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:

Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper–molecular solid catalyst

Nature Energy volume 5, pages 605–613 (2020)Cite this article

Subjects

Abstract

Ammonia (NH3) is essential for modern agriculture and industry and is a potential energy carrier. NH3 is traditionally synthesized by the Haber–Bosch process at high temperature and pressure. The high-energy input of this process has motivated research into electrochemical NH3 synthesis via nitrogen (N2)–water reactions under ambient conditions. However, the future of this low-cost process is compromised by the low yield rate and poor selectivity, ascribed to the inert N≡N bond and ultralow solubility of N2. Obtaining NH3 directly from non-N2 sources could circumvent these challenges. Here we report the eight-electron direct electroreduction of nitrate to NH3 catalysed by copper-incorporated crystalline 3,4,9,10-perylenetetracarboxylic dianhydride. The catalyst exhibits an NH3 production rate of 436 ± 85 μg h−1 cm−2 and a maximum Faradaic efficiency of 85.9% at −0.4 V versus a reversible hydrogen electrode. This notable performance is achieved by the catalyst regulating the transfer of protons and/or electrons to the copper centres and suppressing hydrogen production.

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: Screening of the element with the highest activity for the selective reduction of NO3− into NH3 when incorporated in PTCDA.
Fig. 2: Electrocatalytic performances of O-Cu–PTCDA.
Fig. 3: Characterization of the structure and composition of O-Cu–PTCDA.
Fig. 4: DFT calculations of the adsorption energy of the reactants and free energy for H2 formation.
Fig. 5: DFT calculations of the possible reaction pathways for NO3− reduction.

Similar content being viewed by others

Data availability

The authors declare that the data supporting the findings of this study are available in the paper and Supplementary Information. Additional datasets related to this study are available from the corresponding authors on reasonable request. Source data are provided with this paper.

References

  1. Christensen, C. H., Johannessen, T., Sørensen, R. Z. & Nørskov, J. K. Towards an ammonia-mediated hydrogen economy? Catal. Today 111, 140–144 (2006).

    Article  Google Scholar 

  2. Lan, R., Irvine, J. T. & Tao, S. Ammonia and related chemicals as potential indirect hydrogen storage materials. Int. J. Hydrog. Energy 37, 1482–1494 (2012).

    Article  Google Scholar 

  3. Licht, S. et al. Ammonia synthesis by N2 and steam electrolysis in molten hydroxide suspensions of nanoscale Fe2O3. Science 345, 637–640 (2014).

    Article  Google Scholar 

  4. van der Ham, C. J., Koper, M. T. & Hetterscheid, D. G. Challenges in reduction of dinitrogen by proton and electron transfer. Chem. Soc. Rev. 43, 5183–5191 (2014).

    Article  Google Scholar 

  5. Foster, S. L. et al. Catalysts for nitrogen reduction to ammonia. Nat. Catal. 1, 490–500 (2018).

    Article  Google Scholar 

  6. Chen, G. F. et al. Ammonia electrosynthesis with high selectivity under ambient conditions via a Li+ incorporation strategy. J. Am. Chem. Soc. 139, 9771–9774 (2017).

    Article  Google Scholar 

  7. Suryanto, B. H. et al. Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia. Nat. Catal. 2, 290–296 (2019).

    Article  Google Scholar 

  8. Stirling, A., Pápai, I., Mink, J. & Salahub, D. R. Density functional study of nitrogen oxides. J. Chem. Phys. 100, 2910–2923 (1994).

    Article  Google Scholar 

  9. Menció, A. et al. Nitrate pollution of groundwater; all right,… but nothing else? Sci. Total Environ. 539, 241–251 (2016).

    Article  Google Scholar 

  10. Garcia-Segura, S., Lanzarini-Lopes, M., Hristovski, K. & Westerhoff, P. Electrocatalytic reduction of nitrate: fundamentals to full-scale water treatment applications. Appl. Catal. B 236, 546–568 (2018).

    Article  Google Scholar 

  11. Hirakawa, H., Hashimoto, M., Shiraishi, Y. & Hirai, T. Selective nitrate-to-ammonia transformation on surface defects of titanium dioxide photocatalysts. ACS Catal. 7, 3713–3720 (2017).

    Article  Google Scholar 

  12. Ren, H. T., Jia, S. Y., Zou, J. J., Wu, S. H. & Han, X. A facile preparation of Ag2O/P25 photocatalyst for selective reduction of nitrate. Appl. Catal. B 176, 53–61 (2015).

