臭氧(O3) 具強氧化能力和無殘留污染特性，近年來在科學技術和日常生活的許多領域中也被廣泛應用，包括化學合成、半導體表面處理、水消毒、食品加工和醫療等。然現今市售臭氧機價格依然偏高，耗能也大，此為瓶頸所在。二氧化鈦 (TiO2) 作為光觸媒時，僅吸收紫外光，目前已採用幾種方法來將TiO2吸收光譜擴展到可見光範圍，例如在氫氣氣氛下以高溫高壓下改質，然而，眾所周知，使用氫氣並不安全，需要特殊設備做維護。本研究發展以氮氣改質黑色的TiO2 (TiO2-B)，此與在氫氣氣氛下製備的black-TiO2有相同的性能。改質後的二氧化鈦(N-TiO2-B)用於結合電漿系統進行臭氧合成，藉由觸媒參數機制及反應器設計開發新穎之高能效臭氧生成反應器。研究結果顯示填充N-TiO2-B有最高之臭氧產率53.9 gO3/m3能效高達509 gO3/kWh，與未改質前相比提升約12%，且有良好穩定度。使用管狀反應管相比填充床反應管有較小的放電間隙，且設備較簡易，本研究發展以第一階段改質之N-TiO2-B光觸媒塗佈在管狀反應器，其最佳能效為346 g/kWh，雖不及第一階段之能效，但仍優於大部分研究，因此將觸媒塗佈於管狀反應管進行放電可有效提升電漿觸媒系統之效能，以優化臭氧生成反應器。

With a strong oxidizing capability, ozone (O3) is a non-residual decontamination agent. In recent years, ozone has been widely used in many areas such as chemical synthesis, semiconductor surface treatment, water disinfection, food processing and medical treatment. However, ozone generators on the market are expensive and require a lot of energy to operate, which is the bottleneck for the wide application. TiO2 is a multifunctional material with various applications such as solar cells and pollutant removal. However, due to its large energy gap (3.0-3.2 eV), TiO2 can only absorb ultraviolet light, resulting in low photocatalytic efficiency. Several methods have been used to extend the absorption spectrum of TiO2 to the range of visible light, such as thermal treatment under a hydrogen atmosphere. However, it is well known that working with hydrogen is dangerous and requires special maintenance. In this study, we prepared N-TiO2-B by calcining UR-LTiO2 at 550°C under a nitrogen atmosphere, which has the same properties as black-TiO2 prepared under hydrogen atmosphere. N-TiO2-B prepared is used for ozone synthesis in combination with a plasma system to develop a novel and energy efficient ozone generation reactor by means of optimizing catalyst parameter and reactor design. The results show that N-TiO2-B as a catalyst has the highest ozone yield of 53.9 gO3/m3 with an energy efficiency of 509.32 gO3/kWh, which is about 12% higher than that before the nitrogen treatment and has a good stability. In this study, the best energy efficiency of 346 g/kWh is achieved by coating N-TiO2-B photocatalyst in the cylinder reactor, which was not as good as the packed-bed reactor energy efficiency, but still better than most studies. Therefore, this catalyst can effectively improve the performance of the plasma to enhance the ozone generation rate.

Albetran, H, O’ Connor, B. H, and Low, I. M., Effect of Calcination on Band Gaps for Electrospun Titania Nanofibers Heated in Air-argon Mixtures, Materials & Design, 92, 480-485, (2016).
Asahi, R, and Morikawa, T., Nitrogen Complex Species and its Chemical Nature in TiO2 for Visible-light Sensitized Photocatalysis, Chemical Physics, 339, 57–63 (2007).
Bayarri, B, Cruz-Alcalde, A, and Lopez-Vinent, N., Can Ozone Inactivate SARS-CoV-2? A Review of Mechanisms and Performance on Viruses, Journal of Hazardous Materials, 415, 125658, (2021).
Bouzoubaa, A, Markovits, A, Calatayud, M, and Minot, C., Comprison of the Reduction of Matel Oxide Surfaces：TiO2-Anatase, TiO2-Rutile and SnO2-Rutile, Surface Science, 583(1), 107-117, (2005).
Brueggemann, N., T. Puehmeier, R. Fiekens, F.J. Richardt, and M. Salvermoser, Cooling Conditions of Ozone Generators, Ozone: Science and Engineering, 196-201 (2017).
Chang, M. B, and Wu, S. J., Experimental Study on Ozone Synthesis via Dielectric Barrier Discharges, Ozone Science. Engineering, 19, 241-254, (1997).
Chen, H. L, Lee, H. M, Chen, S. H, Wei, T. H, and Chang, M. B., Influence of Ar Addition on Ozone Generation in Non-Thermal Plasmas, Plasma Sources Science and Technology, 19, 065009, (2010).
