Abstract
Industrial-scale ethylene production occurs primarily by fossil-powered steam cracking of ethane—a high-temperature, high-energy process. An alternative, photochemical, pathway powered by sunlight and operating under ambient conditions could potentially mitigate some of the associated greenhouse gas emissions. Here we report the photocatalytic dehydrogenation of ethane to ethylene and hydrogen using LaMn1−xCuxO3. This perovskite oxide possesses redox-active Lewis acid sites, comprising Mn(III) and Mn(IV), and Lewis base sites, comprising O(-II) and OH(-I), collectively dubbed surface-frustrated Lewis pairs. We find that tuning the relative proportions of these sites optimizes the activity, selectivity and yield for ethane dehydrogenation. The highest ethylene production rate and ethane conversion achieved were around 1.1 mmol g−1 h−1 and 4.9%, respectively. We show a simple outdoor prototype to demonstrate the viability of a solar ethylene process. In addition, techno-economic analysis revealed the economic potential of an industrial-scale solar ethylene production from ethane.
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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.
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Acknowledgements
L.H., D.J. and X.Z. acknowledge the financial support from the National Natural Science Foundation of China (51920105005, 52025061, 52172221 and 52272229), the National Key R&D Program of China (2021YFF0502000), the Natural Science Foundation of Jiangsu Province (BK20220027), the Suzhou Key Laboratory of Functional Nano and Soft Materials, and the Collaborative Innovation Center of Suzhou Nano Science and Technology. G.A.O. acknowledges the financial support of the following agencies: Ontario Ministry of Research and Innovation; Ministry of Economic Development, Employment and Infrastructure; Ministry of the Environment and Climate Change; Best in Science; Ministry of Research Innovation and Science Low Carbon Innovation Fund; Ontario Centre of Excellence Solutions 2030 Challenge Fund; Alexander von Humboldt Foundation; Imperial Oil; University of Toronto Connaught Innovation Fund; Connaught Global Challenge Fund; and the Natural Sciences and Engineering Research Council of Canada. R.S. acknowledges the financial support from the China Postdoctoral Science Foundation (2020M681710) and the Zhejiang University Global Partnership Fund. We also acknowledge G. Vezina of Hydrofuel Canada Inc. for financial support from June 2023. Thanks go to D. Burns from the Chemistry Department of University of Toronto for the NMR test and C. Sun from Swinburne University of Technology and Z. Huang from Xi’an Jiaotong University for helping analysing and reviewing DFT calculation results.
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R.S. and G.Z. contributed equally to this work. R.S. and G.A.O. conceived and designed the experiments. G.A.O., L.H. and X.Z. supervised the project. R.S. prepared the materials and performed the XRD, XPS, NMR and photocatalytic characterizations. R.S., L.W. and Junchuan Sun did the in situ DRIFTS test. C.J.V.P. performed the thermogravimetric analysis test and helped with the reactor design. Z.C., C.A., C.Q., D.J., J.G., C.L. and Jiahui Shen performed the UV–vis, PL, TEM, C2H6 adsorption isotherms and C2H6-TPD. G.C. carried out the coke test and ethane-TPSR. C.M. and Y.-F.X. did the GC-MS test. Z.L. helped the sample synthesis. N.T.N. performed the BET test. G.Z., A.W. and Y.F. performed the DFT calculations. R.S., G.Z., Y.F. and J.Y.Y.L. did the data analysis. J.M.R.-F. and C.T.M. did the TEA and wrote the corresponding content. R.S., G.Z., C.J.V.P., A.A.T., J.Y., L.H., X.Z. and G.A.O. co-wrote the paper. All authors discussed the results and commented on the paper.
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Song, R., Zhao, G., Restrepo-Flórez, J.M. et al. Ethylene production via photocatalytic dehydrogenation of ethane using LaMn1−xCuxO3. Nat Energy 9, 750–760 (2024). https://doi.org/10.1038/s41560-024-01541-7
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DOI: https://doi.org/10.1038/s41560-024-01541-7
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