    Article  Google Scholar 

  13. Dima, G. E., De Vooys, A. C. A. & Koper, M. T. M. Electrocatalytic reduction of nitrate at low concentration on coinage and transition-metal electrodes in acid solutions. J. Electroanal. Chem. 554, 15–23 (2003).

    Article  Google Scholar 

  14. De Vooys, A. C. A., Van Santen, R. A. & Van Veen, J. A. R. Electrocatalytic reduction of NO3– on palladium/copper electrodes. J. Mol. Catal. A 154, 203–215 (2000).

    Article  Google Scholar 

  15. Chen, T., Li, H., Ma, H. & Koper, M. T. M. Surface modification of Pt(100) for electrocatalytic nitrate reduction to dinitrogen in alkaline solution. Langmuir 31, 3277–3281 (2015).

    Article  Google Scholar 

  16. Pérez-Gallent, E., Figueiredo, M. C., Katsounaros, I. & Koper, M. T. Electrocatalytic reduction of nitrate on copper single crystals in acidic and alkaline solutions. Electrochim. Acta 227, 77–84 (2017).

    Article  Google Scholar 

  17. Ford, C. L., Park, Y. J., Matson, E. M., Gordon, Z. & Fout, A. R. A bioinspired iron catalyst for nitrate and perchlorate reduction. Science 354, 741–743 (2016).

    Article  Google Scholar 

  18. Zheng, H., Wisedchaisri, G. & Gonen, T. Crystal structure of a nitrate/nitrite exchanger. Nature 497, 647–651 (2013).

    Article  Google Scholar 

  19. Oosterkamp, M. J., Mehboob, F., Schraa, G., Plugge, C. M. & Stams, A. J. Nitrate and (per)chlorate reduction pathways in (per)chlorate-reducing bacteria. Biochem. Soc. Trans. 39, 230–235 (2011).

    Article  Google Scholar 

  20. Seefeldt, L. C., Hoffman, B. M. & Dean, D. R. Mechanism of Mo-dependent nitrogenase. Annu. Rev. Biochem. 78, 701–722 (2009).

    Article  Google Scholar 

  21. Khomutov, N. E. & Stamkulov, U. S. Nitrate reduction at various metal electrodes. Sov. Electrochem. 7, 312–316 (1971).

    Google Scholar 

  22. Andersen, S. Z. et al. A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements. Nature 570, 504–508 (2019).

    Article  Google Scholar 

  23. Tsuneto, A., Kudo, A. & Sakata, T. Efficient electrochemical reduction of N2 to NH3 catalyzed by lithium. Chem. Lett. 22, 851–854 (1993).

    Article  Google Scholar 

  24. Gayen, P. et al. Electrocatalytic reduction of nitrate using Magnéli phase TiO2 reactive electrochemical membranes doped with Pd-based catalysts. Environ. Sci. Technol. 52, 9370–9379 (2018).

    Article  Google Scholar 

  25. Machida, M., Sato, K., Ishibashi, I., Hasnat, M. A. & Ikeue, K. Electrocatalytic nitrate hydrogenation over an H+-conducting solid polymer electrolyte membrane-modified cathode assembly. Chem. Commun. 7, 732–734 (2006).

    Article  Google Scholar 

  26. Chaplin, B. P., Shapley, J. R. & Werth, C. J. The selectivity and sustainability of a Pd–In/γ-Al2O3 catalyst in a packed-bed reactor: the effect of solution composition. Catal. Lett. 130, 56–62 (2009).

    Article  Google Scholar 

  27. Hasnat, M. A., Karim, M. R. & Machida, M. Electrocatalytic ammonia synthesis: role of cathode materials and reactor configuration. Catal. Commun. 10, 1975–1979 (2009).

    Article  Google Scholar 

  28. Mo, Z. et al. Electrochemical recognition for tryptophan enantiomers based on 3,4,9,10-perylenetetracarboxylic acid–chitosan composite film. J. Solid State Electrochem. 22, 2405–2412 (2018).

    Article  Google Scholar 

  29. Luo, W., Allen, M., Raju, V. & Ji, X. An organic pigment as a high-performance cathode for sodium-ion batteries. Adv. Energy Mater. 4, 1400554 (2014).

