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Perspectives on Plasmas in Contact with Liquids for Chemical Processing and Materials Synthesis

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Abstract

Plasmas and gas discharges in contact with liquids have played an important role in the history of chemical processing and scientific inquiry, leading to the discoveries of elements such as argon and compounds such as ozone. Recently-developed atmospheric-pressure plasma sources have renewed the study of plasma–liquid systems with applications in chemical processing, materials synthesis, and chemical analysis. In many cases, these approaches utilize glow discharge electrolysis configurations where a DC plasma replaces one of the metal electrodes in a standard electrolytic cell. These configurations have been used to great effect for the synthesis of various nanomaterials and more recently, in the processing of carbon dioxide. In this work, we overview recent developments using plasmas as electrodes in electrolytic cells for chemical processing, drawing parallels to conventional electrochemistry and electrocatalysis. In particular, we highlight recent studies on the fundamental chemical processes at the plasma–liquid interface, including new interfacial measurement techniques used to probe charge transfer. We conclude with an overview of opportunities for these configurations in the future and highlight the need for further fundamental study.

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Fig. 1
Fig. 2

Courtesy of R. Mohan Sankaran, Case Western Reserve University

Fig. 3
Fig. 4

Adapted with permission from [51]. Copyright (2011) American Chemical Society

Fig. 5

Copyright 2014 IEEE. Adapted, with permission, from [54]

Fig. 6

Reprinted with permission from [55]. Copyright 2013 American Chemical Society

Fig. 7

Used with permission from [56]

Fig. 8

Used with permission from [60]

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References

  1. Qiao J, Liu Y, Hong F, Zhang J (2014) A review of catalysts for the electro reduction of carbon dioxide to produce low-carbon fuels. Chem Soc Rev 43:631

    Article  CAS  Google Scholar 

  2. Ni M, MKH Leung, DYC Leung, Sumathy K (2007) A review and recent developments in photocatalytic water-splitting using TiO2 for hydrogen production. Renew Sustain Energy Rev 11:401

    Article  CAS  Google Scholar 

  3. Liu H, Song C, Zhang L, Zhang J, Wang H, Wilkinson DP (2006) A review of anode catalysis in the direct methanol fuel cell. J Power Sources 155:95

    Article  CAS  Google Scholar 

  4. SKS Gupta (2015) Contact glow discharge electrolysis: its origin, plasma diagnostics and non-faradaic chemical effects. Plasma Sources Sci Technol 24:063001

    Article  Google Scholar 

  5. Cavendish H (1784) Experiments on air. Phil Trans Royal Soc London 75:372

    Article  Google Scholar 

  6. Rayleigh L, Ramsay W (1895) Argon, a new constituent of the atmosphere. Proc Roy Soc London 57:265

    Article  Google Scholar 

  7. Schönbein CF (1840) Beobachtungen über den bei der Elektrolysation des Wassers und dem Ausströmen der gewöhnliehen Elektricität aus Spitzen sich entwikkelnden Geruch. Ann Phys 126:616

    Article  Google Scholar 

  8. Birkeland KR (1889) On the oxidation of atmospheric nitrogen in electric arcs. Nature 58:98

    Google Scholar 

  9. Gubkin J (1887) Electrolytische Metallabscheidung an der freien Oberfläche einer Salzlösung. Ann Phys Chem 32:114

    Article  Google Scholar 

  10. Klemenc A (1927) Zur Kenntnis der elektrolytischen Reduktion und der Reaktionen im Glimmbogen an der Phasengrenze Flüssigkeit-Gas. Z Physik Chem A 130:378

    CAS  Google Scholar 

  11. Bruggeman P, Leys C (2009) Non-thermal plasmas in and in contact with liquids. J Phys D 42:053001

    Article  Google Scholar 

  12. Mariotti D, Sankaran RM (2010) Microplasmas for nanomaterials synthesis. J Phys D 43:323001

    Article  Google Scholar 

  13. Hickling A (1971) Electrochemical processes in glow discharge at the gas-solution interface. In: Bockris JO’M, Conway BE (eds) Modern aspects of electrochemistry, vol 6. Springer, New York, pp 329–373

    Google Scholar 

  14. Denaro AR, Hickling A (1958) Glow-discharge electrolysis in aqueous solutions. J Electrochem Soc 105:265

    Article  CAS  Google Scholar 

  15. Cserfalvi T, Mezei P, Apai P (1993) Emission studies on a glow discharge in atmospheric pressure air using water as a cathode. J Phys D 26:2184

    Article  CAS  Google Scholar 

  16. Mezei P, Cserfalvi T (2007) Electrolyte cathode atmospheric glow discharges for direct solution analysis. Appl Spectrosc Rev 42:573

