Formation of Nitrogen Oxides by Nanosecond Pulsed Plasma Discharges in Gas–Liquid Reactors

  • Robert J. WandellEmail author
  • Huihui Wang
  • Radha K. M. Bulusu
  • Rachel O. Gallan
  • Bruce R. Locke
Original Paper


A gas–liquid-film flow reactor with a nanosecond pulsed power supply was utilized to produce nitrogen oxides from Ar/N2 mixtures (gas phase) and deionized water (liquid phase). Chemical analysis of the stable products found in both the gas and liquid phases was performed and chemical quenching was incorporated for the liquid phase samples in order to eliminate post plasma reactions. Significant amounts of NO and NO2 in the gas phase and \({\text{NO}}_{2}^{ - }\) and \({\text{NO}}_{3}^{ - }\) in the liquid phase were determined using FTIR spectroscopy and ion chromatography, respectively. The production rate of all nitrogen oxides produced increased significantly with N2 concentration while H2O2 formation decreased slightly. The gas temperature of the plasma was approximately 525 K and was unaffected by N2 concentration while the electron density ranged from 1 × 1017 cm−3 in pure Ar to 5.5 × 1017 cm−3 in 28% N2. The role of the \({\cdot {\text{OH}}}\) in the reaction pathway was assessed by adding CO as a gas phase radical scavenger showing that \({\cdot {\text{OH}}}\) is essential for conversion of the gas phase NO and NO2 into water soluble \({\text{NO}}_{2}^{ - }\) and \({\text{NO}}_{3}^{ - }\). Conversely, atomic oxygen originating from water is likely responsible for NO and NO2 generation. Experiments with N2/O2/Ar mixtures and air showed a significant increase in NO2 production caused by the additional generation of reactive oxygen species. An overall energy yield for all nitrogen oxides produced in the most efficient case was 50 eV/molecule.


Non-thermal plasma Nitrogen fixation Plasma activated water Nanosecond discharge Nitrogen oxides 



This work was supported by the National Science Foundation (CBET 1702166) and Florida State University.


  1. 1.
    Fridman AA (2008) Plasma chemistry. Cambridge University Press, CambridgeGoogle Scholar
  2. 2.
    Locke BR, Lukes P, Brisset JL (2012) Elementary chemical and physical phenomena in electrical discharge plasma in gas–liquid environments and in liquids. In: Parvulescu MMVI, Lukes P (eds) Plasma chemistry and catalysis in gases and liquids. Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimGoogle Scholar
  3. 3.
    Lukes P, Locke BR, Brisset JL (2012) Aqueous-phase chemistry of electrical discharge plasma in water and in gas-liquid environments. In: Parvulescu MMVI, Lukes P (eds) Plasma chemistry and catalysis in gases and liquids. Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimGoogle Scholar
  4. 4.
    Patil B, Wang Q, Hessel V, Lang J (2015) Plasma N2-fixation: 1900–2014. Catal Today 256:49–66Google Scholar
  5. 5.
    Itikawa Y (2009) Cross sections for electron collisions with oxygen molecules. J Phys Chem Ref Data 38(1):1–20Google Scholar
  6. 6.
    Polak LS, Slovetsky DI, Todesaite RD (1975) Sov Phys High Energy Chem 9:142Google Scholar
  7. 7.
    Azizov RI, Zhivotov VK, Krotov MF, Rusanov VD, Tarasov YV, Fridman AA, Sholin GV (1980) Synthesis of nitrogen oxides in a nonequilibrium UHF discharge under electron cyclotron resonance conditions. Sov Phys High Energy Chem 14(4):275–277Google Scholar
  8. 8.
    Mizuno A, Shimizu K, Chakrabarti A, Dascalescu L, Furuta S (1995) NOx removal process using pulsed discharge plasma. IEEE Trans Ind Appl 31(5):957–963Google Scholar
  9. 9.
    van Veldhuizen EM, Rutgers WR, Bityurin VA (1996) Energy efficiency of NO removal by pulsed corona discharges. Plasma Chem Plasma Proc 16(2):227–247Google Scholar
  10. 10.
