Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Ethylene production via photocatalytic dehydrogenation of ethane using LaMn1xCuxO3

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 LaMn1xCuxO3. 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.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Structural characterization of the catalyst.
Fig. 2: Photocatalytic ethane-to-ethylene performance.
Fig. 3: C2H6-TPSR and XPS results.
Fig. 4: Reaction pathway study.
Fig. 5: TEA results.

Similar content being viewed by others

Data availability

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.

References

  1. Kim, S. & Oh, S. Impact of US shale gas on the vertical and horizontal dynamics of ethylene price. Energies 13, 4479 (2020).

  2. Pan, Y. et al. Titanium silicalite-1 nanosheet-supported platinum for non-oxidative ethane dehydrogenation. ACS Catal. 11, 9970–9985 (2021).

    Article  Google Scholar 

  3. McFarland, E. Unconventional chemistry for unconventional natural gas. Science 338, 340–342 (2012).

    Article  Google Scholar 

  4. Chernyak, S. A., Corda, M., Dath, J.-P., Ordomsky, V. V. & Khodakov, A. Y. Light olefin synthesis from a diversity of renewable and fossil feedstocks: state-of the-art and outlook. Chem. Soc. Rev. 51, 7994–8044 (2022).

    Article  Google Scholar 

  5. Yu, K. et al. High-temperature pretreatment effect on Co/SiO2 active sites and ethane dehydrogenation. ACS Catal. 12, 11749–11760 (2022).

  6. Zhang, L. et al. Visible-light-driven non-oxidative dehydrogenation of alkanes at ambient conditions. Nat. Energy 7, 1042–1051 (2022).

    Article  Google Scholar 

  7. Wan, L. et al. Cu2O nanocubes with mixed oxidation-state facets for (photo)catalytic hydrogenation of carbon dioxide. Nat. Catal. 2, 889–898 (2019).

    Article  Google Scholar 

  8. Song, S. et al. A selective Au-ZnO/TiO2 hybrid photocatalyst for oxidative coupling of methane to ethane with dioxygen. Nat. Catal. 4, 1032–1042 (2021).

    Article  Google Scholar 

  9. Cai, M. et al. Greenhouse-inspired supra-photothermal CO2 catalysis. Nat. Energy 6, 807–814 (2021).

    Article  Google Scholar 

  10. Xu, Y.-F. et al. High-performance light-driven heterogeneous CO2 catalysis with near-unity selectivity on metal phosphides. Nat. Commun. 11, 5149 (2020).

    Article  Google Scholar 

  11. Hwang, J. et al. Perovskites in catalysis and electrocatalysis. Science 358, 751–756 (2017).

    Article  Google Scholar 

  12. Xu, Y. F., Lee, M., Jun, Y. & Ozin, G. A. Perovskite, the chameleon CO2 photocatalyst. Cell Rep. Phys. Sci. 2, 100300 (2021).

    Article  Google Scholar 

  13. Zhao, B. et al. A tailored double perovskite nanofiber catalyst enables ultrafast oxygen evolution. Nat. Commun. 8, 14586 (2017).

    Article  Google Scholar 

  14. Chen, W., Han, J., Wei, Y. & Zheng, A. Frustrated Lewis pair in zeolite cages for alkane activations. Angew. Chem. Int. Ed. 61, e202116269 (2022).

    Article  Google Scholar 

  15. Huang, Z.-Q., Zhang, T., Chang, C.-R. & Li, J. Dynamic frustrated Lewis pairs on ceria for direct nonoxidative coupling of methane. ACS Catal. 9, 5523–5536 (2019).

    Article  Google Scholar 

  16. Chen, R.-K. et al. The aldolization nature of Mn4+-nonstoichiometric oxygen pair sites of perovskite-type LaMnO3 in the conversion of ethanol. ACS Sustain. Chem. Eng. 6, 11949–11958 (2018).

    Article  Google Scholar 

  17. Celorrio, V. et al. Mean intrinsic activity of single Mn sites at LaMnO3 nanoparticles towards the oxygen reduction reaction. ChemElectroChem 5, 3044–3051 (2018).

    Article  Google Scholar 

  18. Hu, L. et al. Cu2+ intercalation activates bulk redox reactions of MnO2 for enhancing capacitive performance. Nano Energy 74, 104891 (2020).