    Article  CAS  Google Scholar 

  17. Webb MR, Hieftje GM (2009) Spectrochemical analysis by using discharge devices with solution electrodes. Anal Chem 81:862

    Article  CAS  Google Scholar 

  18. Jamorz P, Greda K, Pohl P (2012) Development of direct-current, atmospheric-pressure, glow discharges generated in contact with flowing electrolyte solutions for elemental analysis by optical emission spectrometry. Trends Anal Chem 41:105

    Article  Google Scholar 

  19. Schwarz AJ, Ray SJ, Hieftje GM (2015) Automatable on-line generation of calibration curves and standard additions in solution-cathode glow discharge optical emission spectrometry. Spectrochim Acta Part B 105:77–83

    Article  Google Scholar 

  20. Richmonds C, Sankaran RM (2008) Plasma-solution electrochemistry: rapid synthesis of colloidal metal NPs by microplasma reduction of aqueous cations. Appl Phys Lett 93:131501

    Article  Google Scholar 

  21. Chen Q, Kaneko T, Hatakeyama R (2012) Reductants in gold nanoparticle synthesis using gas–liquid interfacial discharge plasmas. Appl Phys Express 5:086201

    Article  Google Scholar 

  22. Patel J, Nemcova L, Maguire P, Graham WG, Mariotti D (2013) Synthesis of surfactant-free electrostatically stabilized gold nanoparticles by plasma-inducted liquid chemistry. Nanotechnology 24:245604

    Article  CAS  Google Scholar 

  23. Shirai N, Uchida S, Tochikubo F (2014) Synthesis of metal nanoparticles by dual plasma electrolysis using atmospheric dc glow discharge in contact with liquid. Jpn J Appl Phys 53:046202

    Article  Google Scholar 

  24. Brettholle M, Hofft O, Klarhofer L, Mathes S, Maus-Friedrichs W, Zein El Abedin S, Krischok S, Janek J, Endres F (2010) Plasma electrochemistry in ionic liquids: deposition of copper nanoparticles. Phys Chem Chem Phys 12:1750–1755

    Article  CAS  Google Scholar 

  25. Kulbe N, Hofft O, Ulbrich A, Zein El Abedin S, Krischok S, Janek J, Polleth M, Endres F (2011) Plasma electrochemistry in 1-butyl-3-methylimidazolium dicyanamide: copper nanoparticle from CuCl and CuCl2. Plasma Processes Polym 8:32–37

    Article  CAS  Google Scholar 

  26. Hofft O, Endres F (2011) Plasma electrochemistry in ionic liquids: an alternative route to generate nanoparticles. Phys Chem Chem Phys 13:13472–13478

    Article  Google Scholar 

  27. Kaneko T, Baba K, Hatakeyama R (2009) Gas–liquid interfacial plasmas: basic properties and applications to nanomaterial synthesis. Plasma Phys Control Fusion 51:124011

    Article  Google Scholar 

  28. Lee SW, Janyasupab M, Liu C-C, Sankaran RM (2013) Fabrication of Ir nanoparticle-based biosensors by plasma electrochemical reduction for enzyme-free detection of hydrogen peroxide. Catal Today 211:137–142

    Article  CAS  Google Scholar 

  29. Endres F, Hofft O, von Brisinski NS (2014) Plasma electrochemistry in ionic liquids: from silver to silicon nanoparticles. J Mol Liq 192:59–66

    Article  Google Scholar 

  30. Ghosh S, Bishop B, Morrison I, Akolkar R, Scherson D, Sankaran RM (2015) Generation of a direct-current, atmospheric-pressure microplasma at the surface of a liquid water microjet for continuous plasma–liquid processing. J Vaccum Sci Technol A 33:021312

    Article  Google Scholar 

  31. Mariotti D, Švrček V, Hamilton JW, Schmidt M, Kondo M (2012) Silicon nanocrystals in liquid media: optical properties and surface stabilization by microplasma-induced non-equilibrium liquid chemistry. Adv Funct Mater 22:954–964

    Article  CAS  Google Scholar 

  32. McKenna J, Patel J, Mitra S, Soin N, Švrček V, Maguire P, Mariotti D (2011) Synthesis and surface engineering of nanomaterials by atmospheric-pressure microplasmas. Euro Phys J 56:24020

    Google Scholar 

  33. Chen Q, Li J, Li Y (2015) A review of plasma-liquid interactions for nanomaterial synthesis. J Phys D 48:424005

    Article  Google Scholar 

  34. Mezei P, Cserfalvi T (2012) A critical review of published data on the gas temperature and the electron density in the electrolyte cathode atmospheric glow discharges. Sensors 12:6576–6586