Chen, X. B, Liu, L, and Huang, F. Q., Black Titanium Dioxide (TiO2) Nanomaterials, Chemical Society Reviews, 44, 7, 1861-1885, (2015).
Chen, X. B, Liu, L, Yu, P. Y, and Mao, S, S., Increasing Solar Absorption for Photocatalysis with Black Hydrogenated Titanium Dioxide Nanocrystals, Science, 331, 746-750 (2011).
Christensen, P. A, Yonar, T, and Zakaria, K., The Electrochemical Generation of Ozone: A Review, Ozone: Science & Engineering, 35, 149–167, (2013).
Claus, H., Ozone Generation by Ultraviolet Lamps, Photochemistry and Photobiology, 97, 3, 471-476, (2021).
de Souza, H. M, Savi, G. D, Gomes, T, Cardoso, W. A, Cargnin, M, and Angioletto E., Ozone Application in COVID-19 Triage Areas and Its Efficiency of Microbial Decontamination, Ozone: Science & Engineering, 43, 4, 306-316, (2021).
Dohan, J. M, and Masschelein, W. J., The Photochemical Generation of Ozone: Present State of the Art, Ozone: Science & Engineering, 9, 4, 315-334, (1987).
Eliasson, B, Hirth, M, and Kogelschatz, U., Ozone Synthesis From Oxygen in Dielectric Barrier Discharges, Journal of Physics D：Applied Physics, 20(11), 1421-1437, (1987).
Eliasson, B, and Kogelschatz, U., Ozone Generation with Narrow–Band UV Radiation, Ozone: Science & Engineering, 13, 3, 365-373, (1991).
Elvis, A. M. and Ekta, J. S., Ozone Therapy: A Clinical Review, Journal of Natural Science, Biology and Medicine, 2(1), 66-70, (2011).
Foller, P. C, and Kelsall, G. H., Ozone Generation via the Electrolysis of Fluoboric Acid Using Glassy Carbon Anodes and Air Depolarized Cathodes, Journal of Applied Electrochemistry, 23(10), 996-1010, (1993).
Gamboa, J. A, and Pasquevich, D. M., Effect of Chlorine Atmosphere on the Anatase-Rutile Transformation, Journal of the American Ceramic Society, 75(11), 2934-2938, (1992).
Glaze, W. H, Kang, J. W, and Chapin, D. H., The Chemistry of Water Treatment Processes Involving Ozone, Hydrogen Peroxide and Ultraviolet Radiation, Ozone: Science & Engineering, 9, 4, 335-352, (1987).
Hayashi, M, Ochiai, T, Tago, S, Saito, H, Yahaji, T, and Fujishima, A., Electrolytic Ozone Generation at Pt/Ti Electrode Prepared by Multiple Electrostrike Method, Chemistry Letters, 48(6), 574-577, (2019).
Hu, H, Lin, Y, Hu, Y. H., Phase Role of White TiO2 Precursor in Its Reduction to Black TiO2, Physics Letters A, 383, 2978-2982, (2019).
Ivoning, J, van Santen, R. A., Electrostatic Potential Calculations on Crystalline TiO2：The Surface Reducibility of Rutile and Anatase, Chemical Physics Letters, 101(6), 541-547, (1983).
Janotti, A, Van de Walle, C. G., Fundamentals of Zinc Oxide as a Semiconductor, Reports on Progress in Physics, 72(12), 126501, (2009).
Jodzis, S., Effective Ozone Generation in Oxygen Using a Mesh Electrode in an Ozonizer with Variable Linear Velocity, Ozone: Science & Engineering, 34, 378–386, (2012).
Katal, R, Kholghi Eshkalak, S, Masudy-Panah, S, Kosari, M, Saeedikhani, M, Zarinejad, M, and Ramakrishna., Evalution of Solar-Driven Photocatalytic Activity of Thermal Treated TiO2 under Various Atmospheres, Nanomaterials, 9, 163, (2019).
Katal, R, Salehi, M, Davood Abadi Farahani, M. H, Masudy-Panah, S, Ong, S. L, and Hu, J., Preparation of a New Type of Black TiO2 under a Vacuum Atmosphere for Sunlight Photocatalysis, ACS Applied Materials & Interfaces, (2018).
Kitayama, J., and M. Kuzumoto, Analysis of Ozone Generation from air in Silent Discharge, Journal of Physics D: Applied Physics, 23, 3032-3040 (1999).
Kogelschatz, U , Eliasson, B, and Hirth, M., Ozone Generation from Oxygen and Air. Discharge Physics and Reaction Mechanisms, Ozone: Science & Engineering, 10, 367-378, (1988).
Li, M, Yan, Y, Jin, Q, Liu, M, Zhu, B, Wang, L, Li, T, Tang, X. J, and Zhu, X. Y., Experimental Study on Ozone Generation from Oxygen in Double Surface Dielectric Barrier Discharge, Vacuum, 157, 249–258, (2018).
