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:

Economically viable electrocatalytic ethylene production with high yield and selectivity

Abstract

Electrocatalytic semihydrogenation of acetylene provides a clean pathway to the production of ethylene (C2H4), one of the most widely used petrochemical feedstocks. However, its performance is still well below that of the thermocatalytic route, leaving the practical feasibility of this electrochemical process questionable. Here our techno-economic analysis shows that this process becomes profitable if the Faraday efficiency exceeds 85% at a current density of 0.2 A cm−2. As a result, we design a Cu nanoparticle catalyst with coordinatively unsaturated sites to steer the reaction towards these targets. Our electrocatalyst synthesized on gas diffusion layer coated carbon paper enables a high C2H4 yield rate of 70.15 mmol mg−1 h−1 and a Faraday efficiency of 97.7% at an industrially relevant current density of 0.5 A cm−2. Combined characterizations and calculations reveal that this performance can be attributed to the favourable combination of a higher energy barrier for the coupling of active hydrogen atoms (H*) and weak absorption of *C2H4. The former suppresses the competitive hydrogen evolution reaction, whereas the latter avoids overhydrogenation and C–C coupling. Further life cycle assessment evidences the economic feasibility and sustainability of the process. Our work suggests a way towards rational design and manipulation of nanocatalysts that could find wider and greener catalytic applications.

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: TEA and theoretical-calculation-guided design of electrodes.
Fig. 2: In situ formation of ED-Cu NPs from the electrodeposition of copper nitrate.
Fig. 3: Performance of C2H4 production through the ESAE process.
Fig. 4: The hydrogenation pathway and mechanism of C2H4 production.
Fig. 5: Sustainability evaluation of the process.

Similar content being viewed by others

Data availability

The spreadsheets used for the cost analyses and CO2 emissions and for Supplementary Tables 17 are available in Supplementary Data 1 and 2. Source data are provided with this paper.

References

  1. Leow, W. R. et al. Chloride-mediated selective electrosynthesis of ethylene and propylene oxides at high current density. Science 368, 1228–1233 (2020).

    CAS  Google Scholar 

  2. Jiang, K. et al. Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction. Nat. Catal. 1, 111–119 (2018).

    CAS  Google Scholar 

  3. Chai, Y. et al. Control of zeolite pore interior for chemoselective alkyne/olefin separations. Science 368, 1002–1006 (2020).

    CAS  Google Scholar 

  4. Bodke, A. S., Olschki, D. A., Schmidt, L. D. & Ranzi, E. High selectivities to ethylene by partial oxidation of ethane. Science 285, 712–715 (1999).

    CAS  Google Scholar 

  5. Gomez, E., Yan, B., Kattel, S. & Chen, J. G. Carbon dioxide reduction in tandem with light-alkane dehydrogenation. Nat. Rev. Chem. 3, 638–649 (2019).

    CAS  Google Scholar 

  6. Gao, Y. et al. Recent advances in intensified ethylene production—a review. ACS Catal. 9, 8592–8621 (2019).

    CAS  Google Scholar 

  7. Zhao, B. et al. Unveiling the activity origin of iron nitride as catalytic material for efficient hydrogenation of CO2 to C2+ hydrocarbons. Angew. Chem. Int. Ed. 60, 4496–4500 (2021).

    CAS  Google Scholar 

  8. Jiang, W. et al. Pd-modified ZnO–Au enabling alkoxy intermediates formation and dehydrogenation for photocatalytic conversion of methane to ethylene. J. Am. Chem. Soc. 143, 269–278 (2021).

    CAS  Google Scholar 

  9. Jiao, X. et al. Conversion of waste plastics into value-added carbonaceous fuels under mild conditions. Adv. Mater. 33, 2005192 (2021).

