journal article·2024-01Open access

Calcium-mediated nitrogen reduction for electrochemical ammonia synthesis

Xianbiao Fu, Valerie A. Niemann, Yuanyuan Zhou, Shaofeng Li, Ke Zhang, Jakob B. Pedersen, Mattia Saccoccio, Suzanne Z. Andersen, Kasper Enemark-Rasmussen, Peter Benedek, Aoni Xu, Niklas H. Deissler, Jon Bjarke Valbæk Mygind, Adam C. Nielander, Jakob Kibsgaard, Peter C. K. Vesborg, Jens K. Nørskov, Thomas F. Jaramillo, Ib Chorkendorff

Nature Materials· Volume 23· Issue 1

Abstract

Ammonia (NH3) is a key commodity chemical for the agricultural, textile and pharmaceutical industries, but its production via the Haber-Bosch process is carbon-intensive and centralized. Alternatively, an electrochemical method could enable decentralized, ambient NH3 production that can be paired with renewable energy. The first verified electrochemical method for NH3 synthesis was a process mediated by lithium (Li) in organic electrolytes. So far, however, elements other than Li remain unexplored in this process for potential benefits in efficiency, reaction rates, device design, abundance and stability. In our demonstration of a Li-free system, we found that calcium can mediate the reduction of nitrogen for NH3 synthesis. We verified the calcium-mediated process using a rigorous protocol and achieved an NH3 Faradaic efficiency of 40 ± 2% using calcium tetrakis(hexafluoroisopropyloxy)borate (Ca[B(hfip)4]2) as the electrolyte. Our results offer the possibility of using abundant materials for the electrochemical production of NH3, a critical chemical precursor and promising energy vector.
Source: europepmc · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Ammonia Synthesis and Nitrogen Reduction · Hydrogen Storage and Materials · Caching and Content Delivery

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (53)