    Yamamoto T, Yang CL, Beltran MR, Kravets Z (2000) Plasma-assisted chemical process for NOx control. IEEE Trans Ind Appl 36(3):923–927Google Scholar
  11. 11.
    Wang ZH, Li B, Ehn A, Sun ZW, Li ZS, Bood J, Alden M, Cen KF (2010) Investigation of flue-gas treatment with O3 injection using NO and NO2 planar laser-induced fluorescence. Fuel 89(9):2346–2352Google Scholar
  12. 12.
    Huang LW, Matsuda H (2004) Removal of NO by a pulsed-corona reactor combined with in situ absorption. AIChE J 50(11):2676–2681Google Scholar
  13. 13.
    Lin H, Gao X, Luo ZY, Cen KF, Pei MX, Huang Z (2004) Removal of NOx from wet flue gas by corona discharge. Fuel 83(9):1251–1255Google Scholar
  14. 14.
    Mok YS (2006) Absorption-reduction technique assisted by ozone injection and sodium sulfide for NOx removal from exhaust gas. Chem Eng J 118(1–2):63–67Google Scholar
  15. 15.
    Wang ZH, Zhou JH, Fan JR, Cen KF (2006) Direct numerical simulation of ozone injection technology for NOx control in flue gas. Energy Fuels 20(6):2432–2438Google Scholar
  16. 16.
    Mok YS, Kim JH, Nam IS, Ham SW (2000) Removal of NO and formation of byproducts in a positive-pulsed corona discharge reactor. Ind Eng Chem Res 39(10):3938–3944Google Scholar
  17. 17.
    Hu XD, Zhao GB, Legowski SF, Radosz M (2005) Moisture effect on NOx conversion in a nonthermal plasma reactor. Environ Eng Sci 22(6):854–869Google Scholar
  18. 18.
    Yin SE, Sun BM, Gao XD, Xiao HP (2009) The effect of oxygen and water vapor on nitric oxide conversion with a dielectric barrier discharge reactor. Plasma Chem Plasma Process 29(6):421–431Google Scholar
  19. 19.
    Morgan MM, Cuddy MF, Fisher ER (2010) Gas-phase chemistry in inductively coupled plasmas for NO removal from mixed gas systems. J Phys Chem A 114(4):1722–1733Google Scholar
  20. 20.
    Yan K, Kanazawa S, Ohkubo T, Nomoto Y (1999) Oxidation and reduction processes during NOx removal with corona-induced nonthermal plasma. Plasma Chem Plasma Process 19(3):421–443Google Scholar
  21. 21.
    Li D, Xiao Z, Aftab TB, Xu S (2018) Flue gas denitration by wet oxidation absorption methods: current status and development. Environ Eng Sci 35(11):1151–1164Google Scholar
  22. 22.
    Jogi I, Erme K, Levoll E, Raud J, Stamate E (2018) Plasma and catalyst for the oxidation of NOx. Plasma Sources Sci Technol 27(3):035001Google Scholar
  23. 23.
    Talebizadeh P, Babaie M, Brown R, Rahimzadeh H, Ristovski Z, Arai M (2014) The role of non-thermal plasma technique in NOx treatment: a review. Renew Sustain Energy Rev 40:886–901Google Scholar
  24. 24.
    Kim HH (2004) Nonthermal plasma processing for air-pollution control: a historical review, current issues, and future prospects. Plasma Process Polym 1(2):91–110Google Scholar
  25. 25.
    Beckers F, Hoeben W, Pemen AJM, van Heesch EJM (2013) Low-level NOx removal in ambient air by pulsed corona technology. J Phys D Appl Phys 46(29):6Google Scholar
  26. 26.
    Zhao GB, Garikipati SVB, Hu XD, Argyle MD, Radosz M (2005) Effect of oxygen on nonthermal plasma reactions of nitrogen oxides in nitrogen. AIChE J 51(6):1800–1812Google Scholar
  27. 27.
