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

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Abstract

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 https://doi.org/10.5281/zenodo.10809171 (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.

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Acknowledgements

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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Contributions

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). https://doi.org/10.1038/s44160-024-00552-2

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