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:

Deprotonated 2-thiolimidazole serves as a metal-free electrocatalyst for selective acetylene hydrogenation

Nature Chemistry (2024)Cite this article

Subjects

Abstract

Metal-free catalysts offer a desirable alternative to traditional metal-based electrocatalysts. However, metal-free catalysts, featuring defined active sites, rarely show activities as promising as metal-based materials. Here we report 2-thiolimidazole as an efficient metal-free catalyst for selective electrocatalytic hydrogenation of acetylene into ethylene. Under alkaline conditions, the sulfhydryl and imino groups of 2-thiolimidazole are spontaneously deprotonated into dianions. Deprotonation thus enriches the negative charges of pyridinic N sites in 2-thiolimidazole to enhance the adsorption of electrophilic acetylene through the σ-configuration. Ethylene partial current densities show a volcano relationship with the negative charges of the pyridinic N sites in various imidazole derivatives. Consequently, the deprotonated 2-thiolimidazole exhibits an ethylene partial current density and faradaic efficiency competitive with metal-based catalysts like Cu and Pd. This work highlights the tunability and promising potential of metal-free molecules in electrocatalysis.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Fig. 1: Comparison of electrocatalytic performance for 2TIm and metal-based electrocatalysts in a three-electrode flow cell.
Fig. 2: Electrocatalytic acetylene semihydrogenation catalysed by 2TIm in a two-electrode flow cell.
Fig. 3: Mechanistic investigations.
Fig. 4: Mechanistic studies with different imidazole derivatives.

Similar content being viewed by others

Data availability

The data that support the findings of this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

References

  1. Greeley, J. et al. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nat. Chem. 1, 552–556 (2009).

    Article  CAS  PubMed  Google Scholar 

  2. Huang, Z.-F. et al. Chemical and structural origin of lattice oxygen oxidation in Co–Zn oxyhydroxide oxygen evolution electrocatalysts. Nat. Energy 4, 329–338 (2019).

    Article  CAS  Google Scholar 

  3. Zhong, M. et al. Accelerated discovery of CO2 electrocatalysts using active machine learning. Nature 581, 178–183 (2020).

    Article  CAS  PubMed  Google Scholar 

  4. Gong, M. et al. Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis. Nat. Commun. 5, 4695 (2014).

    Article  CAS  PubMed  Google Scholar 

  5. Strmcnik, D. et al. Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption. Nat. Chem. 5, 300–306 (2013).

    Article  CAS  PubMed  Google Scholar 

  6. Duchesne, P. N. et al. Golden single-atomic-site platinum electrocatalysts. Nat. Mater. 17, 1033–1039 (2018).

    Article  CAS  PubMed  Google Scholar 

  7. Wang, Y. et al. Enhanced nitrate-to-ammonia activity on copper–nickel alloys via tuning of intermediate adsorption. J. Am. Chem. Soc. 142, 5702–5708 (2020).

    Article  CAS  PubMed  Google Scholar 

  8. Gong, K., Du, F., Xia, Z., Durstock, M. & Dai, L. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323, 760–764 (2009).

    Article  CAS  PubMed  Google Scholar 

  9. Jiao, Y., Zheng, Y., Davey, K. & Qiao, S.-Z. Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped graphene. Nat. Energy 1, 16130 (2016).

    Article  CAS  Google Scholar 

  10. Kumar, B. et al. Renewable and metal-free carbon nanofibre catalysts for carbon dioxide reduction. Nat. Commun. 4, 2819 (2013).

    Article  Google Scholar 

  11. Zhang, J., Zhao, Z., Xia, Z. & Dai, L. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat. Nanotechnol. 10, 444–452 (2015).

    Article  CAS  PubMed  Google Scholar 

  12. Zhang, S. et al. Polyethylenimine-enhanced electrocatalytic reduction of CO2 to formate at nitrogen-doped carbon nanomaterials. J. Am. Chem. Soc. 136, 7845–7848 (2014).

    Article  CAS  PubMed  Google Scholar 

  13. Guo, D. et al. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science 351, 361–365 (2016).

    Article  CAS  PubMed  Google Scholar 

  14. Zhao, Y. et al. Few-layer graphdiyne doped with sp-hybridized nitrogen atoms at acetylenic sites for oxygen reduction electrocatalysis. Nat. Chem. 10, 924–931 (2018).

    Article  CAS  PubMed  Google Scholar 

  15. Cui, P., Zhao, L., Long, Y., Dai, L. & Hu, C. Carbon-based electrocatalysts for acidic oxygen reduction reaction. Angew. Chem. Int. Ed. 62, e202218269 (2023).