    Sathiamoorthy G, Kalyana S, Finney WC, Clark RJ, Locke BR (1999) Chemical reaction kinetics and reactor modeling of NOx removal in a pulsed streamer corona discharge reactor. Ind Eng Chem Res 38:1844–1855Google Scholar
  28. 28.
    Huiskamp T, Hoeben W, Beckers F, van Heesch EJM, Pemen AJM (2017) (Sub)nanosecond transient plasma for atmospheric plasma processing experiments: application to ozone generation and NO removal. J Phys D Appl Phys 50(40):16Google Scholar
  29. 29.
    Chirumamilla VR, Hoeben W, Beckers F, Huiskamp T, Van Heesch EJM, Pemen AJM (2016) Experimental investigation on the effect of a microsecond pulse and a nanosecond pulse on NO removal using a pulsed DBD with catalytic materials. Plasma Chem Plasma Process 36(2):487–510Google Scholar
  30. 30.
    Matsumoto T, Wang DY, Namihira T, Akiyama H (2010) Energy efficiency improvement of nitric oxide treatment using nanosecond pulsed discharge. IEEE Trans Plasma Sci 38(10):2639–2643Google Scholar
  31. 31.
    Matsumoto T, Wang D, Namihira T, Akiyama H (2011) Process performances of 2 ns pulsed discharge plasma. Jpn J Appl Phys. Google Scholar
  32. 32.
    Itikawa Y, Mason N (2005) Cross sections for electron collisions with water molecules. J Phys Chem Ref Data 34(1):1–22Google Scholar
  33. 33.
    Brisset JL, Doubla A, Amouroux J, Goldman M, Goldman A (1989) Acid-base character of species created in a point-to-plane corona discharge. 1. Acid effect of the active changeless species. Revue Internationale Des Hautes Temperatures Et Des Refractaires 25(4):229–236Google Scholar
  34. 34.
    Brisset JL, Lelievre J, Doubla A, Amouroux J (1990) Interactions with aqueous solutions of the air corona products. Revue de Physique Appliquee 25:535–543Google Scholar
  35. 35.
    Lelievre J, Dubreuil N, Brisset JL (1995) Electrolysis processes in D.C. corona discharges in humid air. J Phys III France 5:447–457Google Scholar
  36. 36.
    Benstaali B, Boubert P, Cheron BG, Addou A, Brisset JL (2002) Density and rotational temperature measurements of the OH and NO radicals produced by a gliding arc in humid air. Plasma Chem Plasma Process 22(4):553–571Google Scholar
  37. 37.
    Brisset JL, Hnatiuc E (2012) Peroxynitrite: a re-examination of the chemical properties of non-thermal discharges burning in air over aqueous solutions. Plasma Chem Plasma Process 32(4):655–674Google Scholar
  38. 38.
    Daito S, Tochikubo F, Watanabe T (2000) Improvement of NOx removal efficiency assisted by aqueous-phase reaction in corona discharge. Jpn J Appl Phys Pt 1 39(8):4914–4919Google Scholar
  39. 39.
    Xie DY, Sun Y, Zhu TL, Ding L (2016) Removal of NO in mist by the combination of plasma oxidation and chemical absorption. Energy Fuels 30(6):5071–5076Google Scholar
  40. 40.
    Takehana K, Kuroki T, Okubo M (2018) Evaluation on nitrogen oxides and nanoparticle removal and nitrogen monoxide generation using a wet-type nonthermal plasma reactor. J Phys D Appl Phys 51(20):11Google Scholar
  41. 41.
    Burlica R, Locke BR (2008) Pulsed plasma gliding arc discharges with water spray. IEEE Trans Ind Appl 44(2):482–489Google Scholar
  42. 42.
    Burlica R, Shih KY, Locke BR (2010) Formation of H2 and H2O2 in a water-spray gliding arc nonthermal plasma reactor. Ind Eng Chem Res 49(14):6342–6349Google Scholar
  43. 43.
    Wandell R, Locke B (2014) Low power pulsed plasma discharge in a water film reactor. IEEE Trans Plasma Sci in pressGoogle Scholar
  44. 44.
