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Plasma Catalytic Conversion of Nitrogen and Hydrogen to Ammonia Over Silico Alumino Phosphate (SAPO) Zeolites

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Abstract

Herein, we demonstrate the catalytic activity of microporous Silico Alumino Phosphate (SAPOs) crystals for the assisted plasma synthesis of ammonia. SAPOs can aid as effective catalysts for the synthesis of ammonia via non-thermal plasma using an atmospheric dielectric barrier discharge (DBD) reactor. We studied three prototypical zeolites having crystallographic limiting pore apertures of 3.4 Å (SAPO-56), 3.8 Å (SAPO-34) and 3.9 Å (SAPO-11). We describe a fundamental insight on the effect of the Si/Al ratio and the pore size on ammonia synthesis rate for the different SAPOs. The resultant SAPO-11 displayed ammonia synthesis rates as high as 0.19 micromoles NH3/ min m2 at 20 watts, approximately 1.5 times better compared to other SAPOs. The results indicate that ammonia synthesis is promoted by a lower Si/Al ratio (< 0.25) of the SAPO. Moreover, we observed that SAPO-34 (3.8 Å) and SAPO-11 (3.9 Å) which allow diffusion of N2 (3.6 Å) in to the pores lead to a higher ammonia yield. The lower intensity observed in optical emission spectroscopy (OES) for SAPO-34 suggests the diffusion of plasma activated species onto the surface and the pores. Proving the importance of porosity in plasma catalysis.

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References

  1. Tanabe Y, Nishibayashi Y (2013) Developing more sustainable processes for ammonia synthesis. Coord Chem Rev 257:2551–2564

    Article  CAS  Google Scholar 

  2. http://ictpost.com/global-ammonia-capacity-to-reach-250-million-tons-per-year-by-2018/, Global Ammonia Capacity to reach 250 million tons per year by 2018, in, 2015

  3. Erisman JW, Sutton MA, Galloway J, Klimont Z, Winiwarter W (2008) How a century of ammonia synthesis changed the world. Nat Geosci 1:636

    Article  CAS  Google Scholar 

  4. R. Schlogl, Ammonia Synthesis in: "Handbook of Heterogeneous Catalysis", Department of Inorganic Chemistry, Fritz-Haber-Institute of the MPG, Germany (1991)

  5. Carreon ML (2019) Plasma catalytic ammonia synthesis: state of the art and future directions. J Phys D 52:483001

    Article  CAS  Google Scholar 

  6. Rouwenhorst KHR, Mani S, Lefferts L (2022) Improving the energy yield of plasma-based ammonia synthesis with in situ adsorption. ACS Sustain Chem Eng 10:1994–2000

    Article  CAS  Google Scholar 

  7. Wang Y, Yang W, Xu S, Zhao S, Chen G, Weidenkaff A, Hardacre C, Fan X, Huang J, Tu X (2022) Shielding protection by mesoporous catalysts for improving plasma-catalytic ambient ammonia synthesis. J Am Chem Soc 144:12020–12031

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  8. Chen Z, Jaiswal S, Diallo A, Sundaresan S, Koel BE (2022) Effect of porous catalyst support on plasma-assisted catalysis for ammonia synthesis. J Phys Chem A 126:8741–8752

    Article  PubMed  CAS  Google Scholar 

  9. Neyts EC, Ostrikov K, Sunkara MK, Bogaerts A (2015) Plasma catalysis: synergistic effects at the nanoscale. Chem Rev 115:13408–13446

    Article  PubMed  CAS  Google Scholar 

  10. Mehta P, Barboun P, Herrera FA, Kim J, Rumbach P, Go DB, Hicks JC, Schneider WF (2018) Overcoming ammonia synthesis scaling relations with plasma-enabled catalysis. Nat Catal 1:269–275

    Article  Google Scholar 

  11. Barboun P, Mehta P, Herrera FA, Go DB, Schneider WF, Hicks JC (2019) Distinguishing plasma contributions to catalyst performance in plasma-assisted ammonia synthesis. ACS Sustain Chem Eng 7:8621–8630

