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Cited by 711Ammonia Synthesis and Nitrogen ReductionCatalytic Processes in Materials ScienceHydrogen Storage and Materials

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Breaking scaling relations to achieve low-temperature ammonia synthesis through LiH-mediated nitrogen transfer and hydrogenation

Wang, Peikun, Chang, Fei, Gao, Wenbo, Guo, Jianping, Wu, Guotao, He, Teng, Chen, Ping·2017·Nature Chemistry
DOI 10.1038/nchem.2595
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Abstract

Ammonia synthesis under mild conditions is a goal that has been long sought after. Previous investigations have shown that adsorption and transition-state energies of intermediates in this process on transition metals (TMs) scale with each other. This prevents the independent optimization of these energies that would result in the ideal catalyst: one that activates reactants well, but binds intermediates relatively weakly. Here we demonstrate that these scaling relations can be broken by intervening in the TM-mediated catalysis with a second catalytic site, LiH. The negatively charged hydrogen atoms of LiH act as strong reducing agents, which remove activated nitrogen atoms from the TM or its nitride (TMN), and as an immediate source of hydrogen, which binds nitrogen atoms to form LiNH 2 . LiNH 2 further splits H 2 heterolytically to give off NH 3 and regenerate LiH. This synergy between TM (or TMN) and LiH creates a favourable pathway that allows both early and late 3d TM-LiH composites to exhibit unprecedented lower-temperature catalytic activities.

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Research works printed but not linked: 48