    Article  CAS  Google Scholar 

  35. Oehmigen K, Hähnel M, Brandenburg R, Wilke C, Weltmann K-D, von Woedtke T (2010) The role of acidification for antimicrobial activity of atmospheric pressure plasma in liquids. Plasma Process Polym 7:250

    Article  CAS  Google Scholar 

  36. CAJ van Gils, Hofmann S, BKHL Boekema, Brandenburg R, Bruggeman PJ (2013) Mechanisms of bacterial inactivation in the liquid phase induced by a remote RF cold atmospheric pressure plasma jet. J Phys D 46:175203

    Article  Google Scholar 

  37. Locke BR, Shih K-Y (2011) Review of the methods to form hydrogen peroxide in electrical discharge plasma with liquid water. Plasma Sources Sci Technol 20:034006

    Article  Google Scholar 

  38. Vasko CA, Liu DX, vanVeldhuizen EM, Iza F, Bruggeman PJ (2014) Hydrogen peroxide production in an atmospheric pressure RF glow discharge: comparison of models and experiments. Plasma Chem Plasma Process 34:1081–1099

    Article  CAS  Google Scholar 

  39. Graves DB (2012) The emerging role of reactive oxygen and nitrogen species in redox biology and some implications for plasma applications to medicine and biology. J Phys D 45:263001

    Article  Google Scholar 

  40. Norberg SA, Tian W, Johnsen E, Kushner MJ (2014) Atmospheric pressure plasma jets interacting with liquid covered tissue: touching and not-touching the liquid. J Phys D 47:475203

    Article  Google Scholar 

  41. 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 48:495201

    Article  Google Scholar 

  42. Liu DX, Liu ZC, Chen C, Yang AJ, Li D, Rong MZ, Chen HL, Shama G, Kong MG (2016) Aqueous reactive species induced by a surface air discharge: heterogeneous mass transfer and liquid chemistry pathways. Sci Rep 6:23737

    Article  CAS  Google Scholar 

  43. Lindsey AD, Graves DB, Shannon SC (2016) Fully coupled simulation of the plasma liquid interface and interfacial coefficient effects. J Phys D 49:235204

    Article  Google Scholar 

  44. Yusupov M, Neyts EC, Simon P, Berdiyorov G, Snoeckx R, ACT van Duin, Bogaerts A (2014) Reactive molecular dynamics simulations of oxygen species in a liquid water layer of interest for plasma medicine. J Phys D 47:025205

    Article  Google Scholar 

  45. T Cserfalvi, P Mezei (1996) Operating mechanism of the electrolyte cathode atmospheric glow discharge. Fresen J Anal Chem 355:813–819

    CAS  Google Scholar 

  46. Denaro AR, Hough KO (1972) Glow-discharge electrolysis of sulphuric acid solutions. Electrochim Acta 17:549

    Article  CAS  Google Scholar 

  47. Khlyustova AV, Maksimov AL, Khorev MS (2008) Radiation of metal atoms in the plasma of an atmospheric pressure glow discharge with an electrolyte cathode. Surf Eng Appl Electrochem 44:370

    Article  Google Scholar 

  48. Marcus RK, Davis WC (2001) An atmospheric pressure glow discharge optical emission source for the direct sampling of liquid media. Anal Chem 73:2903–2910

    Article  CAS  Google Scholar 

  49. Schwartz AJ, Ray SJ, Elish E, Storey AP, Rubinshtein AA, Chan GC, Pfeuffer KP, Hieftje GM (2012) Visual observations of an atmospheric-pressure solution-cathode glow discharge. Talanta 102:26

    Article  CAS  Google Scholar 

  50. Quarles CD, Gonzalez J, Choi I, Ruiz J, Mao X, Marcus RK, Russo RE (2012) Liquid sampling-atmospheric pressure glow discharge optical emission spectroscopy detection of laser ablation produced particles: a feasibility study. Spectrochim Acta Part B 76:190

    Article  CAS  Google Scholar 

  51. Richmonds C, Witzke M, Bartling B, Lee SW, Wainright J, Liu C-C, Sankaran RM (2011) Electron-transfer reactions at the plasma–liquid interface. J Am Chem Soc 133:17582

    Article  CAS  Google Scholar 

  52. Buxton GV, Greenstock CL, Helman WP, Ross AB (1988) Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (OH/O) in aqueous solution. J Phys Chem Ref Data 17:513–886

    Article  CAS  Google Scholar 

  53. Witzke M, Rumbach P, Go DB, Sankaran RM (2012) Evidence for the electrolysis of water by plasmas formed at the surface of aqueous solutions. J Phys D 45:44201