    Article  CAS  Google Scholar 

  12. Van’t Veer K, Reniers F, Bogaerts (2020) Zero-dimensional modeling of unpacked and packed bed dielectric barrier discharges: the role of vibrational kinetics in ammonia synthesis. Plasma Sources Sci Technol 29:045020

    Article  Google Scholar 

  13. Herrera FA, Brown GH, Barboun P, Turan N, Mehta P, Schneider WF, Hicks JC, Go DB (2019) The impact of transition metal catalysts on macroscopic dielectric barrier discharge (DBD) characteristics in an ammonia synthesis plasma catalysis reactor. J Phys D 52:224002

    Article  CAS  Google Scholar 

  14. Hong J, Steven P, Anthony B, Murphy (2018) Plasma catalysis as an alternative route for ammonia production: status, mechanisms, and prospects for progress. ACS Sustain Chem Eng 6:15–31

    Article  CAS  Google Scholar 

  15. Hong J, Prawer S, Murphy AB (2014) Production of ammonia by heterogeneous catalysis in a packed-bed dielectric-barrier discharge: influence of argon addition and voltage. IEEE Plasma Sci 42:2338–2339

    Article  Google Scholar 

  16. Patil BS, Van Kaathoven ASR, Peeters FJJ, Cherkasov N, Lang J, Wang Q, Hessel V (2020) Deciphering the synergy between plasma and catalyst support for ammonia synthesis in a packed dielectric barrier discharge reactor. J Phys D 53:144003

    Article  CAS  Google Scholar 

  17. Peng P, Li Y, Cheng Y, Deng S, Chen P, Ruan R (2016) Atmospheric pressure ammonia synthesis using non-thermal plasma assisted catalysis. Plasma Chem Plasma Process 36:1201–1210

    Article  CAS  Google Scholar 

  18. Akay G, Zhang K (2017) Process intensification in ammonia synthesis using novel coassembled supported microporous catalysts promoted by nonthermal plasma. Ind Eng Chem Res 56:457–468

    Article  CAS  Google Scholar 

  19. Shah J, Wu T, Lucero J, Carreon MA, Carreon ML (2018) Nonthermal plasma synthesis of ammonia over Ni-MOF-74. ACS Sustain Chem Eng 7:377–383

    Article  Google Scholar 

  20. Gorky F, Lucero JM, Crawford JM, Blake B, Carreon MA, Carreon ML (2021) Plasma-induced catalytic conversion of nitrogen and hydrogen to ammonia over zeolitic imidazolate frameworks ZIF-8 and ZIF-67. ACS Appl Mater Interfaces 13:21338–21348

    Article  PubMed  CAS  Google Scholar 

  21. Kruszelnicki J, Engeling KW, Foster JE, Kushner MJ (2020) Interactions between atmospheric pressure plasmas and metallic catalyst particles in packed bed reactors. J Phys D Appl Phys 54:104001

    Article  Google Scholar 

  22. Shah JR, Gorky F, Lucero J, Carreon MA, Carreon ML (2020) Ammonia synthesis via atmospheric plasma catalysis: zeolite 5A, a case of study. Ind Eng Chem Res 59:5167–5176

    Article  CAS  Google Scholar 

  23. Gorky F, Carreon MA, Carreon ML (2020) Experimental strategies to increase ammonia yield in plasma catalysis over LTA and BEA zeolites. IOP SciNotes 1:024801

    Article  Google Scholar 

  24. Xie Z, Zhu M, Nambo A, Jasinski JB, Carreon MA (2013) Microwave-assisted synthesized SAPO-56 as a catalyst in the conversion of CO2 to cyclic carbonates. Dalton Trans 42:6732–6735

    Article  PubMed  CAS  Google Scholar 

  25. J.L. Falconer, M.A. Carreon, S. Li, R.D. Noble, Synthesis of zeolites and zeolite membranes using multiple structure directing agents, in, U.S. Patents, US 8,302,782 B2, 2012.