    Article  CAS  Google Scholar 

  16. Xue, L. et al. Zigzag carbon as efficient and stable oxygen reduction electrocatalyst for proton exchange membrane fuel cells. Nat. Commun. 9, 3819 (2018).

    Article  PubMed  PubMed Central  Google Scholar 

  17. Shui, J., Wang, M., Du, F. & Dai, L. N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells. Sci. Adv. 1, e1400129 (2015).

    Article  PubMed  PubMed Central  Google Scholar 

  18. Zheng, Y. et al. Hydrogen evolution by a metal-free electrocatalyst. Nat. Commun. 5, 3783 (2014).

    Article  PubMed  Google Scholar 

  19. Wu, J. et al. A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates. Nat. Commun. 7, 13869 (2016).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  20. Xie, J. et al. Metal-free fluorine-doped carbon electrocatalyst for CO2 reduction outcompeting hydrogen evolution. Angew. Chem. Int. Ed. 57, 9640–9644 (2018).

    Article  CAS  Google Scholar 

  21. Pan, B. et al. Toward highly selective electrochemical CO2 reduction using metal-free heteroatom-doped carbon. Adv. Sci. 7, 2001002 (2020).

    Article  CAS  Google Scholar 

  22. Huang, L. et al. Direct synthesis of ammonia from nitrate on amorphous graphene with near 100% efficiency. Adv. Mater. 35, e2211856 (2023).

    Article  PubMed  Google Scholar 

  23. Zhang, C. et al. A pentagonal defect-rich metal-free carbon electrocatalyst for boosting acidic O2 reduction to H2O2 production. J. Am. Chem. Soc. 145, 11589–11598 (2023).

    Article  CAS  PubMed  Google Scholar 

  24. MacMillan, D. W. C. The advent and development of organocatalysis. Nature 455, 304–308 (2008).

    Article  CAS  PubMed  Google Scholar 

  25. Yang, J. et al. CO2-mediated organocatalytic chlorine evolution under industrial conditions. Nature 617, 519–523 (2023).

    Article  CAS  PubMed  Google Scholar 

  26. Wu, S. et al. Highly durable organic electrode for sodium-ion batteries via a stabilized α-C radical intermediate. Nat. Commun. 7, 13318 (2016).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  27. Janoschka, T. et al. An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials. Nature 527, 78–81 (2015).

    Article  CAS  PubMed  Google Scholar 

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

    Article  CAS  PubMed  PubMed Central  Google Scholar 

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

    Article  CAS  Google Scholar 

  30. Zhao, B.-H. et al. Economically viable electrocatalytic ethylene production with high yield and selectivity. Nat. Sustain. 6, 827–837 (2023).

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  33. Xue, G., Huang, X.-Y., Dong, J. & Zhang, J. The formation of an effective anti-corrosion film on copper surfaces from 2-mercaptobenzimidazole solution. J. Electroanal. Chem. 310, 139–148 (1991).

    Article  CAS  Google Scholar 

  34. Finšgar, M. 2-Mercaptobenzimidazole as a copper corrosion inhibitor: part II. Surface analysis using X-ray photoelectron spectroscopy. Corros. Sci. 72, 90–98 (2013).

    Article  Google Scholar 

  35. Platzer, G., Okon, M. & McIntosh, L. P. pH-dependent random coil 1H, 13C, and 15N chemical shifts of the ionizable amino acids: a guide for protein pKa measurements. J. Biomol. NMR 60, 109–129 (2014).

    Article  CAS  PubMed  Google Scholar 

  36. Richmond, W. N., Faguy, P. W. & Weibel, S. C. An in situ infrared spectroscopic study of imidazole films on copper electrodes. J. Electroanal. Chem. 448, 237–244 (1998).

    Article  CAS  Google Scholar 

  37. Biswas, N., Thomas, S., Sarkar, A., Mukherjee, T. & Kapoor, S. Adsorption of methimazole on silver nanoparticles: FTIR, Raman, and surface-enhanced Raman scattering study aided by density functional theory. J. Phys. Chem. C 113, 7091–7100 (2009).

    Article  CAS  Google Scholar 

  38. Chandra, S., Chowdhury, J., Ghosh, M. & Talapatra, G. B. Genesis of enhanced Raman bands in SERS spectra of 2-mercaptoimidazole: FTIR, Raman, DFT, and SERS. J. Phys. Chem. A 116, 10934–10947 (2012).

    Article  CAS  PubMed  Google Scholar 

  39. Wang, X., Xu, C., Jaroniec, M., Zheng, Y. & Qiao, S. Z. Anomalous hydrogen evolution behavior in high-pH environment induced by locally generated hydronium ions. Nat. Commun. 10, 4876 (2019).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  40. Mahmood, N. et al. Electrocatalysts for hydrogen evolution in alkaline electrolytes: mechanisms, challenges, and prospective solutions. Adv. Sci. 5, 1700464 (2018).