  1. 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). · DOI
  2. Burgess, B. K. & Lowe, D. J. Mechanism of molybdenum nitrogenase. Chem. Rev. 96, 2983–3011 (1996). · DOI
  3. Schlögl, R. Catalytic synthesis of ammonia—a ‘never-ending story’? Angew. Chem. Int. Ed. 42, 2004–2008 (2003). · DOI
  4. Kojima, R. & Aika, K. Cobalt molybdenum bimetallic nitride catalysts for ammonia synthesis. Chem. Lett. 29, 514–515 (2000). · DOI
  5. Jacobsen, C. J. H. et al. Catalyst design by interpolation in the periodic table: bimetallic ammonia synthesis catalysts. J. Am. Chem. Soc. 123, 8404–8405 (2001). · DOI
  6. Kitano, M. et al. Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store. Nat. Chem. 4, 934–940 (2012). · DOI
  7. Zhu, D., Zhang, L. H., Ruther, R. E. & Hamers, R. J. Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction. Nature Mater. 12, 836–841 (2013). · DOI
  8. Licht, S. et al. Ammonia synthesis by N2 and steam electrolysis in molten hydroxide suspensions of nanoscale Fe2O3 . Science 345, 637–640 (2014). · DOI
  9. Yandulov, D. V. & Schrock, R. R. Catalytic reduction of dinitrogen to ammonia at a single molybdenum center. Science 301, 76–78 (2003). · DOI
  10. Arashiba, K., Miyake, Y. & Nishibayashi, Y. A molybdenum complex bearing PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia. Nat. Chem. 3, 120–125 (2011). · DOI
  11. Anderson, J. S., Rittle, J. & Peters, J. C. Catalytic conversion of nitrogen to ammonia by an iron model complex. Nature 501, 84–88 (2013). · DOI
  12. Montemore, M. M. & Medlin, J. W. Scaling relations between adsorption energies for computational screening and design of catalysts. Catal. Sci. Technol. 4, 3748–3761 (2014). · DOI
  13. Pallassana, V. & Neurock, M. Electronic factors governing ethylene hydrogenation and dehydrogenation activity of pseudomorphic Pd–ML/Re(0001), Pd–ML/Ru(0001), Pd(111), and Pd–ML/Au(111) surfaces. J. Catal. 191, 301–317 (2000). · DOI
  14. Calle-Vallejo, F., Loffreda, D., Koper, M. T. M. & Sautet, P. Introducing structural sensitivity into adsorption-energy scaling relations by means of coordination numbers. Nat. Chem. 7, 403–410 (2015). · DOI
  15. Nørskov, J. K., Bligaard, T., Rossmeisl, J. & Christensen, C. H. Towards the computational design of solid catalysts. Nat. Chem. 1, 37–46 (2009). · DOI · Paper page
  16. Chen, Y., Salciccioli, M. & Vlachos, D. G. An efficient reaction pathway search method applied to the decomposition of glycerol on platinum. J. Phys. Chem. C 115, 18707–18720 (2011). · DOI
  17. Medford, A. J. et al. From the Sabatier principle to a predictive theory of transition-metal heterogeneous catalysis. J. Catal. 328, 36–42 (2015). · DOI
  18. Vojvodic, A. et al. Exploring the limits: a low-pressure, low-temperature Haber–Bosch process. Chem. Phys. Lett. 598, 108–112 (2014). · DOI
  19. Akagi, F., Matsuo, T. & Kawaguchi, H. Dinitrogen cleavage by a diniobium tetrahydride complex: formation of a nitride and its conversion into imide species. Angew. Chem. Int. Ed. 46, 8778–8781 (2007). · DOI
  20. Avenier, P. et al. Dinitrogen dissociation on an isolated surface tantalum atom. Science 317, 1056–1060 (2007). · DOI
  21. Shima, T. et al. Dinitrogen cleavage and hydrogenation by a trinuclear titanium polyhydride complex. Science 340, 1549–1552 (2013). · DOI
  22. Pfirrmann, S., Limberg, C., Herwig, C., Stosser, R. & Ziemer, B. A dinuclear nickel(I) dinitrogen complex and its reduction in single-electron steps. Angew. Chem. Int. Ed. 48, 3357–3361 (2009). · DOI
  23. King, D. A. & Sebba, F. Catalytic synthesis of ammonia over vanadium nitride containing oxygen. 1. The reaction mechanism. J. Catal. 4, 253–259 (1965). · DOI
  24. Mittasch, A. Early studies of multicomponent catalysts. Adv. Catal. 2, 81–104 (1950). · DOI
  25. Ertl, G. Surface science and catalysis—studies on the mechanism of ammonia synthesis: the P. H. Emmett award address. Catal. Rev. Sci. Eng. 21, 201–223 (1980). · DOI
  26. Fernandez, E. M. et al. Scaling relationships for adsorption energies on transition metal oxide, sulfide, and nitride surfaces. Angew. Chem. Int. Ed. 47, 4683–4686 (2008). · DOI
  27. Scholten, J. J. F. & Zwietering, P. Kinetics of the chemisorption of nitrogen on ammonia-synthesis catalysts. Trans. Faraday Soc. 53, 1363–1370 (1957). · DOI
  28. Stoltze, P. & Nørskov, J. K. Bridging the ‘pressure gap’ between ultrahigh-vacuum surface physics and high-pressure catalysis. Phys. Rev. Lett. 55, 2502–2505 (1985). · DOI
  29. Chen, P., Xiong, Z. T., Luo, J. Z., Lin, J. Y. & Tan, K. L. Interaction of hydrogen with metal nitrides and imides. Nature 420, 302–304 (2002). · DOI
  30. Leng, H. Y., Ichikawa, T., Hino, S. & Fujii, H. Investigation of reaction between LiNH2 and H2 . J. Alloys Compd 463, 462–465 (2008). · DOI
  31. Goshome, K. et al. Ammonia synthesis via non-equilibrium reaction of lithium nitride in hydrogen flow condition. Mater. Trans. 56, 410–414 (2015). · DOI
  32. Chen, P., Xiong, Z. T., Luo, J. Z., Lin, J. Y. & Tan, K. L. Interaction between lithium amide and lithium hydride. J. Phys. Chem. B 107, 10967–10970 (2003). · DOI
  33. Tanabe, Y. & Nishibayashi, Y. Developing more sustainable processes for ammonia synthesis. Coord. Chem. Rev. 257, 2551–2564 (2013). · DOI
  34. Schlögl, R. in Handbook of Heterogeneous Catalysis (eds Ertl, G., Knözinger, H., Schüth, F. & Weitkamp, J.) 2501–2575 (Wiley, 2008). · DOI
  35. Hagen, S. et al. Ammonia synthesis with barium-promoted iron–cobalt alloys supported on carbon. J. Catal. 214, 327–335 (2003). · DOI
  36. Rosowski, F. et al. Ruthenium catalysts for ammonia synthesis at high pressures: preparation, characterization, and power-law kinetics. Appl. Catal. A 151, 443–460 (1997). · DOI
  37. Miyaoka, H. et al. Improvement of reaction kinetics by metal chloride on ammonia and lithium hydride system. Int. J. Hydrogen Energy 37, 16025–16030 (2012). · DOI
  38. Kojima, R. & Aika, K. Cobalt molybdenum bimetallic nitride catalysts for ammonia synthesis. Part 2. Kinetic study. Appl. Catal. A 218, 121–128 (2001). · DOI
  39. Fastrup, B., Muhler, M., Nielsen, H. N. & Nielsen, L. P. The interaction of H2 and N2 with iron catalysts used for NH3 synthesis—a temperature-programmed desorption and reaction study. J. Catal. 142, 135–146 (1993). · DOI
  40. Koel, B. E. & Kim, J. in Handbook of Heterogeneous Catalysis (eds Ertl, G., Knözinger, H., Schüth, F. & Weitkamp, J.) 1593–1624 (Wiley, 2008). · DOI
  41. Aika, K., Takano, T. & Murata, S. Preparation and characterization of chlorine-free ruthenium catalyst and the promoter effect in ammonia synthesis. 3. A magnesia-supported ruthenium catalyst. J. Catal. 136, 126–140 (1992). · DOI
  42. Yin, S. F., Xu, B. Q., Zhou, X. P. & Au, C. T. A mini-review on ammonia decomposition catalysts for on-site generation of hydrogen for fuel cell applications. Appl. Catal. A 277, 1–9 (2004). · DOI
  43. Guo, J. P. et al. Lithium imide synergizes with 3d transition metal nitrides leading to unprecedented catalytic activities. Angew. Chem. Int. Ed. 54, 2950–2954 (2015). · DOI
  44. Hino, S., Ichikawa, T. & Kojima, Y. Thermodynamic properties of metal amides determined by ammonia pressure-composition isotherms. J. Chem. Thermodyn. 42, 140–143 (2010). · DOI
  45. Binnewies, M. & Milke, E. Thermochemical Data of Elements and Compounds 2nd edn (Wiley, 2002). · DOI
  46. Zhang, J. Studies on Thermodynamics and Kinetics of Ferromanganese Nitriding PhD thesis, Chongqing Univ. (2004).
  47. Aika, K. & Tamaru, K. in Ammonia: Catalysis and Manufacture (ed. Nielsen, A.) 103–148 (Springer, 1995). · DOI
  48. Imai, Y., Sohma, M. & Suemasu, T. Energetic stability and magnetic moment of tri-, tetra-, and octa-ferromagnetic element nitrides predicted by first-principle calculations. J. Alloys Compd 611, 440–445 (2014). · DOI