    CAS  Google Scholar 

  10. Schobert, H. Production of acetylene and acetylene-based chemicals from coal. Chem. Rev. 114, 1743–1760 (2014).

    CAS  Google Scholar 

  11. Ma, J. et al. Pyrolysis of pulverized coal to acetylene in magnetically rotating hydrogen plasma reactor. Fuel Process. Technol. 167, 721–729 (2017).

    CAS  Google Scholar 

  12. Bond, R. L., Galbraith, I. F., Ladner, W. R. & McConnell, G. I. T. Production of acetylene from coal, using a plasma jet. Nature 200, 1313–1314 (1963).

    CAS  Google Scholar 

  13. Yan, B., Xu, P., Guo, C. Y., Jin, Y. & Cheng, Y. Experimental study on coal pyrolysis to acetylene in thermal plasma reactors. Chem. Eng. J. 207–208, 109–116 (2012).

    Google Scholar 

  14. Zhang, L. et al. Efficient electrocatalytic acetylene semihydrogenation by electron-rich metal sites in N-heterocyclic carbene metal complexes. Nat. Commun. 12, 6574 (2021).

    CAS  Google Scholar 

  15. Studt, F. et al. Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene. Science 320, 1320–1322 (2008).

    CAS  Google Scholar 

  16. Cao, Y. et al. Adsorption site regulation to guide atomic design of Ni–Ga catalysts for acetylene semi‐hydrogenation. Angew. Chem. Int. Ed. 132, 11744–11749 (2020).

    Google Scholar 

  17. Wang, S. et al. Highly efficient ethylene production via electrocatalytic hydrogenation of acetylene under mild conditions. Nat. Commun. 12, 7072 (2021).

    CAS  Google Scholar 

  18. Bu, J. et al. Selective electrocatalytic semihydrogenation of acetylene impurities for the production of polymer-grade ethylene. Nat. Catal. 4, 557–564 (2021).

    CAS  Google Scholar 

  19. Shi, R. et al. Room-temperature electrochemical acetylene reduction to ethylene with high conversion and selectivity. Nat. Catal. 4, 565–574 (2021).

    CAS  Google Scholar 

  20. Vilé, G., Albani, D., Almora-Barrios, N., López, N. & Pérez-Ramírez, J. Advances in the design of nanostructured catalysts for selective hydrogenation. ChemCatChem 8, 21–33 (2016).

    Google Scholar 

  21. Vilé, G. et al. A stable single-site palladium catalyst for hydrogenations. Angew. Chem. Int. Ed. 54, 11265–11269 (2015).

    Google Scholar 

  22. Omar, S. et al. Density functional theory analysis of dichloromethane and hydrogen interaction with Pd clusters: first step to simulate catalytic hydrodechlorination. J. Phys. Chem. C 115, 14180–14192 (2011).

    CAS  Google Scholar 

  23. Huang, F. et al. Insight into the activity of atomically dispersed Cu catalysts for semihydrogenation of acetylene: impact of coordination environments. ACS Catal. 12, 48–57 (2022).

    CAS  Google Scholar 

  24. Semagina, N. & Kiwi‐Minsker, L. Recent advances in the liquid‐phase synthesis of metal nanostructures with controlled shape and size for catalysis. Catal. Rev. 51, 147–217 (2009).

    CAS  Google Scholar 

  25. Xing, Z., Hu, L., Ripatti, D. S., Hu, X. & Feng, X. Enhancing carbon dioxide gas-diffusion electrolysis by creating a hydrophobic catalyst microenvironment. Nat. Commun. 12, 136 (2021).

    CAS  Google Scholar 

  26. Nguyen, T. N. & Dinh, C.-T. Gas diffusion electrode design for electrochemical carbon dioxide reduction. Chem. Soc. Rev. 49, 7488–7504 (2020).

    CAS  Google Scholar 

  27. Yang, K., Kas, R., Smith, W. A. & Burdyny, T. Role of the carbon-based gas diffusion layer on flooding in a gas diffusion electrode cell for electrochemical CO2 reduction. ACS Energy Lett. 6, 33–40 (2021).