    Article  Google Scholar 

  19. Zhao, L. et al. Synthesis of CeMnOx hollow microsphere with hierarchical structure and its excellent catalytic performance for toluene combustion. Appl. Catal. B 245, 502–512 (2019).

    Article  Google Scholar 

  20. Toupin, M., Brousse, T. & Bélanger, D. Influence of microstructure on the charge storage properties of chemically synthesized manganese dioxide. Chem. Mater. 14, 3946–3952 (2002).

    Article  Google Scholar 

  21. Tong, Y. et al. Vibronic superexchange in double perovskite electrocatalyst for efficient electrocatalytic oxygen evolution. J. Am. Chem. Soc. 140, 11165–11169 (2018).

    Article  Google Scholar 

  22. Guo, J. et al. High-performance, scalable, and low-cost copper hydroxyapatite for photothermal CO2 reduction. ACS Catal. 10, 13668–13681 (2020).

    Article  Google Scholar 

  23. Liu, X. et al. In situ modulation of A-site vacancies in LaMnO3.15 perovskite for surface lattice oxygen activation and boosted redox reactions. Angew. Chem. Int. Ed. 60, 26747–26754 (2021).

    Article  Google Scholar 

  24. Yan, T. et al. Bismuth atom tailoring of indium oxide surface frustrated Lewis pairs boosts heterogeneous CO2 photocatalytic hydrogenation. Nat. Commun. 11, 6095 (2020).

    Article  Google Scholar 

  25. Ma, J. et al. Design of frustrated Lewis pair in defective TiO2 for photocatalytic non-oxidative methane coupling. Chem Catal. 2, 1775–1792 (2022).

    Article  Google Scholar 

  26. Yan, T. et al. Polymorph selection towards photocatalytic gaseous CO2 hydrogenation. Nat. Commun. 10, 2521 (2019).

  27. Duan, X. et al. Simultaneously constructing active sites and regulating Mn–O strength of Ru-substituted perovskite for efficient oxidation and hydrolysis oxidation of chlorobenzene. Adv. Sci. 10, 2205054 (2023).

    Article  Google Scholar 

  28. Kim, W. J. et al. Geometric frustration of Jahn–Teller order in the infinite-layer lattice. Nature 615, 237–243 (2023).

    Article  Google Scholar 

  29. Karamullaoglu, G., Onen, S. & Dogu, T. Oxidative dehydrogenation of ethane and isobutane with chromium–vanadium–niobium mixed oxide catalysts. Chem. Eng. Process. 41, 337–347 (2002).

    Article  Google Scholar 

  30. Malysheva, L., Onipko, A., Valiokas, R. & Liedberg, B. First-principle DFT and MP2 modeling of infrared reflection–absorption spectra of oriented helical ethylene glycol oligomers. J. Phys. Chem. B 109, 13221–13227 (2005).

    Article  Google Scholar 

  31. Muslehiddinoglu, J. Characterization of Supported and Promoted Silver Epoxidation Catalysts Using Molecular Probes. PhD thesis, The Pennsylvania State Univ. (2002).

  32. Hill, I. R. & Levin, I. W. Vibrational spectra and carbon–hydrogen stretching mode assignments for a series of n-alkyl carboxylic acids. J. Chem. Phys. 70, 842–851 (1979).

    Article  Google Scholar 

  33. Zhang, Q. et al. Novel cyclic sulfonium-based ionic liquids: synthesis, characterization, and physicochemical properties. Chem. Eur. J. 15, 765–778 (2009).

    Article  Google Scholar 

  34. Woo, S.-J. et al. Highly selective and durable photochemical CO2 reduction by molecular Mn(I) catalyst fixed on a particular dye-sensitized TiO2 platform. ACS Catal. 9, 2580–2593 (2019).

    Article  Google Scholar 

  35. Li, X. et al. Hydrothermal synthesis of bi-functional nanostructured manganese tungstate catalysts for selective oxidation. Faraday Discuss. 188, 99–113 (2016).

    Article  Google Scholar 

  36. Lebron, G. B. & Tan, T. L. Integrated band intensities of ethylene (12C2H4) by Fourier transform infrared spectroscopy. Int. J. Spectrosc. 2012, 474639 (2012).