  26. Gorky F, Nambo A, Carreon ML (2021) Cold plasma-metal organic framework MOF-177 breathable system for atmospheric remediation. J CO2 Utilization 51:101642

    Article  CAS  Google Scholar 

  27. Gorky F, Nguyen HM, Krishnan K, Lucero JM, Carreon ML, Carreon MA (2023) Plasma-induced desorption of methane and carbon dioxide over silico alumino phosphate zeolites. ACS Appl Energy Mater 6:4380–4389

    Article  CAS  Google Scholar 

  28. Wilson ST, Broach RW, Blackwell CS, Bateman CA, McGuire NK, Kirchner RM (1999) Synthesis, characterization and structure of SAPO-56, a member of the ABC double-six-ring family of materials with stacking sequence AABBCCBB. Microporous Mesoporous Mater 28:125–137

    Article  CAS  Google Scholar 

  29. Wu T, Feng X, Carreon ML, Carreon MA (2017) Synthesis of SAPO-56 with controlled crystal size. J Nanopart Res 19:1–8

    Article  Google Scholar 

  30. Gorky F, Best A, Jasinski J, Allen BJ, Alba-Rubio AC, Carreon ML (2020) Plasma catalytic ammonia synthesis on Ni nanoparticles: the size effect. J Catal 393:369–380

    Article  Google Scholar 

  31. Wang Y, Craven M, Yu X, Ding J, Bryant P, Huang J, Tu X (2019) Plasma-enhanced catalytic synthesis of ammonia over a Ni/Al2O3 catalyst at near-room temperature: insights into the importance of the catalyst surface on the reaction mechanism. ACS Catal 9:10780–10793

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  32. Li G, Foo C, Yi X, Chen W, Zhao P, Gao P, Yoskamtorn T, Xiao Y, Day S, Tang CC (2021) Induced active sites by adsorbate in zeotype materials. J Am Chem Soc 143:8761–8771

    Article  PubMed  CAS  Google Scholar 

  33. Li Y, Su X, Maximov AL, Bai X, Wang Y, Wang W, Kolesnichenko NV, Bukina ZM, Wu W (2020) Highly selective MTO reaction over a nanosized ZSM-5 zeolite modified by Fe via the low-temperature dielectric barrier discharge plasma method. Russ J Appl Chem 93:137–148

    Article  CAS  Google Scholar 

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Acknowledgements

Maria L. Carreon acknowledges the Department of Energy Office of Science DE-SC0023261, NSF-CBET award No.1947303, and NSF-CAREER award No. 2235247. The authors want to express their gratitude to the late Dr. Moises A. Carreon, an expert on zeolites, without whom this project would never have been possible.   

Funding

Department of Energy Office of Science DE-SC0023261, NSF-CBET award No. 2203166, and NSF-CAREER award No. 2235247.

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Authors and Affiliations

  1. Mechanical Engineering Department, University of Massachusetts Lowell, 1 University Avenue, Lowell, MA, 01854, USA

    Fnu Gorky & Maria L. Carreon

  2. Bert Thin Films, LLC, 625 Myrtle St, Louisville, KY, 40298, USA

    Apolo Nambo

  3. Chemical and Biological Engineering Department, Colorado School of Mines, 1613 Illinois Street, Golden, CO, 8040, USA

    Moises A. Carreon

Authors
  1. Fnu Gorky
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  2. Apolo Nambo
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  3. Moises A. Carreon
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  4. Maria L. Carreon
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Contributions

FG: Performed ammonia synthesis experiments; Formal Analysis, Methodology, Reviewing and Editing; AN: XRD characterization of zeolites; results analysis, writing and editing; MAC: synthesis and characterization of zeolites; MLC: Project conceptualization, supervision, funding acquisition, project administration, reviewing and editing.

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Correspondence to Maria L. Carreon.

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All experiments in this study were carried out in adherence to ethical standards, and no ethical concerns were encountered during the course of the experiments or preparation of this manuscript.

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Gorky, F., Nambo, A., Carreon, M.A. et al. Plasma Catalytic Conversion of Nitrogen and Hydrogen to Ammonia Over Silico Alumino Phosphate (SAPO) Zeolites. Plasma Chem Plasma Process (2023). https://doi.org/10.1007/s11090-023-10397-w

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