    Burlica R, Kirkpatrick M, Locke B (2006) Formation of reactive species in gliding arc discharges with liquid water. J Electrostat 64(1):35–43Google Scholar
  45. 45.
    Seinfeld JH, Pandis SN (1998) Atmospheric chemistry and physics. Wiley, New YorkGoogle Scholar
  46. 46.
    Malik MA (2016) Nitric oxide production by high voltage electrical discharges for medical uses: a review. Plasma Chem Plasma Process 36(3):737–766Google Scholar
  47. 47.
    Patil BS, Peeters FJJ, van Rooij GJ, Medrano JA, Gallucci F, Lang J, Wang Q, Hessel V (2018) Plasma assisted nitrogen oxide production from air: using pulsed powered gliding arc reactor for a containerized plant. AIChE J 64(2):526–537Google Scholar
  48. 48.
    Thirumdas R, Kothakota A, Annapure U, Siliveru K, Blundell R, Gatt R, Valdramidis VP (2018) Plasma activated water (PAW): chemistry, physico-chemical properties, applications in food and agriculture. Trends Food Sci Technol 77:21–31Google Scholar
  49. 49.
    Jablonowski H, von Woedtke T (2015) Research on plasma medicine-relevant plasma-liquid interaction: What happened in the past five years? Clin Plasma Med 3(2):42–52Google Scholar
  50. 50.
    Cherkasov N, Ibhadon AO, Fitzpatrick P (2015) A review of the existing and alternative methods for greener nitrogen fixation. Chem Eng Process 90:24–33Google Scholar
  51. 51.
    He Y, Chen ZW, Li Z, Niu GD, Tang J (2018) Non-thermal plasma fixing of nitrogen into nitrate: solution for renewable electricity storage? Front Optoelectron 11(1):92–96Google Scholar
  52. 52.
    Wang WZ, Patil B, Heijkers S, Hessel V, Bogaerts A (2017) Nitrogen fixation by gliding arc plasma: better insight by chemical kinetics modelling. Chemsuschem 10(10):2145–2157Google Scholar
  53. 53.
    Liu ZC, Liu DX, Chen C, Li D, Yang AJ, Rong MZ, Chen HL, Kong MG (2015) Physicochemical processes in the indirect interaction between surface air plasma and deionized water. J Phys D Appl Phys 48(49):20Google Scholar
  54. 54.
    Liu DX, Liu ZC, Chen C, Yang AJ, Li D, Rong MZ, Chen HL, Kong MG (2016) Aqueous reactive species induced by a surface air discharge: heterogeneous mass transfer and liquid chemistry pathways. Sci Rep. Google Scholar
  55. 55.
    Liu ZC, Liu DX, Chen C, Liu ZJ, Yang AJ, Rong MZ, Chen HL, Kong MG (2018) Post-discharge evolution of reactive species in the water activated by a surface air plasma: a modeling study. J Phys D Appl Phys 51(17):12Google Scholar
  56. 56.
    Brisset JL, Moussa D, Doubla A, Hnatiuc E, Hnatiuc B, Youbi GK, Herry JM, Naitali M, Bellon-Fontaine MN (2008) Chemical reactivity of discharges and temporal post-discharges in plasma treatment of aqueous media: examples of gliding discharge treated solutions. Ind Eng Chem Res 47(16):5761–5781Google Scholar
  57. 57.
    Brisset JL, Pawlat J (2016) Chemical effects of air plasma species on aqueous solutes in direct and delayed exposure modes: discharge, post-discharge and plasma activated water. Plasma Chem Plasma Process 36(2):355–381Google Scholar
  58. 58.
    Lukes P, Dolezalova E, Sisrova I, Clupek M (2014) Aqueous-phase chemistry and bactericidal effects from an air discharge plasma in contact with water: evidence for the formation of peroxynitrite through a pseudo-second-order post-discharge reaction of H2O2 and HNO2. Plasma Sources Sci Technol 23(1):15Google Scholar
  59. 59.