    Article  Google Scholar 

  41. Guan, Q. et al. Reactive metal–biopolymer interactions for semihydrogenation of acetylene. ACS Catal. 9, 11146–11152 (2019).

    Article  CAS  Google Scholar 

  42. Marenich, A. V., Cramer, C. J. & Truhlar, D. G. Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J. Phys. Chem. B 113, 6378–6396 (2009).

  43. Becke, A. D. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, 5648–5652 (1993).

  44. Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).

  45. Andrae, D., Häußermann, U., Dolg, M., Stoll, H. & Preuß, H. Energy-adjustedab initio pseudopotentials for the second and third row transition elements. Theoret. Chim. Acta 77, 123–141 (1990).

  46. Nørskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell Cathode. J. Phys. Chem. B 108, 17886–17892 (2004).

  47. Weinhold, F. & Landis C. R. Discovering Chemistry with Natural Bond Orbitals (John Wiley & Sons, 2012).

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (52373308 (J.Z.), 22005245 (J.Z.), 52101271 (L.Z.) and 22202123 (Z.W.)), the Key Research and Development Program of Shaanxi Province (2023-YBGY-284 (J.Z.) and 2024GX-YBXM-379 (L.Z.)), the Fundamental Research Funds for the Central Universities (G2022KY0606 (J.Z.) and G2020KY05306 (L.Z.)) and the Guangdong Basic and Applied Basic Research Foundation (2020A1515111017 (L.Z.)). We thank C. Liu at Shanxi University for help with the simulations.

Author information

Author notes

  1. These authors contributed equally: Lei Zhang, Rui Bai.

Authors and Affiliations

  1. State Key Laboratory of Solidification Processing and School of Materials Science and Engineering, Northwestern Polytechnical University, Xi’an, P. R. China

    Lei Zhang, Rui Bai, Jin Lin, Zhenpeng Liu & Jian Zhang

  2. Key Laboratory of Special Functional and Smart Polymer Materials of Ministry of Industry and Information Technology and Department of Advanced Chemical Engineering, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi’an, P. R. China

    Lei Zhang, Jun Bu, Siying An & Jian Zhang

  3. Institute of Molecular Science, Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Shanxi University, Taiyuan, P. R. China

    Zhihong Wei

Authors
  1. Lei Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Rui Bai
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jin Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jun Bu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Zhenpeng Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Siying An
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Zhihong Wei
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jian Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

L.Z. and J.Z. conceived and designed the experiments. J.Z. supervised the project. L.Z. and R.B. carried out experiments and analysed the results. J.L. and Z.L. performed the characterization of the catalyst. J.B. optimized the electrochemical and product analysis set-ups. S.A. contributed to the electrochemical measurements. Z.W. conducted the grand canonical calculations. L.Z. and J.Z. assembled the figures and cowrote the manuscript. All authors discussed the results and commented on the paper.

Corresponding authors

Correspondence to Zhihong Wei or Jian Zhang.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Chemistry thanks Liang Yu 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. 1–37, Tables 1–5 and Discussion.

Supplementary Data 1

Statistical source data for Supplementary Fig. 1.

Supplementary Data 2

Statistical source data for Supplementary Fig. 3.

Supplementary Data 3

Statistical source data for Supplementary Fig. 4.

Supplementary Data 4

Statistical source data for Supplementary Fig. 5.

Supplementary Data 5

Statistical source data for Supplementary Fig. 7.

Supplementary Data 6

Statistical source data for Supplementary Fig. 9.

Supplementary Data 7

Statistical source data for Supplementary Fig. 12.

Supplementary Data 8

Statistical source data for Supplementary Fig. 16.

Supplementary Data 9

Statistical source data for Supplementary Fig. 26.

Supplementary Data 10

Statistical source data for Supplementary Fig. 27.

Supplementary Data 11

Statistical source data for Supplementary Fig. 31.

Supplementary Data 12

Statistical source data for Supplementary Fig. 36.

Source data

Source Data Fig. 1

Statistical source data for Fig. 1.

Source Data Fig. 2

Statistical source data for Fig. 2.

Source Data Fig. 3

Statistical source data for Fig. 3.

Source Data Fig. 4

Statistical source data for Fig. 4.

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

Zhang, L., Bai, R., Lin, J. et al. Deprotonated 2-thiolimidazole serves as a metal-free electrocatalyst for selective acetylene hydrogenation. Nat. Chem. (2024). https://doi.org/10.1038/s41557-024-01480-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1038/s41557-024-01480-6

Search

Advanced 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