本研究以硝酸鋅、醋酸鋅作為起始物，利用沉澱法、水熱法、微波水熱法合成奈米氧化鋅(ZnO)，利用XRD、SEM、XPS、BET等方法鑑定其表面特性，再以光催化程序(ZnO/UV)降解結晶紫(Crystal Violet, CV)染料，並鑑定反應中間產物及探討可能降解路徑。
以醋酸鋅作為起始物利用沉澱法(PA)、水熱法(HA)與微波水熱法(MA)合成之PA11/UV、HA4/UV與MA5/UV去除率分別為80.57、96.72與84.29%。
以硝酸鋅作為起始物合成ZnO中，沉澱法(PN)、水熱法(HN)與微波水熱法(MN)合成之PN1/UV、HN7/UV與MN12/UV之去除率分別可達92.97、92.14與98.04 %。綜合以上結果，以MN12/UV之去除率最佳。
ZnO/UV程序去除CV染料之主要可能反應機制包括(1)發色基團之去甲基化(N-de-methylated)、(2)羥化 (Hydroxylation)反應與(3)破壞發色基團之共振結構(Cleavage of conjugated chromophore structure)。本研究之結果，有助於未來應用於染料降解之應用。

關鍵字：氧化鋅、沉澱法、水熱法、微波水熱法、結晶紫

Three methods were developed and investigated in this research to synthesize Zinc oxide (ZnO), namely, precipitation (PA), hydrothermal (HA) and microwave-hydrothermal (MA) methods using Zinc Acetate and Zinc Nitrate as precursors, respectively. The resulting ZnOs were characterized by SEM-EDS, HRXPS, TEM, XRD, and BET. The photo catalytic properties of these ZnOs were investigated as well, through ZnO/UV processes for degradation of Crystal Violet (CV). Reaction intermediates and potential reactions pathways were identified and proposed, respectively.
For zinc acetate as for precursors, the removal efficiencies for CV are 80.57, 96.72 and 84.29% for PA11/UV, HA4/UV and MA5/UV, respectively. PA11, HA4 and MA5 are prepared by PA, HA, and MA methods, respectively.
For zinc nitrate as for precursors, the removal efficiencies for CV are 92.97, 92.14 and 98.04%, respectively for PN1/UV, HN7/UV and MN12/UV respectively. PN1, HN7 and MN12 are prepared by PA, HA, MA methods, respectively.
The reaction intermediates of the ZnO/UV processes were separated, identified and characterized by HPLC-ESI-MS. Potential reaction pathways for ZnO/UV process include (1) N-de-methylated, (2) hydroxylation and (3) cleavage of conjugated chromospheres structure. The reaction mechanisms proposed in this study would be useful for future application of advanced oxidation technology for removal of dyes in wastewaters.
Key words: zinc oxide, precipitation, hydrothermal, microwave-hydrothermal, crystal violet

摘要 I
Abstract II
表目錄 VI
圖目錄 VII
第一章 緒論 1
1-1 研究背景 1
1-2 研究目的 3
第二章 文獻回顧 4
2-1 染料及染整廢水之特性與危害 4
2-1-1 染料之特性 4
2-1-2 三苯基甲烷類染料 6
2-1-3 染整廢水特性 7
2-2染料廢水處理技術 9
2-3 半導體的光催化機制 13
2-4 氧化鋅的材料特性 14
2-5 氧化鋅的光催化反應 16
2-6 奈米氧化鋅的製備 18
第三章 實驗材料與方法 20
3-1 研究方法 20
3-2實驗材料與設備 21
3-2-1實驗藥品 21
3-2-2實驗設備 22
3-3實驗步驟 23
3-3-1沉澱法合成氧化鋅 23
3-3-2水熱法合成奈米氧化鋅 26
3-3-3 微波水熱法合成氧化鋅 29
3-3-4合成氧化鋅結合UV光催化處理程序 32
3-4分析儀器 33
3-4-1 高效液相層析電灑質譜儀 33
3-4-2 比表面積分析儀 34
3-4-3 酸鹼度計 35
3-4-4 場發射掃描式電子顯微鏡 36
3-4-5 X光粉末繞射儀 36
3-4-6 高解析電子能譜儀 37
第四章 結果與討論 38
4-1 醋酸鋅合成ZnO 38
4-1-1 以醋酸鋅沉澱法合成ZnO 39
4-1-2 以醋酸鋅水熱法合成ZnO 53
4-1-3 以醋酸鋅微波水熱法合成ZnO 64
4-1-4 以醋酸鋅合成ZnO/UV程序對CV染料降解之中間產 76
物分析 76
4-2 硝酸鋅合成氧化鋅 78
4-2-1以硝酸鋅沉澱法合成ZnO 78
4-2-2 以硝酸鋅水熱法合成ZnO 88
4-2-3 以硝酸鋅微波水熱法合成ZnO 99
4-2-4 以硝酸鋅合成ZnO/UV程序對CV染料降解之中間產 108
4-3 綜合討論 115
第五章 結論 117
參考文獻 118

