion efficiency. J. Am. Chem. Soc. 142, 7276–7282 (2020).

    Article  CAS  PubMed  Google Scholar 

  24. Scialdone, O. et al. Electrochemical reduction of carbon dioxide to formic acid at a tin cathode in divided and undivided cells: effect of carbon dioxide pressure and other operating parameters. Electrochim. Acta 199, 332–341 (2016).

    Article  CAS  Google Scholar 

  25. Edwards, J. P. et al. Efficient electrocatalytic conversion of carbon dioxide in a low-resistance pressurized alkaline electrolyzer. Appl. Energy 261, 114305 (2020).

    Article  CAS  Google Scholar 

  26. Gabardo, C. M. et al. Combined high alkalinity and pressurization enable efficient CO2 electroreduction to CO. Energy Environ. Sci. 11, 2531–2539 (2018).

    Article  CAS  Google Scholar 

  27. Ebadi Amooghin, A. et al. Substantial breakthroughs on function-led design of advanced materials used in mixed matrix membranes (MMMs): a new horizon for efficient CO2 separation. Prog. Mater Sci. 102, 222–295 (2019).

    Article  CAS  Google Scholar 

  28. Li, X. et al. Efficient CO2 capture by functionalized graphene oxide nanosheets as fillers to fabricate multi-permselective mixed matrix membranes. ACS Appl. Mater. Interfaces 7, 5528–5537 (2015).

    Article  CAS  PubMed  Google Scholar 

  29. Lee, J.-Y. et al. Surface-attached brush-type CO2-philic poly(PEGMA)/PSf composite membranes by UV/ozone-induced graft polymerization: fabrication, characterization, and gas separation properties. J. Membr. Sci. 589, 117214 (2019).

    Article  CAS  Google Scholar 

  30. Li, P. et al. High-performance multilayer composite membranes with mussel-inspired polydopamine as a versatile molecular bridge for CO2 separation. ACS Appl. Mater. Interfaces 7, 15481–15493 (2015).

    Article  CAS  PubMed  Google Scholar 

  31. Xiao, H., Cheng, T. & Goddard, W. A. 3rd 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).

    Article  CAS  PubMed  Google Scholar 

  32. Luc, W. et al. Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate. Nat. Catal. 2, 423–430 (2019).

    Article  CAS  Google Scholar 

  33. Luo, W., Nie, X., Janik, M. J. & Asthagiri, A. Facet dependence of CO2 reduction paths on Cu electrodes. ACS Catal. 6, 219–229 (2015).

    Article  Google Scholar 

  34. Liu, X. et al. pH effects on the electrochemical reduction of CO2 towards C2 products on stepped copper. Nat. Commun. 10, 32 (2019).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  35. Zijlstra, B. et al. First-principles microkinetics simulations of electrochemical reduction of CO2 over Cu catalysts. Electrochim. Acta 335, 135665 (2020).

    Article  CAS  Google Scholar 

  36. Campbell, C. T. The degree of rate control: a powerful tool for catalysis research. ACS Catal. 7, 2770–2779 (2017).

    Article  CAS  Google Scholar 

  37. Yadav, L. D. S. in Organic Spectroscopy (ed. Yadav, L. D. S.) 195–223 (Springer, 2005).

  38. Ionin, B. I. & Ershov, B. A. in NMR Spectroscopy in Organic Chemistry (eds Ionin, B. I. & Ershov, B. A.) 125–167 (Springer, 1970).

  39. Lin, L. S., Song, J., Yang, H. H. & Chen, X. Yolk–shell nanostructures: design, synthesis, and biomedical applications. Adv. Mater. 30, 1704639 (2018).

  40. Yu, Z. et al. Kinetics driven by hollow nanoreactors: an opportunity for controllable catalysis. Angew. Chem. Int. Ed. 62, e202213612 (2023).

    Article  CAS  Google Scholar 

  41. Li, B., Ma, J. G. & Cheng, P. Silica-protection-assisted encapsulation of Cu2O nanocubes into a metal-organic framework (ZIF-8) to provide a composite catalyst. Angew. Chem. Int. Ed. 57, 6834–6837 (2018).

    Article  CAS  Google Scholar 

  42. 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).

  43. Wen, G. et al. Continuous CO2 electrolysis using a CO2 exsolution-induced flow cell. Nat. Energy 7, 978–988 (2022).

    Article  CAS  Google Scholar 

  44. Cai, Y. Source data of “Self-pressurizing nanocatalytic capsules for CO2 electroreduction to acetate or propanol”. Zenodo (2024).

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We thank B. Sun and J.-J. Zhang for discussion and reading the paper. We thank Y. Wu and his team at Nanjing University for gas permeation characterization. W.Z. acknowledges support from the National Natural Science Foundation of China (22176086), the Natural Science Foundation of Jiangsu Province (BK20210189), the Carbon Peaking and Carbon Neutrality Technological Innovation Foundation of Jiangsu Province (BE2022861), the State Key laboratory of Pollution Control and Resource Reuse (PCRR-ZZ-202106), the Fundamental Research Funds for the Central Universities (021114380183), the Research Funds from Frontiers Science Center for Critical Earth Material Cycling of Nanjing University and Research Funds for Jiangsu Distinguished Professor. J.-J.Z. acknowledges support from the Excellent Research Program of Nanjing University (ZYJH004) and the Shandong Provincial Natural Science Foundation (ZR2020ZD37).

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Authors and Affiliations



Y.C. conceived the idea and designed the experiments. Y.C. and R.Y. performed the catalytic performance evaluations. L.X. performed the electrochemically active surface area test and improved the colour palette of the figures. J.F., Z.L., K.L., Y.-C.C., S.D., Z.L., J.-R.Z., J.-J.Z., Y.L. and W.Z. discussed the results and commented on the paper. Y.C., J.F. and W.Z. co-wrote the paper. Y.L. was involved in the concept discussion and paper preparation and revision. W.Z. supervised the whole project and was involved in paper preparation and revision.

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Correspondence to Yuehe Lin or Wenlei Zhu.

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Nature Synthesis thanks Min-Rui Gao, Federica Proietto and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Cai, Y., Yang, R., Fu, J. et al. Self-pressurizing nanoscale capsule catalysts for CO2 electroreduction to acetate or propanol. Nat. Synth (2024).

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