  37. Haji, S. & Erkey, C. Investigation of rhodium catalyzed hydroformylation of ethylene in supercritical carbon dioxide by in situ FTIR spectroscopy. Tetrahedron 58, 3929–3941 (2002).

    Article  Google Scholar 

  38. Dhahak, A., Hild, G., Rouaud, M., Mauviel, G. & Burkle-Vitzthum, V. Slow pyrolysis of polyethylene terephthalate: online monitoring of gas production and quantitative analysis of waxy products. J. Anal. Appl. Pyrolysis 142, 104664 (2019).

    Article  Google Scholar 

  39. Lebron, G. B. & Tan, T. L. High-resolution Fourier transform infrared spectrum of the ν11 band of ethylene (12C2H4). J. Mol. Spectrosc. 288, 11–13 (2013).

    Article  Google Scholar 

  40. Rønne, M. H. et al. Ligand-controlled product selectivity in electrochemical carbon dioxide reduction using manganese bipyridine catalysts. J. Am. Chem. Soc. 142, 4265–4275 (2020).

    Article  Google Scholar 

  41. Li, F. et al. Photocatalytic ethane conversion on rutile TiO2(110): identifying the role of the ethyl radical. Chem. Sci. 15, 307–316 (2024).

    Article  Google Scholar 

  42. Deringer, V. L., Tchougréeff, A. L. & Dronskowski, R. Crystal orbital Hamilton population (COHP) analysis as projected from plane-wave basis sets. J. Phys. Chem. A 115, 5461–5466 (2011).

    Article  Google Scholar 

  43. Zhao, Y. et al. Methane adsorption properties of Mn-modified graphene: a first-principles study. Adv. Theory Simul. 3, 2000035 (2020).

    Article  Google Scholar 

  44. Chen, C.-C., Yeh, C.-H., Chang, C.-C. & Ho, J.-J. Conversion of CO2 and C2H6 to propanoic acid on an iridium-modified graphene oxide surface: quantum-chemical investigation. Ind. Eng. Chem. Res. 54, 1539–1546 (2015).

    Article  Google Scholar 

  45. Ryan, M. F., Fiedler, A., Schroeder, D. & Schwarz, H. Radical-like behavior of manganese oxide cation in its gas-phase reactions with dihydrogen and alkanes. J. Am. Chem. Soc. 117, 2033–2040 (1995).

    Article  Google Scholar 

  46. Ozin, G. Accelerated optochemical engineering solutions to CO2 photocatalysis for a sustainable future. Matter 5, 2594–2614 (2022).

    Article  Google Scholar 

  47. Tao, J., Perdew, J. P., Tang, H. & Shahi, C. Origin of the size-dependence of the equilibrium van der Waals binding between nanostructures. J. Chem. Phys. 148, 074110 (2018).

    Article  Google Scholar 

  48. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

    Article  Google Scholar 

  49. Mulwa, W. M., Dejene, B. F., Onani, M. O. & Ouma, C. N. M. Effect of Cu2+ doping on the structural, electronic and optical properties of ZnAl2O4: a combined experimental and DFT+U study. J. Lumin. 184, 7–16 (2017).

    Article  Google Scholar 

  50. Lee, A. et al. Photo-accelerated fast charging of lithium-ion batteries. Nat. Commun. 10, 4946 (2019).

    Article  Google Scholar 

  51. Dronskowski, R. & Blöchl, P. E. Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations. J. Phys. Chem. 97, 8617–8624 (1993).

    Article  Google Scholar 

Download references

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.

Author information

Authors and Affiliations

Authors

Contributions

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.

Corresponding authors

Correspondence to Le He, Xiaohong Zhang or Geoffrey A. Ozin.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

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

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–46, Tables 1–11, Notes 1–14 and references.

Supplementary Data 1

Source data

Source Data Fig. 1

Raw data used in Fig. 1.

Source Data Fig. 2

Raw data used in Fig. 2.

Source Data Fig. 3

Raw data used in Fig. 3.

Source Data Fig. 4

Raw data used in Fig. 4.

Source Data Fig. 5

Raw data used in Fig. 5.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Song, R., Zhao, G., Restrepo-Flórez, J.M. et al. Ethylene production via photocatalytic dehydrogenation of ethane using LaMn1xCuxO3. Nat Energy 9, 750–760 (2024). https://doi.org/10.1038/s41560-024-01541-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-024-01541-7

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing