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Optimizing Nitrogen Reduction Reaction on Nitrides: A Computational Study on Crystallographic Orientation

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Abstract

Pursuing an environmentally friendly alternative to the Haber–Bosch process, using density functional theory (DFT) we explore further the merit of transition metal nitride (TMN) surfaces as catalysts for the nitrogen reduction reaction (NRR). Prior studies by our group have investigated the (100) and (111) facets of these TMNs and found the (100) to be favored in all cases. Many of the (100) facets of TMNs showed promising activity for ammonia (NH3) formation. Recent experiments investigating the polycrystalline growth of these TMNs indicated the substantial presence of the (110) facet as well, and so we explore the properties of this surface orientation and compare it to the (100) facets previously reported. The only (110) facets of TMN that showed any promise was VN, but it suffered from high activation energies for N2 adsorption compared to the activation energy of N migration from the bulk, which would likely lead to decomposition of the catalyst. The (110) facets showed overall worse catalytic activity than the (100). The most important outcome of this study is that the presence of the (110) facet of these TMNs in the catalyst structure will be detrimental to the activity of the catalyst. Great care must be taken when investigating the performance of these catalysts by engineering the surface to only include the surface orientation of interest.

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Data Availability

The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

Code Availability

The VASP code was used for the DFT calculations of this manuscript and the corresponding details of that are provided in the manuscript.

References

  1. The Facts About Ammonia (2004) New York State. https://www.health.ny.gov/environmental/emergency/chemical_terrorism/ammonia_tech.htm#:~:text=Ammonia%20is%20also%20used%20as,and%20industrial%2Dstrength%20cleaning%20solutions. Accessed 22 Mar 2021

  2. Chen S et al (2019) Horizons in sustainable industrial chemistry and catalysis. Elsevier, Amsterdam. https://doi.org/10.1016/B978-0-444-64127-4.00002-1

    Book  Google Scholar 

  3. Valera-Medina A et al (2018) Ammonia for power. Prog Energy Combust Sci. https://doi.org/10.1016/j.pecs.2018.07.001

    Article  Google Scholar 

  4. Qing G et al (2020) Recent advances and challenges of electrocatalytic N2 reduction to ammonia. Chem Rev. https://doi.org/10.1021/acs.chemrev.9b00659

    Article  PubMed  Google Scholar 

  5. Guo X et al (2019) Recent progress in electrocatalytic nitrogen reduction. J Mater Chem A. https://doi.org/10.1039/C8TA11201K

    Article  Google Scholar 

  6. Lee J, Tan LL, Chai SP (2021) Heterojunction photocatalysts for artificial nitrogen fixation: fundamentals, latest advances and future perspectives. Nanoscale. https://doi.org/10.1039/D1NR00783A

    Article  PubMed  PubMed Central  Google Scholar 

  7. Shen H et al (2021) Electrochemical ammonia synthesis: mechanistic understanding and catalyst design. Chem. https://doi.org/10.1016/j.chempr.2021.01.009

    Article  Google Scholar 

  8. Rouwenhorst KHR et al (2021) Techno-economic challenges of green ammonia as an energy vector, 1st edn. Academic Press, Cambridge. https://doi.org/10.1016/B978-0-12-820560-0.00004-7

    Book  Google Scholar 

  9. Xue X, Chen R, Yan C et al (2019) Review on photocatalytic and electrocatalytic artificial nitrogen fixation for ammonia synthesis at mild conditions: advances, challenges and perspectives. Nano Res. https://doi.org/10.1007/s12274-018-2268-5

    Article  Google Scholar 

  10. Giddey S, Badwal SPS, Kulkarni A (2013) Review of electrochemical ammonia production technologies and materials. Int J Hydrog Energy. https://doi.org/10.1016/j.ijhydene.2013.09.054

    Article  Google Scholar 

  11. Liu PY et al (2021) Enhanced electrocatalytic nitrogen reduction reaction performance by interfacial engineering of MOF-based sulfides FeNi2S4/NiS hetero-interface. Appl Catal B Environ. https://doi.org/10.1016/j.apcatb.2021.119956

    Article  Google Scholar 

  12. Zheng J et al (2021) Structural insight into [Fe–S2–Mo] motif in electrochemical reduction of N2 over Fe1-supported molecular MoS2. Chem Sci. https://doi.org/10.1039/D0SC04575F

    Article  PubMed  PubMed Central  Google Scholar 

  13. Nørskov JK et al (2004) Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J Phys Chem B. https://doi.org/10.1021/jp047349j

    Article  Google Scholar 

  14. Montoya JH, Tsai C, Vojvodic A, Nørskov JK (2015) The challenge of electrochemical ammonia synthesis: a new perspective on the role of nitrogen scaling relations. Chemsuschem. https://doi.org/10.1002/cssc.201500322

    Article  PubMed  Google Scholar 

  15. Skúlason E et al (2012) A theoretical evaluation of possible transition metal electrocatalysts for N2 reduction. Phys Chem Chem Phys. https://doi.org/10.1039/C1CP22271F

    Article  PubMed  Google Scholar 

  16. Doornkamp C, Ponec V (2000) The universal character of the Mars and Van Krevelen mechanism. J Mol Catal A Chem. https://doi.org/10.1016/S1381-1169(00)00319-8

    Article  Google Scholar 

  17. Yang X et al (2018) Mechanistic insights into electrochemical nitrogen reduction reaction on vanadium nitride nanoparticles. J Am Chem Soc. https://doi.org/10.1021/jacs.8b08379

    Article  PubMed  PubMed Central  Google Scholar 

  18. Abghoui Y, Skúlason E (2017) Electrochemical synthesis of ammonia via Mars-van Krevelen mechanism on the (111) facets of group III–VII transition metal mononitrides. Catal Today. https://doi.org/10.1016/j.cattod.2016.06.009

    Article  Google Scholar 

  19. Abghoui Y et al (2015) Enabling electrochemical reduction of nitrogen to ammonia at ambientconditions through rational catalyst design. Phys Chem Chem Phys. https://doi.org/10.1039/C4CP04838E

    Article  PubMed  Google Scholar 

  20. Abghoui Y et al (2016) Electroreduction of N2 to ammonia at ambient conditions on mononitrides of Zr, Nb, Cr, and V: A DFT guide for experiments. ACS Catal. https://doi.org/10.1021/acscatal.5b01918

    Article  Google Scholar 

  21. Zhang L et al (2018) Efficient electrochemical N2 reduction to NH3 on MoN nanosheets array under ambient conditions. ACS Sustain Chem Eng. https://doi.org/10.1021/acssuschemeng.8b01438

    Article  PubMed  PubMed Central  Google Scholar 

  22. Guo W et al (2021) Understanding the lattice nitrogen stability and deactivation pathways of cu-bic CrN nanoparticles in the electrochemical nitrogen reduction reaction. J Mater Chem A. https://doi.org/10.1039/D0TA11727G

    Article  Google Scholar 

  23. Zhang X et al (2018) Highly efficient electrochemical ammonia synthesis via nitrogen reduction reactions on a VN nanowire array under ambient conditions. Chem Commun. https://doi.org/10.1039/C8CC00459E

    Article  Google Scholar 

  24. Hanifpour F et al (2021) Experimental performance of theoretically derived transition metal nitrides as catalysts for electrochemical reduction of N2 to NH3. Submitted

  25. Hammer B, Hansen LB, Nørskov JK (1999) Improved adsorption energetics within densityfunctional theory using revised Perdew-Burke-Ernzerhof functionals. Phys Rev B. https://doi.org/10.1103/PhysRevB.59.7413

    Article  Google Scholar 

  26. Kresse G, Furthmüller J (1996) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev. https://doi.org/10.1103/PhysRevB.54.11169

    Article  Google Scholar 

  27. Blöchl PE (1994) Projector augmented-wave method. Phys Rev B. https://doi.org/10.1103/PhysRevB.50.17953

    Article  Google Scholar 

  28. Henkelman G, Uberuaga BP, Jónsson H (2000) A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J Chem Phys. https://doi.org/10.1063/1.1329672

    Article  Google Scholar 

  29. Greenlee LF, Renner JN, Foster SL (2018) The use of controls for consistent and accurate measurements of electrocatalytic ammonia synthesis from dinitrogen. ACS Catal. https://doi.org/10.1021/acscatal.8b02120

    Article  Google Scholar 

  30. Abghoui Y, Skúlason E (2017) Hydrogen evolution reaction catalyzed by transition-metal nitrides. J Phys Chem C. https://doi.org/10.1021/acs.jpcc.7b06811

    Article  Google Scholar 

  31. Abghoui Y (2021) Superiority of the (100) over the (111) facets of the nitrides for hydrogen evolution reaction. Top Catal. https://doi.org/10.1007/s11244-021-01474-5

    Article  Google Scholar 

  32. Pan J, Hansen HA, Vegge T (2020) Vanadium oxynitrides as stable catalysts for electrochemical reduction of nitrogen to ammonia: the role of oxygen. J Mater Chem A. https://doi.org/10.1039/D0TA08313E

    Article  Google Scholar 

  33. Abghoui Y, Skúlason E (2017) Onset potentials for different reaction mechanisms of nitrogen activation to ammonia on transition metal nitride electro-catalysts. Catal Today. https://doi.org/10.1016/j.cattod.2016.11.047

    Article  Google Scholar 

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Acknowledgements

Financial support is acknowledged from the Icelandic Research Fund (Grant Numbers 185051-051 and 196437-051) and the Research Fund of the University of Iceland. The calculations were carried out on the Icelandic high-performance computer, Garpur.

Funding

Icelandic research Fund (Grant Numbers 185051-051 and 196437-051), and research fund of the University of Iceland.

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Authors and Affiliations

  1. Science Institute of the University of Iceland, Reykjavik, Iceland

    Matthías Gudmundsson, Viktor Ellingsson, Egill Skúlason & Younes Abghoui

  2. Faculty of Industrial Engineering, Mechanical Engineering and Computer Science, University of Iceland, Reykjavik, Iceland

    Egill Skúlason

Authors
  1. Matthías Gudmundsson
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  2. Viktor Ellingsson
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  3. Egill Skúlason
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  4. Younes Abghoui
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Correspondence to Younes Abghoui.

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Gudmundsson, M., Ellingsson, V., Skúlason, E. et al. Optimizing Nitrogen Reduction Reaction on Nitrides: A Computational Study on Crystallographic Orientation. Top Catal 65, 252–261 (2022). https://doi.org/10.1007/s11244-021-01485-2

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