    CAS  Google Scholar 

  28. Gu, Y. et al. Two-dimensional porous molybdenum phosphide/nitride heterojunction nanosheets for pH-universal hydrogen evolution reaction. Angew. Chem. Int. Ed. 60, 6673–6681 (2021).

    CAS  Google Scholar 

  29. Haase, F. T. et al. Size effects and active state formation of cobalt oxide nanoparticles during the oxygen evolution reaction. Nat. Energy 7, 765–773 (2022).

    CAS  Google Scholar 

  30. Xie, L. et al. Molecular engineering of a 3D self-supported electrode for oxygen electrocatalysis in neutral media. Angew. Chem. Int. Ed. 58, 18883–18887 (2019).

    CAS  Google Scholar 

  31. Lum, Y. et al. Tuning OH binding energy enables selective electrochemical oxidation of ethylene to ethylene glycol. Nat. Catal. 3, 14–22 (2020).

    CAS  Google Scholar 

  32. Shin, H., Hansen, K. U. & Jiao, F. Techno-economic assessment of low-temperature carbon dioxide electrolysis. Nat. Sustain. 4, 911–919 (2021).

    Google Scholar 

  33. Gao, Y. et al. Field-induced reagent concentration and sulfur adsorption enable efficient electrocatalytic semihydrogenation of alkynes. Sci. Adv. 8, eabm9477 (2022).

    CAS  Google Scholar 

  34. Durante, C. An electrochemical way to pure ethylene. Nat. Catal. 4, 537–538 (2021).

    CAS  Google Scholar 

  35. Wu, Y., Liu, C., Wang, C., Lu, S. & Zhang, B. Selective transfer semihydrogenation of alkynes with H2O (D2O) as the H (D) source over a Pd–P cathode. Angew. Chem. Int. Ed. 59, 21170–21175 (2020).

    CAS  Google Scholar 

  36. Li, H. et al. σ-alkynyl adsorption enables electrocatalytic semihydrogenation of terminal alkynes with easy-reducible/passivated groups over amorphous PdSx nanocapsules. J. Am. Chem. Soc. 144, 19456–19465 (2022).

    CAS  Google Scholar 

  37. Higgins, D., Hahn, C., Xiang, C., Jaramillo, T. F. & Weber, A. Z. Gas-diffusion electrodes for carbon dioxide reduction: a new paradigm. ACS Energy Lett. 4, 317–324 (2019).

    CAS  Google Scholar 

  38. Cheng, W., Zhang, H., Luan, D. & Lou, X. W. Exposing unsaturated Cu1-O2 sites in nanoscale Cu-MOF for efficient electrocatalytic hydrogen evolution. Sci. Adv. 7, eabg2580 (2021).

    CAS  Google Scholar 

  39. Wu, Y. et al. Converting copper sulfide to copper with surface sulfur for electrocatalytic alkyne semi-hydrogenation with water. Nat. Commun. 12, 3881 (2021).

    CAS  Google Scholar 

  40. Han, J. et al. A reconstructed porous copper surface promotes selectivity and efficiency toward C2 products by electrocatalytic CO2 reduction. Chem. Sci. 11, 10698–10704 (2020).

    CAS  Google Scholar 

  41. Tao, Z., Wu, Z., Wu, Y. & Wang, H. Activating copper for electrocatalytic CO2 reduction to formate via molecular interactions. ACS Catal. 10, 9271–9275 (2020).

    CAS  Google Scholar 

  42. Lei, Q. et al. Investigating the origin of enhanced C2+ selectivity in oxide-/hydroxide-derived copper electrodes during CO2 electroreduction. J. Am. Chem. Soc. 142, 4213–4222 (2020).

    CAS  Google Scholar 

  43. Ma, C. Y. et al. Mesoporous Co3O4 and Au/Co3O4 catalysts for low-temperature oxidation of trace ethylene. J. Am. Chem. Soc. 132, 2608–2613 (2010).