    Article  Google Scholar 

  30. Park, J. Y., Jung, Y. S., Cho, J. & Choi, W. K. Chemical reaction of sputtered Cu film with PI modified by low energy reactive atomic beam. Appl. Surf. Sci. 252, 5877–5891 (2006).

    Article  Google Scholar 

  31. Zhu, D., Zhang, L., Ruther, R. E. & Hamers, R. J. Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction. Nat. Mater. 12, 836–841 (2013).

    Article  Google Scholar 

  32. Green, L. C. et al. Analysis of nitrate, nitrite, and [15N] nitrate in biological fluids. Anal. Biochem. 126, 131–138 (1982).

    Article  Google Scholar 

  33. Watt, G. W. & Chrisp, J. D. Spectrophotometric method for determination of hydrazine. Anal. Chem. 24, 2006–2008 (1952).

    Article  Google Scholar 

  34. Segall, M. D. et al. First-principles simulation: ideas, illustrations and the CASTEP code. J. Phys. Condens. Matter 14, 2717–2744 (2002).

    Article  Google Scholar 

  35. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  Google Scholar 

  36. Hamann, D. R., Schlüter, M. & Chiang, C. Norm-conserving pseudopotentials. Phys. Rev. Lett. 43, 1494–1497 (1979).

    Article  Google Scholar 

  37. Bajdich, M., García-Mota, M., Vojvodic, A., Nørskov, J. K. & Bell, A. T. Theoretical investigation of the activity of cobalt oxides for the electrochemical oxidation of water. J. Am. Chem. Soc. 135, 13521–13530 (2013).

    Article  Google Scholar 

Download references

Acknowledgements

G.-F.C. thanks the Alexander von Humboldt Foundation for a postdoctoral fellowship. This work was financially supported by the National Natural Science Foundation of China (21536005, 51621001 and 21776099), the Post-Doctoral Innovative Talents Project (BX20190119) and National Key R&D Program (2016YFA0202601). A portion of this work was conducted at Argonne National Laboratory. Argonne National Laboratory is operated for the DOE Office of Science by UChicago Argonne, LLC, under contract no. DE-AC02-06CH11357. Use of the Advanced Photon Source (beamline 9BM), Office of Science user facilities, was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract no. DE-AC02-06CH11357.

Author information

Author notes

  1. These authors contributed equally: Gao-Feng Chen, Yifei Yuan.

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, China

    Gao-Feng Chen, Haifeng Jiang, Shi-Yu Ren, Liang-Xin Ding & Haihui Wang

  2. Department of Colloids Chemistry, Max Planck Institute of Colloids and Interfaces, Potsdam, Germany

    Gao-Feng Chen

  3. Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA

    Yifei Yuan & Jun Lu

  4. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, IL, USA

    Lu Ma & Tianpin Wu

Authors
  1. Gao-Feng Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yifei Yuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Haifeng Jiang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Shi-Yu Ren
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Liang-Xin Ding
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Lu Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Tianpin Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jun Lu
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Haihui Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

G.-F.C. conducted most of experiments. Y.Y. analysed the microscopic and spectroscopic data. L.M. and T.W. conducted the X-ray absorption measurements. G.-F.C., Y.Y., J.L. and H.W. conceived the idea and designed the experiments. G.-F.C., Y.Y., S.-Y.R., H.J., L.-X.D., J.L. and H.W. analysed the data and interpreted the results. S.-Y.R., H.J. and L.-X.D. participated in discussions and data analysis. J.L. and H.W. supervised the project. G.-F.C. and Y.Y. co-wrote the manuscript. All the authors contributed to discussions and the writing of the manuscript.

Corresponding authors

Correspondence to Jun Lu or Haihui Wang.

Ethics declarations

Competing interests

The authors declare no competing interests.

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. 1–42, Notes 1–7, Supplementary Tables 1–3 and refs. 1–9.

Supplementary Data 1

Replicates data for Supplementary Figs. 2, 5–12, 14 and 36–42.

Source data

Source Data Fig. 1

Experimental source data and DFT calculation source data.

Source Data Fig. 2

Experimental source data.

Source Data Fig. 3

Unprocessed TEM and elemental mapping images and experimental source data.

Source Data Fig. 4

DFT calculations source data

Source Data Fig. 5

DFT calculations source data.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chen, GF., Yuan, Y., Jiang, H. et al. Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper–molecular solid catalyst. Nat Energy 5, 605–613 (2020). https://doi.org/10.1038/s41560-020-0654-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-020-0654-1

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