Abstract
Atmospheric-pressure air plasma, powered by alternating current (AC) sine-wave high voltage, can in-situ regenerate deactivated Au nanocatalysts during CO oxidation, but it needs high-humidity air as the discharge gas. To overcome the limitation on humidity for in-situ regeneration of air plasma, a square-wave pulsed plasma is applied in this work. Differently from the AC plasma, the pulsed plasma exhibits excellent regeneration performance at any humidity. Further, surface carbonate decomposition, nitrogen oxides poisoning species and electric discharge of the pulsed plasma regeneration are investigated. For the pulsed plasma regeneration at any humidity, the evolution of CO2 concentration with the regeneration time almost keeps the same profile, featuring zero-order kinetics for the carbonate decomposition; on the other hand, whether in the gas phase or on the catalyst surface, there are no formation of poisoning nitrogen oxides. The pulsed plasma at any humidity has the powerful ability in carbonate decomposition and simultaneously prevents the formation of poisoning nitrogen oxides, which is ascribed to its highly centralized energy deposition with high instantaneous power and long interval of instantaneous power. For practical application, normal air is also confirmed to be qualified for the pulsed plasma regeneration.
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References
Haruta M, Kobayashi T, Sano H, Yamada N (1987) Novel gold catalysts for the oxidation of carbon monoxide at a temperature far below 0 °C. Chem Lett 16:405–408
Bonmatí E, Casanovas A, Angurell I, Llorca J (2015) Hydrogen photoproduction from ethanol-water mixtures over Au–Cu alloy nanoparticles supported on TiO2. Top Catal 58:77–84
Kipnis M (2014) Gold in CO oxidation and PROX: the role of reaction exothermicity and nanometer-scale particle size. Appl Catal B 152–153:38–45
Hashmi ASK, Hutchings GJ (2006) Gold catalysis. Angew Chem Int Ed 45:7896–7936
Scirè S, Liotta LF (2012) Supported gold catalysts for the total oxidation of volatile organic compounds. Appl Catal B 125:222–246
Chen MS, Goodman DW (2004) The structure of catalytically active gold on titania. Science 306:252–255
Liu X, He L, Liu Y-M, Cao Y (2013) Supported gold catalysis: from small molecule activation to green chemical synthesis. Acc Chem Res 47:793–804
Zhang S, Li XS, Chen BB, Zhu X, Shi C, Zhu AM (2014) CO oxidation activity at room temperature over Au/CeO2 catalysts: disclosure of induction period and humidity effect. ACS Catal 4:3481–3489
Zhao KF, Tang HL, Qiao BT, Li L, Wang JH (2015) High activity of Au/γ-Fe2O3 for CO oxidation: effect of support crystal phase in catalyst design. ACS Catal 5:3528–3539
Li W, Comotti M, Schüth F (2006) Highly reproducible syntheses of active Au/TiO2 catalysts for CO oxidation by deposition-precipitation or impregnation. J Catal 237:190–196
Wu KC, Tung YL, Chen YL, Chen YW (2004) Catalytic oxidation of carbon monoxide over gold/iron hydroxide catalyst at ambient conditions. Appl Catal B 53:111–116
Chen BB, Zhu X, Crocker M, Wang Y, Shi C (2014) FeOx-supported gold catalysts for catalytic removal of formaldehyde at room temperature. Appl Catal B 154–155:73–81
Denkwitz Y, Makosch M, Geserick J, Hörmann U, Selve S, Kaiser U, Hüsing N, Behm RJ (2009) Influence of the crystalline phase and surface area of the TiO2 support on the CO oxidation activity of mesoporous Au/TiO2 catalysts. Appl Catal B 91:470–480
Karpenko A, Leppelt R, Cai J, Plzak V, Chuvilin A, Kaiser U, Behm RJ (2007) Deactivation of a Au/CeO2 catalyst during the low-temperature water-gas shift reaction and its reactivation: a combined TEM, XRD, XPS, DRIFTS, and activity study. J Catal 250:139–150
Konova P, Naydenov A, Tabakova T, Mehandjiev D (2004) Deactivation of nanosize gold supported on zirconia in CO oxidation. Catal Commun 5:537–542
Saavedra J, Powell C, Panthi B, Pursell CJ, Chandler BD (2013) CO oxidation over Au/TiO2 catalyst: pretreatment effects, catalyst deactivation, and carbonates production. J Catal 307:37–47
Tripathi A, Kamble V, Gupta N (1999) Microcalorimetry, adsorption, and reaction studies of CO, O2, and CO + O2 over Au/Fe2O3, Fe2O3, and polycrystalline gold catalysts. J Catal 187:332–342
Konova P, Naydenov A, Venkov C, Mehandjiev D, Andreeva D, Tabakova T (2004) Activity and deactivation of Au/TiO2 catalyst in CO oxidation. J Mol Catal A 213:235–240
Oh HS, Costello CK, Cheung C, Kung HH, Kung MC (2001) Regeneration of Au/γ-Al2O3 deactivated by CO oxidation. Stud Surf Sci Catal 139:375–381
Kim HH, Tsubota S, Daté M, Ogata A, Futamura S (2007) Catalyst regeneration and activity enhancement of Au/TiO2 by atmospheric pressure nonthermal plasma. Appl Catal A 329:93–98