Show source-provided references
1. Iriawan, H. et al. Methods for nitrogen activation by reduction and oxidation. Nat. Rev. Methods Primers 1, 56 (2021).10.1038/s43586-021-00053-y ↗
2. Chen, J. G. et al. Beyond fossil fuel-driven nitrogen transformations. Science 360, eaar6611 (2018).10.1126/science.aar6611 ↗
3. Fu, X. B., Zhang, J. H. & Kang, Y. J. Recent advances and challenges of electrochemical ammonia synthesis. Chem. Catal. 2, 2590–2613 (2022).10.1016/j.checat.2022.09.001 ↗
4. Mineral Commodity Summaries 2022 (US Geological Survey, 2022).
5. Erisman, J. W., Sutton, M. A., Galloway, J., Klimont, Z. & Winiwarter, W. How a century of ammonia synthesis changed the world. Nat. Geosci. 1, 636–639 (2008).10.1038/ngeo325 ↗
6. Choi, J. et al. Identification and elimination of false positives in electrochemical nitrogen reduction studies. Nat. Commun. 11, 5546 (2020).
7. Andersen, S. Z. et al. A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements. Nature 570, 504–508 (2019).10.1038/s41586-019-1260-x ↗
8. Greenwood, N. N., Earnshaw, E. A. Chemistry of the Elements (Pergamon, 1984).
9. Fichter, F., Girard, P.-L. & Erlenmeyer, H. Elektrolytische Bindung von komprimiertem Stickstoff bei gewöhnlicher Temperatur. Helv. Chim. Acta 13, 1228–1236 (1930).10.1002/hlca.19300130604 ↗
10. Tsuneto, A., Kudo, A. & Sakata, T. Efficient electrochemical reduction of N2 to NH3 catalyzed by lithium. Chem. Lett. 22, 851–854 (1993).10.1246/cl.1993.851 ↗
11. Tsuneto, A., Kudo, A. & Sakata, T. Lithium-mediated electrochemical reduction of high-pressure N2 to NH3. J. Electroanal. Chem. 367, 183–188 (1994).10.1016/0022-0728(93)03025-K ↗
12. Andersen, S. Z. et al. Increasing stability, efficiency, and fundamental understanding of lithium-mediated electrochemical nitrogen reduction. Energy Environ. Sci. 13, 4291–4300 (2020).10.1039/D0EE02246B ↗
13. Cai, X. Y. et al. Lithium-mediated electrochemical nitrogen reduction: mechanistic insights to enhance performance. iScience 24, 103105 (2021).10.1016/j.isci.2021.103105 ↗
14. Lazouski, N., Chung, M. J., Williams, K., Gala, M. L. & Manthiram, K. Non-aqueous gas diffusion electrodes for rapid ammonia synthesis from nitrogen and water-splitting-derived hydrogen. Nat. Catal. 3, 463–469 (2020).10.1038/s41929-020-0455-8 ↗
15. Li, K. et al. Enhancement of lithium-mediated ammonia synthesis by addition of oxygen. Science 374, 1593–1597 (2021).10.1126/science.abl4300 ↗
16. Li, K. et al. Increasing current density of Li-mediated ammonia synthesis with high surface area copper electrodes. ACS Energy Lett. 7, 36–41 (2022).10.1021/acsenergylett.1c02104 ↗
17. McEnaney, J. M. et al. Ammonia synthesis from N2 and H2O using a lithium cycling electrification strategy at atmospheric pressure. Energy Environ. Sci. 10, 1621–1630 (2017).10.1039/C7EE01126A ↗
18. Lazouski, N., Schiffer, Z. J., Williams, K. & Manthiram, K. Understanding continuous lithium-mediated electrochemical nitrogen reduction. Joule 3, 1127–1139 (2019).10.1016/j.joule.2019.02.003 ↗
19. Suryanto, B. H. R. et al. Nitrogen reduction to ammonia at high efficiency and rates based on a phosphonium proton shuttle. Science 372, 1187–1191 (2021).10.1126/science.abg2371 ↗
20. Du, H. L. et al. Electroreduction of nitrogen with almost 100% current-to-ammonia efficiency. Nature 609, 722–727 (2022).10.1038/s41586-022-05108-y ↗
21. Li, S. et al. Electrosynthesis of ammonia with high selectivity and high rates via engineering of the solid–electrolyte interphase. Joule 6, 2083–2101 (2022).10.1016/j.joule.2022.07.009 ↗
22. Fu, X. et al. Continuous-flow electrosynthesis of ammonia by nitrogen reduction and hydrogen oxidation. Science 379, 707–712 (2023).10.1126/science.adf4403 ↗
23. Frank, A. R. On the utilisation of the atmospheric nitrogen in the production of calcium cyanamide, and its use in agriculture and chemistry. Trans. Faraday Soc. 4, 99–114 (1908).10.1039/tf9080400099 ↗
24. Rösch, B. et al. Dinitrogen complexation and reduction at low-valent calcium. Science 371, 1125–1128 (2021).10.1126/science.abf2374 ↗
25. Chen, X. Y. et al. Oxygen vacancy engineering of calcium cobaltate: a nitrogen fixation electrocatalyst at ambient condition in neutral electrolyte. Nano Res. 14, 501–506 (2021).10.1007/s12274-020-3043-y ↗
26. Kibsgaard, J. et al. The difficulty of proving electrochemical ammonia synthesis. ACS Energy Lett. 4, 2986–2988 (2019).10.1021/acsenergylett.9b02286 ↗