Loeb, B. L., Ozone: Science & Engineering: Thirty-three Years and Growing, Ozone: Science & Engineering, 33, 4, 329-342, (2011).
Malik, M. A., Ozone Synthesis Using Shielded Sliding Discharge: Effect of Oxygen Content and Positive versus Negative Streamer Mode, Ind. Eng. Chem. Res, 53, 12305–12311, (2014).
McLean, L., The Miracle of Ozone Therapy. URL: http://www. zeusinfoservice. com/Articles/The Miracle of Ozone Therapy. pdf 2009.
Michielsen, I, Uytdenhouwen, Y, Pype, J, Michielsen, B, Mertens, J, Reniers, F, Meynen, V, and Bogaerts, A., CO2 Dissociation in a Packed Bed DBD Reactor: First Steps Towards a Better Understanding of Plasma Catalysis, Chemical Engineering Journal, 326, 477-488, (2017).
Mokoena, M. L, Brink, C. B, Harvey, B. H, and Oliver, D. W., Appraisal of Ozone as Biologically Active Molecule and Experimental Tool in Biomedical Sciences, Medicinal Chemistry Research, 20(9), 1687-1695, (2010).
Nemmich, S., A. Tilmatine, Z. Dey, N. Hammadi, K. Nassour, and S. Messal, Optimal Sizing of a DBD Ozone Generator Using Response Surface Modeling, Ozone: Science and Engineering, 37, 3-8 (2015).
Pekárek, S, Mikesˇ, J, and Kry ́sa, J., Comparative Study of TiO2 and ZnO Photocatalysts for the Enhancement of Ozone Generation by Surface Dielectric Barrier Discharge in Air, Catalysis, 502, 122-128, (2015).
Pekárek, S., Non-Thermal Plasma Ozone Generation, Acta Polytech, 43, 47-51, (2003).
Rip, R.G, and A. Netzer, Handbook of Ozone Technology and Application, ISBN, 325 (1982).
Skalny J. D, Mikoviny T, Mason N J, and Sobek V., The Effect of Gaseous Diluents on Ozone Generation from Oxygen, Ozone: Science & Engineering, 24, 29, (2002).
Su, T, Yang, Y, Na, Y, Fan, R, Li, L, Wie, L, Yang, B, and Cao, W., An Insight into the Role of Oxygen Vacancy in Hydrogenated TiO2 Nanocrystals in the Performance of Dye-Sensitized Solar Cells, ACS Applied Materials & Interfaces, 7(6), 3754-3763, (2015).
Sung, Y.M., and T. Sakoda, Optimum Conditions for Ozone Formation in a Micro Dielectric Barrier Discharge, Surface and Coatings Technology, 197(2-3), 148-153, (2005).
Tauc, J, Grigorovici, R, and Vancu, A., Optical Properties and Electronic Structure of Amorphous Germanium, Physica Status, 15(2), 627-637, (1966).
Tauc, J., Absorption Edge And Internal Electric Fields in Amorphous Semiconductors, Materials Research Bulletin, 5(8), 721-729, (1970).
Ullattil, S. G, Narendranath, S. B, Pillai, S. C, and Periyat, P., Black TiO2 Nanomaterials: A Review of Recent Advance, Chemical Engineering Journal, 343, 708-736 (2018).
Xu, X., Dielectric Barrier Discharge - Properties and Applicantions, Thin Solid Films, 390(1-2), 237-242, (2001).
Yu, J. W, Jung, G. B, Chen, C. W, Yeh, C. C, Nguyen, X. V, Ma C. C, Hsieh, C. W, and Lin, C. L., Innovative Anode Catalyst Designed to Reduce the Degradation in Ozone Generation via PEM Water Electrolysis, Renewable Energy, 129, 800-805, (2018).
Yuan, D. K, Wang, Z.H, Ding, C, He, Y, Whiddon, R, and Cen, K.F., Ozone Production in Parallel Multichannel Dielectric Barrier Discharge from Oxygen and Air: The Influence of Gas Pressure, Journal of Physics D：Applied Physics, 49(45), 455203, (2016).
Yuan, D. K, Ding, C, He, Y, Wang, Z. H, Kumar, S, Zhu, Y. Q, and Cen, K. F., Characteristics of Dielectric Barrier Discharge Ozone Synthesis for Different Pulse Modes, Plasma Chem. Plasma Process, 37, 1165–1173, (2017).
李昀恩，以LaFeO3/Black-TiO2行光催化反應以去除甲苯及異丙醇之可行性探討，國立中央大學碩士論文 (2018)。
儲憶凡，以電漿觸媒系統提升臭氧生成效率之可行性評估，國立中央大學碩士論文(2020)。