    Article  Google Scholar 

  54. Rumbach P, Griggs N, Sankaran RM, Go DB (2014) Visualization of electrolytic reactions at a plasma–liquid interface. IEEE Trans Plasma Sci 42:2610

    Article  Google Scholar 

  55. Rumbach P, Witzke M, Sankaran RM, Go DB (2013) Decoupling interfacial reactions between plasmas and liquids: charge transfer vs. plasma neutral reactions. J Am Chem Soc 135:16264

    Article  CAS  Google Scholar 

  56. Rumbach P, Bartels DM, Sankaran RM, Go DB (2015) The solvation of electrons by an atmospheric pressure plasma. Nat Commun 6:7248

    Article  CAS  Google Scholar 

  57. Bartels DM, Takahashi K, Cline JA, Marin TW, Jonah CD (2005) Pulse radiolysis of supercritical water. 3. Spectrum and thermodynamics of the hydrated electron. J Phys Chem A 109:1299

    Article  CAS  Google Scholar 

  58. Rumbach P, Bartels DM, Sankaran RM, Go DB, Corrigendum (2015) The solvation of electrons by an atmospheric-pressure plasma. Nat Commun 7:11911

    Article  Google Scholar 

  59. Rumbach P, Bartels DM, Sankaran RM, Go DB (2015) The effect of air on solvated electron chemistry at a plasma/liquid interface. J Phys D 48:424100

    Article  Google Scholar 

  60. Rumbach P, Xu R, Go DB (2016) Electrochemical production of oxalate and formate from CO2 by solvated electrons produced using an atmospheric-pressure plasma. J Electrochem Soc 163:F1157–F1161

    Article  CAS  Google Scholar 

  61. Lu Q, Rosen J, Zhou Y, Hutchings GS, Kimmel YC, Chen JG, Jiao F (2014) A selective and efficient electrocatalyst for carbon dioxide reduction. Nat Commun 5

  62. Angamuthu R, Byers P, Lutz M, Spek AL, Bouwman E (2010) Electrocatalytic CO2 conversion to oxalate by a copper complex. Science 327:313–315

    Article  CAS  Google Scholar 

  63. Nakata K, Ozaki T, Terashima C, Fujishima A, Einaga Y (2014) High-yield electrochemical production of formaldehyde from CO2 and seawater. Angew Chem 126:890–893

    Article  Google Scholar 

  64. Gordon S, Hart EJ, Matheson MS, Rabani J, Thomas JK (1963) Reactions of the hydrated electron. Discuss Faraday Soc 36:193–205

    Article  Google Scholar 

  65. Fojtik A, Czapski G, Henglein A (1970) Pulse radiolytic investigation of the carboxyl radical in aqueous solution. J Phys Chem 74:3204–3208

    Article  CAS  Google Scholar 

  66. Lin M, Katsumura Y, Muroya Y, He H, Miyazaki T, Hiroishi D (2008) Pulse radiolysis of sodium formate aqueous solution up to 400 °C: absorption spectra, kinetics and yield of carboxyl radical \({\text{CO}}_2^{ \bullet - }\). Rad Phys Chem 77:1208–1212

    Article  CAS  Google Scholar 

  67. Flyunt R, Schuchmann MN, von Sonntag C (2001) A common carbanion intermediate in the recombination and proton-catalysed disproportionation of the carboxyl radical anion, \({\text{CO}}_2^{ \bullet - },\) in aqueous solution. Chem Eur J 7:796–799

    Article  CAS  Google Scholar 

  68. Bhüler RE, Staehelin J, Hoigné J (1984) Ozone decomposition in water studied by pulse radiolysis. 1. Perhydroxyl (HO2)/hyperoxide (\({\text{O}}_2^ -\)) and \({\text{H}}{{\text{O}}_{\text{3}}}/{\text{O}}_3^ -\) as intermediates. J Phys Chem 88:2560–2564

    Article  Google Scholar 

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Acknowledgements

We would like to acknowledge our collaborators R. Mohan Sankaran, David M. Bartels, and Megan Witzke who have contributed to our work this area. R. Mohan Sankaran also provided Fig. 2 in this manuscript. The authors’ work has been supported by the US Army Research Office under Award Number W911NF-14-1-0241 and the Electrochemical Society Toyota Young Investigator Fellowship.

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Rumbach, P., Go, D.B. Perspectives on Plasmas in Contact with Liquids for Chemical Processing and Materials Synthesis. Top Catal 60, 799–811 (2017). https://doi.org/10.1007/s11244-017-0745-9

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