27. Wang, D. et al. Plating and stripping calcium in an organic electrolyte. Nat. Mater. 17, 16–20 (2018).10.1038/nmat5036 ↗
28. Biria, S., Pathreeker, S., Genier, F. S., Li, H. S. & Hosein, I. D. Plating and stripping calcium at room temperature in an ionic-liquid electrolyte. ACS Appl. Energy Mater. 3, 2310–2314 (2020).10.1021/acsaem.9b02529 ↗
29. Melemed, A. M., Skiba, D. A. & Gallant, B. M. Toggling calcium plating activity and reversibility through modulation of Ca2+ speciation in borohydride-based electrolytes. J. Phys. Chem. C 126, 892–902 (2022).10.1021/acs.jpcc.1c09400 ↗
30. Ta, K. et al. Understanding Ca electrodeposition and speciation processes in nonaqueous electrolytes for next-generation Ca-ion batteries. ACS Appl. Mater. Interfaces 11, 21536–21542 (2019).10.1021/acsami.9b04926 ↗
31. Ponrouch, A., Frontera, C., Barde, F. & Palacin, M. R. Towards a calcium-based rechargeable battery. Nat. Mater. 15, 169–172 (2016).10.1038/nmat4462 ↗
32. Shyamsunder, A., Blanc, L. E., Assoud, A. & Nazar, L. F. Reversible calcium plating and stripping at room temperature using a borate salt. ACS Energy Lett. 4, 2271–2276 (2019).10.1021/acsenergylett.9b01550 ↗
33. Li, Z. Y., Fuhr, O., Fichtner, M. & Zhao-Karger, Z. Towards stable and efficient electrolytes for room-temperature rechargeable calcium batteries. Energy Environ. Sci. 12, 3496–3501 (2019).10.1039/C9EE01699F ↗
34. Nielson, K. V., Luo, J. & Liu, T. L. Optimizing calcium electrolytes by solvent manipulation for calcium batteries. Batter. Supercaps 3, 766–772 (2020).10.1002/batt.202000005 ↗
35. Bitenc, J. et al. Electrochemical performance and mechanism of calcium metal–organic battery. Batter. Supercaps 4, 214–220 (2021).10.1002/batt.202000197 ↗
36. McShane, E. J. et al. A versatile Li0.5FePO4 reference electrode for nonaqueous electrochemical conversion technologies. ACS Energy Lett. 8, 230–235 (2022).10.1021/acsenergylett.2c02190 ↗
37. Vandoveren, H. & Verhoeven, J. A. T. XPS spectra of Ca, Sr, Ba and their oxides. J. Electron Spectrosc. Relat. Phenom. 21, 265–273 (1980).10.1016/0368-2048(80)85055-9 ↗
38. Su, Y. G., Huang, S. S., Wang, T. T., Peng, L. M. & Wang, X. J. Defect-meditated efficient catalytic activity toward p-nitrophenol reduction: a case study of nitrogen doped calcium niobate system. J. Hazard. Mater. 295, 119–126 (2015).10.1016/j.jhazmat.2015.04.036 ↗
39. Gao, W. et al. Production of ammonia via a chemical looping process based on metal imides as nitrogen carriers. Nat. Energy 3, 1067–1075 (2018).10.1038/s41560-018-0268-z ↗
40. Wietelmann, U., Felderhoff, M. & Rittmeyer, P. Ullmann’s Encyclopedia of Industrial Chemistry (Wiley, 2016).
41. Il’inchik, E. A., Volkov, V. V. & Mazalov, L. N. X-ray photoelectron spectroscopy of boron compounds. J. Struct. Chem. 46, 523–534 (2005).10.1007/s10947-006-0133-y ↗
42. Prabakar, S. J. R. et al. Graphite as a long-life Ca2+-intercalation anode and its implementation for rocking-chair type calcium-ion batteries. Adv. Sci. 6, 1902129 (2019).10.1002/advs.201902129 ↗
43. Park, J. et al. Stable and high-power calcium-ion batteries enabled by calcium intercalation into graphite. Adv. Mater. 32, 1904411 (2020).10.1002/adma.201904411 ↗
44. Kohn, W. & Sham, L. J. Self-consistent equations including exchange and correlation effects. Phys. Rev. 140, A1133–A1138 (1965).10.1103/PhysRev.140.A1133 ↗
45. Kresse, G. & Furthmuller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).10.1103/PhysRevB.54.11169 ↗
46. Bahn, S. R. & Jacobsen, K. W. An object-oriented scripting interface to a legacy electronic structure code. Comput. Sci. Eng. 4, 56–66 (2002).10.1109/5992.998641 ↗
47. Hammer, B., Hansen, L. B. & Norskov, J. K. Improved adsorption energetics within density-functional theory using revised Perdew–Burke–Ernzerhof functionals. Phys. Rev. B 59, 7413–7421 (1999).10.1103/PhysRevB.59.7413 ↗
48. Blochl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).10.1103/PhysRevB.50.17953 ↗
49. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).10.1103/PhysRevB.59.1758 ↗
50. Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).10.1103/PhysRevB.13.5188 ↗
51. Henkelman, G., Uberuaga, B. P. & Jonsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).10.1063/1.1329672 ↗
52. Mathew, K. et al. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. J. Chem. Phys. 140, 084106 (2014).10.1063/1.4865107 ↗
53. Mathew, K. et al. Implicit self-consistent electrolyte model in plane-wave density-functional theory. J. Chem. Phys. 151, 234101 (2019).10.1063/1.5132354 ↗