    Su ZZ, Ito K, Takashima K, Katsura S, Onda K, Mizuno A (2002) OH radical generation by atmospheric pressure pulsed discharge plasma and its quantitative analysis by monitoring CO oxidation. J Phys D Appl Phys 35:3192–3198Google Scholar
  60. 60.
    Wandell RJ, Wang HH, Tachibana K, Makled B, Locke BR (2018) Nanosecond pulsed plasma discharge over a flowing water film: characterization of hydrodynamics, electrical, and plasma properties and their effect on hydrogen peroxide generation. Plasma Process Polym. Google Scholar
  61. 61.
    Eisenberg GM (1943) Colorimetric determination of hydrogen peroxide. Ind Eng Chem Anal Ed 15(5):327–328Google Scholar
  62. 62.
    Wang HH, Wandell RJ, Locke BR (2018) The influence of carrier gas on plasma properties and hydrogen peroxide production in a nanosecond pulsed plasma discharge generated in a water-film plasma reactor. J Phys D Appl Phys 51(9):13Google Scholar
  63. 63.
    Wang H, Wandell R, Tachibana K, Vorac J, Locke B (2018) The Influence of liquid conductivity on electrical breakdown and hydrogen peroxide production in a nanosecond pulsed plasma discharge generated in a water-film plasma reactor. J Phys D Appl Phys. Google Scholar
  64. 64.
    Vorac J, Synek P, Potocnakova L, Hnilica J, Kudrle V (2017) Batch processing of overlapping molecular spectra as a tool for spatio-temporal diagnostics of power modulated microwave plasma jet. Plasma Sources Sci Technol 26(2):12Google Scholar
  65. 65.
    Voráč J, Synek P, Procházka V, Hoder T (2017) State-by-state emission spectra fitting for non-equilibrium plasmas: OH spectra of surface barrier discharge at argon/water interface. arXiv preprint arXiv:1703.09978
  66. 66.
    Nikiforov AY, Leys C, Gonzalez MA, Walsh JL (2015) Electron density measurement in atmospheric pressure plasma jets: stark broadening of hydrogenated and non-hydrogenated lines. Plasma Sources Sci Technol 24(3):18Google Scholar
  67. 67.
    Zhu XM, Walsh JL, Chen WC, Pu YK (2012) Measurement of the temporal evolution of electron density in a nanosecond pulsed argon microplasma: using both Stark broadening and an OES line-ratio method. J Phys D Appl Phys 45(29):11Google Scholar
  68. 68.
    Lieberman M, Lichtenberg A (2005) Principles of plasma discharge and materials processing, 2nd edn. John Wiley & Sons, HobokenGoogle Scholar
  69. 69.
    Hagelaar GJM, Pitchford LC (2005) Solving the Boltzmann equation to obtain electron transport coefficients and rate coefficients for fluid models. Plasma Sources Sci Technol 14(4):722–733Google Scholar
  70. 70.
    Janda M, Martišovitš V, Hensel K, Machala Z (2016) Study of transient spark discharge focused at NOx generation for biomedical applications. J Phys Conf Ser 768(1):012009Google Scholar
  71. 71.
    Janda M, Martisovits V, Hensel K, Machala Z (2016) Generation of antimicrobial NOx by atmospheric air transient spark discharge. Plasma Chem Plasma Process 36(3):767–781Google Scholar
  72. 72.
    Janda M, Hensel K, Machala Z (2018) Kinetic plasma chemistry model of pulsed transient spark discharge in air coupled with nanosecond time-resolved imaging and spectroscopy. J Phys D Appl Phys 51(33):10Google Scholar
  73. 73.
    Tarabova B, Lukes P, Janda M, Hensel K, Sikurova L, Machala Z (2018) Specificity of detection methods of nitrites and ozone in aqueous solutions activated by air plasma. Plasma Process Polym 15(6):12Google Scholar
  74. 74.
    Locke BR, Shih KY (2011) Review of the methods to form hydrogen peroxide in electrical discharge plasma with liquid water. Plasma Sources Sci Technol 20(3):15Google Scholar
  75. 75.
