Abstract
Electrolysis that reduces carbon dioxide (CO2) to useful chemicals can, in principle, contribute to a more sustainable and carbon-neutral future1,2,3,4,5,6. However, it remains challenging to develop this into a robust process because efficient conversion typically requires alkaline conditions in which CO2 precipitates as carbonate, and this limits carbon utilization and the stability of the system7,8,9,10,11,12. Strategies such as physical washing, pulsed operation and the use of dipolar membranes can partially alleviate these problems but do not fully resolve them11,13,14,15. CO2 electrolysis in acid electrolyte, where carbonate does not form, has therefore been explored as an ultimately more workable solution16,17,18. Herein we develop a proton-exchange membrane system that reduces CO2 to formic acid at a catalyst that is derived from waste lead–acid batteries and in which a lattice carbon activation mechanism contributes. When coupling CO2 reduction with hydrogen oxidation, formic acid is produced with over 93% Faradaic efficiency. The system is compatible with start-up/shut-down processes, achieves nearly 91% single-pass conversion efficiency for CO2 at a current density of 600 mA cm−2 and cell voltage of 2.2 V and is shown to operate continuously for more than 5,200 h. We expect that this exceptional performance, enabled by the use of a robust and efficient catalyst, stable three-phase interface and durable membrane, will help advance the development of carbon-neutral technologies.
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Data availability
The datasets that support the findings of this study are presented in the text and Supplementary Information. Source data are provided with this paper.
Change history
14 March 2024
A Correction to this paper has been published: https://doi.org/10.1038/s41586-024-07289-0
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Acknowledgements
This work is financially supported by National Science Foundation for Distinguished Young Scholars (no. 22325901), the National Key Research and Development Program of China (nos. 2021YFA1600800 and 2021YFA1501000), the National Natural Science Foundation of China (no.22075092), the Program for HUST Academic Frontier Youth Team (nos. 2018QYTD15 and 2019QYTD11), the Huazhong University of Science and Technology–Queen Mary University of London Strategic Partnership Research Funding (no. 2022-HUST-QMUL-SPRF-03) and the Innovation and Talent Recruitment Base of New Energy Chemistry and Device (no. B21003). We thank beamline BL01B (for finfrared spectroscopy and microspectroscopy) and BL12B X-ray magnetic circular dichroism (XMCD) at NSRL and beamline 1W1B (XAFS) at BSRF. We thank BL20U and BL14W1 at the Shanghai Synchrotron Radiation Facility for providing the beam time. The computational study is supported by Marsden Fund Council from Government funding (no. 21-UOA-237) and a Catalyst: Seeding General Grant (no. 22-UOA-031-CGS), managed by Royal Society Te Apārangi. Z.W. and R.L. acknowledge the use of New Zealand eScience Infrastructure high-performance computing facilities, consulting support and/or training services as part of this research. We acknowledge the support of WNLO of HUST and the Analytical and Testing Center of Huazhong University of Science and Technology for XRD, XPS, Raman, SEM, TEM, FTIR, inductively coupled plasma–mass spectrometry and NMR measurements. We also thank L. Zhuang at Wuhan University, J. L. Gong at Tianjin University, D. F. Gao at the Dalian Institute of Chemical Physics and J. J. Ge at the University of Science and Technology of China for fruitful discussions.
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B.Y.X. conceived and supervised the project. W.F. and B.Y.X. designed and carried out electrochemical experiments. R.L. carried out DFT calculations. Z.W. and B.Y.X. supervised and advised on DFT calculations. W.F., X.L., S.W., F.S., T.Y. and B.Y.X. performed and discussed soft X-ray absorption spectroscopy characterization. W.F., D.W., X.Y. and T.Y. assisted with in situ FTIR experiments. C.H. assisted with ultraviolet experiments. W.F., Y.L. and T.Z. helped with the in situ Raman test. W.G., F.M.L., C.X., Y.Y. and H.N. contributed to results discussion and data analysis. Y.Z. contributed to XPS result discussion. L.D. provided in situ XRD measurements. W.G., Y.M., C.Z., Y.P., G.W., X.G., B.Y. and B.T. commented on and revised the manuscript. W.F., R.L., T.Y., Z.W. and B.Y.X. wrote and revised the manuscript. All authors discussed the results and assisted with manuscript preparation. W.F., W.G. and R.L. contributed equally to this work.
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This file includes techno-economic analysis (comprehensive TEA calculation procedures and outcomes), Supplementary Figs. 1–47 and Tables 1–7 (comparative analysis of CO2 electrolysis performance, TEA parameters, ion chromatography and DFT results).
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Fang, W., Guo, W., Lu, R. et al. Durable CO2 conversion in the proton-exchange membrane system. Nature 626, 86–91 (2024). https://doi.org/10.1038/s41586-023-06917-5
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DOI: https://doi.org/10.1038/s41586-023-06917-5