    CAS  Google Scholar 

  44. McKean, D. C. Individual CH bond strengths in simple organic compounds: effects of conformation and substitution. Chem. Soc. Rev. 7, 399–422 (1978).

    CAS  Google Scholar 

  45. Yamamoto, M. et al. Softened CH stretching vibration of a long-chain n-alkane, n-C44H90, physisorbed on a Ag(111) surface: an infrared reflection absorption spectroscopic study. J. Phys. Chem. B 104, 7370–7376 (2000).

    CAS  Google Scholar 

  46. Sherbo, R. S., Kurimoto, A., Brown, C. M. & Berlinguette, C. P. Efficient electrocatalytic hydrogenation with a palladium membrane reactor. J. Am. Chem. Soc. 141, 7815–7821 (2019).

    CAS  Google Scholar 

  47. De Luna, P. et al. What would it take for renewably powered electrosynthesis to displace petrochemical processes? Science 364, eaav3506 (2019).

    Google Scholar 

  48. Rojas Sánchez, D., Khalilpour, K. & Hoadley, A. F. A. How sustainable is CO2 conversion to ethanol? A life cycle assessment of a new electrocatalytic carbon utilisation process. Sustain. Energy Fuels 5, 5866–5880 (2021).

    Google Scholar 

  49. Chang, X., Malkani, A., Yang, X. & Xu, B. Mechanistic insights into electroreductive C–C coupling between CO and acetaldehyde into multicarbon products. J. Am. Chem. Soc. 142, 2975–2983 (2020).

    CAS  Google Scholar 

  50. Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).

    CAS  Google Scholar 

  51. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996).

    CAS  Google Scholar 

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

    Google Scholar 

  53. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996).

    CAS  Google Scholar 

  54. Mathew, K., Sundararaman, R., Letchworth-Weaver, K., Arias, T. & Hennig, R. G. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. J. Chem. Phys. 140, 084106 (2014).

    Google Scholar 

  55. Henkelman, G. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).

    CAS  Google Scholar 

Download references

Acknowledgements

We acknowledge the National Natural Science Foundation of China (grant no. 21871206 to B.Z.) and L. Zheng at the 1W1B beamline of the Beijing Synchrotron Radiation Facility for supporting this project. We also thank Y. Liu for help with the ATR–FTIR measurements.

Author information

Authors and Affiliations

Authors

Contributions

B.Z. conceived the idea and directed the project. B.-H.Z. and B.Z. designed the experiments. B.-H.Z. and M.W. performed the materials synthesis and electrochemical experiments. B.-H.Z., F.C. and M.W. carried out the in situ experiments. C.C. performed and analysed the DFT calculations. B.-H.Z., Y.W., C.L., Y.Y. and B.Z. analysed the experimental data. B.-H.Z. and F.C. wrote the paper. B.Z. revised the paper. All authors discussed the results and commented on the paper.

Corresponding author

Correspondence to Bin Zhang.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Sustainability thanks Feng Jiao, Christian Durante 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. 1–41, Notes 1–30 and Tables 1–7.

Reporting Summary

Supplementary Video 1

Videos for the ESAE process driven by solar-derived electricity.

Supplementary Data 1

The spreadsheets used for the cost analyses and CO2 emissions.

Supplementary Data 2

Datasets for Supplementary Tables 1–7.

Source data

Source Data Fig. 1

The source data underlying Fig. 1.

Source Data Fig. 2

The source data underlying Fig. 2.

Source Data Fig. 3

The source data underlying Fig. 3.

Source Data Fig. 4

The source data underlying Fig. 4.

Source Data Fig. 5

The source data underlying 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

Zhao, BH., Chen, F., Wang, M. et al. Economically viable electrocatalytic ethylene production with high yield and selectivity. Nat Sustain 6, 827–837 (2023). https://doi.org/10.1038/s41893-023-01084-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41893-023-01084-x

This article is cited by

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