    Locke BR, Thagard SM (2012) Analysis and review of chemical reactions and transport processes in pulsed electrical discharge plasma formed directly in liquid water. Plasma Chem Plasma Process 32(5):875–917Google Scholar
  76. 76.
    Mededovic S, Locke BR (2007) Primary chemical reactions in pulsed electrical discharge channels in water. J Phys D Appl Phys 40(24):7734–7746Google Scholar
  77. 77.
    Hofmann S, van Gessel AFH, Verreycken T, Bruggeman P (2011) Power dissipation, gas temperatures and electron densities of cold atmospheric pressure helium and argon RF plasma jets. Plasma Sources Sci Technol 20(6):12Google Scholar
  78. 78.
    Hsieh KC, Wandell RJ, Bresch S, Locke BR (2017) Analysis of hydroxyl radical formation in a gas-liquid electrical discharge plasma reactor utilizing liquid and gaseous radical scavengers. Plasma Process Polym 14(8):14Google Scholar
  79. 79.
    Lindsay A, Byrns B, King W, Andhvarapou A, Fields J, Knappe D, Fonteno W, Shannon S (2014) Fertilization of radishes, tomatoes, and marigolds using a large-volume atmospheric glow discharge. Plasma Chem Plasma Process 34(6):1271–1290Google Scholar
  80. 80.
    Bian WJ, Song XH, Shi JW, Yin XL (2012) Nitrogen fixed into HNO3 by pulsed high voltage discharge. J Electrostat 70(3):317–326Google Scholar
  81. 81.
    Hessel V, Anastasopoulou A, Wang Q, Kolb G, Lang J (2013) Energy, catalyst and reactor considerations for (near)-industrial plasma processing and learning for nitrogen-fixation reactions. Catal Today 211:9–28Google Scholar
  82. 82.
    van Ham BTJ, Hofmann S, Brandenburg R, Bruggeman PJ (2014) In situ absolute air, O3 and NO densities in the effluent of a cold RF argon atmospheric pressure plasma jet obtained by molecular beam mass spectrometry. J Phys D Appl Phys 47(22):9Google Scholar
  83. 83.
    Park DP, Davis K, Gilani S, Alonzo CA, Dobrynin D, Friedman G, Fridman A, Rabinovich A, Fridman G (2013) Reactive nitrogen species produced in water by non-equilibrium plasma increase plant growth rate and nutritional yield. Curr Appl Phys 13:S19–S29Google Scholar
  84. 84.
    Su ZZ, Ito K, Takashima K, Katsura S, Onda K, Mizuno A (2002) OH radical generation by atmospheric pressure pulsed discharge plasma and its quantitative analysis by monitoring CO oxidation. J Phys D Appl Phys 35(24):3192–3198Google Scholar
  85. 85.
    Tang XL, Wang JG, Yi HH, Zhao SZ, Gao FY, Chu C (2018) Nitrogen fixation and NO conversion using dielectric barrier discharge reactor: identification and evolution of products. Plasma Chem Plasma Process 38(3):485–501Google Scholar
  86. 86.
    Pavlovich MJ, Ono T, Galleher C, Curtis B, Clark DS, Machala Z, Graves DB (2014) Air spark-like plasma source for antimicrobial NOx generation. J Phys D Appl Phys 47(50):10Google Scholar
  87. 87.
    Wandell RJ, Bresch S, Hsieh K, Alabugin IV, Locke BR (2014) Formation of alcohols and carbonyl compounds from hexane and cyclohexane with water in a liquid film plasma reactor. IEEE Trans Plasma Sci 42(5):1195–1205Google Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Robert J. Wandell
    • 1
    Email author
  • Huihui Wang
    • 1
  • Radha K. M. Bulusu
    • 1
  • Rachel O. Gallan
    • 1
  • Bruce R. Locke
    • 1
  1. 1.Department of Chemical and Biomedical Engineering, FAMU-FSU College of EngineeringFlorida State UniversityTallahasseeUSA

Personalised recommendations