Fan HY, Shi C, Li XS, Zhang S, Liu JL, Zhu AM (2012) In-situ plasma regeneration of deactivated Au/TiO2 nanocatalysts during CO oxidation and effect of N2 content. Appl Catal B 119–120:49–55
Zhu B, Li XS, Liu JL, Liu JB, Zhu X, Zhu AM (2015) In-situ regeneration of Au nanocatalysts by atmospheric-pressure air plasma: significant contribution of water vapor. Appl Catal B 179:69–77
Kim HH, Ogata A, Futamura S (2008) Oxygen partial pressure-dependent behavior of various catalysts for the total oxidation of VOCs using cycled system of adsorption and oxygen plasma. Appl Catal B 79:356–367
Kim HH, Teramoto Y, Negishi N, Ogata A (2015) A multidisciplinary approach to understand the interactions of nonthermal plasma and catalyst: a review. Catal Today 256:13–22
Delannoy L, Hassan NE, Musi A, Le To NN, Krafft J-M, Louis C (2006) Preparation of supported gold nanoparticles by a modified incipient wetness impregnation method. J Phys Chem B 110:22471–22478
Ojeda M, Zhan BZ, Iglesia E (2012) Mechanistic interpretation of CO oxidation turnover rates on supported Au clusters. J Catal 285:92–102
Haruta M, Tsubota S, Kobayashi T, Kageyama H, Genet MJ, Delmon B (1993) Low-temperature oxidation of CO over gold supported on TiO2, α-Fe2O3, and Co3O4. J Catal 144:175–192
Bollinger MA, Vannice MA (1996) A kinetic and DRIFTS study of low-temperature carbon monoxide oxidation over Au/TiO2 catalysts. Appl Catal B 8:417–443
Liu H, Kozlov AI, Kozlova AP, Shido T, Asakura K, Iwasawa Y (1999) Active oxygen species and mechanism for low-temperature CO oxidation reaction on a TiO2-supported Au catalyst prepared from Au (PPh3)(NO3) and as-precipitated titanium hydroxide. J Catal 185:252–264
Debeila MA, Coville NJ, Scurrell MS, Hearne GR (2005) The effect of calcination temperature on the adsorption of nitric oxide on Au–TiO2: drifts studies. Appl Catal A 291:98–115
Debeila MA, Coville NJ, Scurrell MS, Hearne GR, Witcomb MJ (2004) Effect of pretreatment variables on the reaction of nitric oxide (NO) with Au–TiO2: DRIFTS studies. J Phys Chem B 108:18254–18260
Chen C, Bai H, Chang C (2007) Effect of plasma processing gas composition on the nitrogen-do** status and visible light photocatalysis of TiO2. J Phys Chem C 111:15228–15235
Dailey BP, Shoolery JN (1955) The electron withdrawal power of substituent groups. J Am Chem Soc 77:3977–3981
Ráhel J, Sherman DM (2005) The transition from a filamentary dielectric barrier discharge to a diffuse barrier discharge in air at atmospheric pressure. J Phys D 38:547–554
Rajasekaran P, Mertmann P, Bibinov N, Wandke D, Viöl W, Awakowicz P (2010) Filamentary and homogeneous modes of dielectric barrier discharge (DBD) in air: investigation through plasma characterization and simulation of surface irradiation. Plasma Process Polym 7:665–675
Williamson JM, Trump DD, Bletzinger P, Ganguly BN (2006) Comparison of high-voltage ac and pulsed operation of a surface dielectric barrier discharge. J Phys D 39:4400–4406
Fang Z, Yang H, Qiu Y (2010) Surface treatment of polyethylene terephthalate films using a microsecond pulse homogeneous dielectric barrier discharges in atmospheric air. IEEE Trans Plasma Sci 38:1615–1623
Fridman A (2008) Plasma chemistry. Cambridge University Press, New York
Liu S, Neiger M (2001) Excitation of dielectric barrier discharges by unipolar submicrosecond square pulses. J Phys D 34:1632–1638
Min BK, Friend CM (2007) Heterogeneous gold-based catalysis for green chemistry: low-temperature CO oxidation and propene oxidation. Chem Rev 107:2709–2724
Widmann D, Behm RJ (2014) Activation of molecular oxygen and the nature of the active oxygen species for CO oxidation on oxide supported Au catalysts. Acc Chem Res 47:740–749
Lu XP, Ye T, Cao YG, Sun ZY, **ong Q, Tang ZY, **ong ZL, Hu J, Jiang ZH, Pan Y (2008) The roles of the various plasma agents in the inactivation of bacteria. J Appl Phys 104:053309
Peyrous R, Pignolet P, Held B (1989) Kinetic simulation of gaseous species created by an electrical discharge in dry or humid oxygen. J Phys D 22:1658–1667
Kogelschatz U, Eliasson B, Hirth M (1988) Ozone generation from oxygen and air: discharge physics and reaction mechanisms. Ozone Sci Eng 10:367–378
Eliasson B, Kogelschatz U (1986) N2O formation in ozonizers. J Chem Phys 83:279–282
Acknowledgements
This work was supported by National Natural Science Foundation of China (11175036) and Fundamental Research Funds for the Central Universities (DUT16LK16).
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Zhu, B., Liu, JL., Li, XS. et al. In Situ Regeneration of Au Nanocatalysts by Atmospheric-Pressure Air Plasma: Regeneration Characteristics of Square-Wave Pulsed Plasma. Top Catal 60, 914–924 (2017). https://doi.org/10.1007/s11244-017-0756-6
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DOI: https://doi.org/10.1007/s11244-017-0756-6