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Metadata

Authors
Wang, P., Chang, F., Gao, W., Guo, J., Wu, G., He, T., & Chen, P.
Affiliations
Dalian Institute of Chemical Physics (CN)
Corresponding author
  • Guo, Jianping
  • Chen, Ping
ORCID
Venue
Nature Chemistry
Publisher
Springer Science and Business Media LLC
Published
2016-08-22
Volume
9
Issue
1
Pages
64-70
ISSN
  • 1755-4330 (ISSN-L)
  • 1755-4349
DOI
10.1038/nchem.2595
OpenAlex
W2510877666
Cited by
711
References
53
Citations by year
2026: 68 · 2025: 102 · 2024: 100 · 2023: 70 · 2022: 99 · 2021: 84 · 2020: 68 · 2019: 58 · 2018: 44 · 2017: 17
FWCI
13.20
Type
journal article
Language
en
Open access
closed
Licence
www.springer.com/tdm (tdm)
Locations
  • Nature Chemistry (publishedVersion)
  • PubMed (publishedVersion)
  • Dalian Institute of Chemical Physics, CAS Institutional Repository (submittedVersion)
Funders
Collaborative Innovation Center of Chemistry for Energy Materials
Topics
  • Physical Sciences › Chemical Engineering › Catalysis › Ammonia Synthesis and Nitrogen Reduction
  • Physical Sciences › Materials Science › Materials Chemistry › Catalytic Processes in Materials Science
  • Physical Sciences › Materials Science › Materials Chemistry › Hydrogen Storage and Materials
Keywords
ammonia synthesis, low-temperature catalysis, lithium hydride, hydrogenation, nitrogen transfer, transition metal catalysts, scaling laws, adsorption energy, transition metal nitrides, lithium amide, 3d transition metals, bimetallic catalysts

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