Ahonen, P.P., Tapper, U., Kauppinen, E.I., Joubert, J.-., Deschanvres, J.-., 2001. Aerosol synthesis of Ti-O powders via in-droplet hydrolysis of titanium alkoxide. Materials Science and Engineering A. 315, 113-121.
Akyol, A., Yatmaz, H.C., Bayramoglu, M., 2004. Photocatalytic decolorization of Remazol Red RR in aqueous ZnO suspensions. Applied Catalysis B: Environmental. 54, 19-24.
Azmi, W., Sani, R.K., Banerjee, U.C., 1998. Biodegradation of triphenylmethane dyes. Enzyme Microb. Technol. 22, 185-191.
Baptista, M.S., Indig, G.L., 1998. Effect of BSA binding on photophysical and photochemical properties of triarylmethane dyes. J Phys Chem B. 102, 4678-4688.
Bellardita, M., Addamo, M., Di Paola, A., Palmisano, L., 2007. Photocatalytic behaviour of metal-loaded TiO2 aqueous dispersions and films. Chem. Phys. 339, 94-103.
Borghei, S.M., Hosseini, S.N., 2008. Comparison of furfural degradation by different photooxidation methods. Chem. Eng. J. 139, 482-488.
Chen, C.-. 2007, "Degradation pathways of ethyl violet by photocatalytic reaction with ZnO dispersions", Journal of Molecular Catalysis A: Chemical, vol. 264, no. 1-2, pp. 82-92.
Chen, C.-., Mai, F.-., Chen, K.-., Wu, C.-. & Lu, C.-. 2007, "Photocatalyzed N-de-methylation and degradation of crystal violet in titania dispersions under UV irradiation", Dyes and Pigments, vol. 75, no. 2, pp. 434-442
Chhor, K., Bocquet, J.F., Colbeau-Justin, C., 2004. Comparative studies of phenol and salicylic acid photocatalytic degradation: Influence of adsorbed oxygen. Mater. Chem. Phys. 86, 123-131.
Chiing-Chang Chen, Chung-Shin Lu, Fu-Der Mai, Chyan-Syang Weng., 2006. Photooxidative N-de-ethylation of anionic triarylmethane dye (sulfan blue) in titanium dioxide dispersions under UV irradiation. Journal of Hazardous Materials B. 137, 1600-1607.
Cho, B.P., Yang, T., Blankenship, L.R., Moody, J.D., Churchwell, M., Beland, F.A., Culp, S.J., 2003. Synthesis and characterization of N-demethylated metabolites of malachite green and leucomalachite green. Chem. Res. Toxicol. 16, 285-294.
Choy, K.L., 2003. Chemical vapour deposition of coatings. Progress in Materials Science. 48, 57-170.
Daneshvar, N., Salari, D., Khataee, A.R., 2004. Photocatalytic degradation of azo dye acid red 14 in water on ZnO as an alternative catalyst to TiO2. J. Photochem. Photobiol. A. 162, 317-322.
Daneshvar, N., Salari, D., Khataee, A.R., 2003. Photocatalytic degradation of azo dye acid red 14 in water: Investigation of the effect of operational parameters. J. Photochem. Photobiol. A. 157, 111-116.
Doerge, D.R., Chang, H.C., Divi, R.L., Churchwell, M.I., 1998. Mechanism for inhibition of thyroid peroxidase by leucomalachite green. Chem. Res. Toxicol. 11, 1098-1104.
Dutta, M., Mridha, S., Basak, D., 2008. Effect of sol concentration on the properties of ZnO thin films prepared by sol-gel technique. Appl. Surf. Sci. 254, 2743-2747.
Duxbury, D.P., 1993. The photochemistry and photophysics of triphenylmethane dyes in solid and liquid media. Chem. Rev. 93, 381-433.
Fang, F., Zhao, D.X., Zhang, J.Y., Shen, D.Z., Lu, Y.M., Fan, X.W., Li, B.H., Wang, X.H., 2008. The influence of growth temperature on ZnO nanowires. Mater Lett. 62, 1092-1095.
Frank, S.N., Bard, A.J., 1977. Heterogeneous photocatalytic oxidation of cyanide and sulfite in aqueous solutions at semiconductor powders. J. Phys. Chem. 81, 1484-1488.
Fujishima A., Rao T. N., Tryk D. A., 2000. Titanium dioxide photocatalysis. Journal of Photochemistry and Photobiology C: Photochemistry Reviews. , 1-21.
Gogate, P.R., Pandit, A.B., 2004. A review of imperative technologies for wastewater treatment I: Oxidation technologies at ambient conditions. Adv. Environ. Res. 8, 501-551.
Gültekin, I., Ince, N.H., 2007. Synthetic endocrine disruptors in the environment and water remediation by advanced oxidation processes. J. Environ. Manage. 85, 816-832.
Hessel, C., Allegre, C., Maisseu, M., Charbit, F., Moulin, P., 2007a. Guidelines and legislation for dye house effluents. J. Environ. Manage. 83, 171-180.
Hessel, C., Allegre, C., Maisseu, M., Charbit, F., Moulin, P., 2007b. Guidelines and legislation for dye house effluents. J. Environ. Manage. 83, 171-180.
Hirano, M., Nakahara, C., Ota, K., Tanaike, O., Inagaki, M., 2003. Photoactivity and phase stability of ZrO2-doped anatase-type TiO2 directly formed as nanometer-sized particles by hydrolysis under hydrothermal conditions. Journal of Solid State Chemistry. 170, 39-47.
Hoffmann, M.R., Martin, S.T., Choi, W., Bahnemann, D.W., 1995. Environmental applications of semiconductor photocatalysis. Chem. Rev. 95, 69-96.
Horikoshi, S., Kajitani, M., Hidaka, H., Serpone, N., 2008. Investigation of factors that influence TiO2 photoassisted degradations under simultaneous illumination by UV and microwave radiation fields. J. Photochem. Photobiol. A. 196, 159-164.

Hsing, H.-., Chiang, P.-., Chang, E.-., Chen, M.-., 2007. The decolorization and mineralization of Acid Orange 6 azo dye in aqueous solution by advanced oxidation processes: A comparative study. J. Hazard. Mater. 141, 8-16.
Huren, A., Qian, Y., Gu, X., Tang, W.Z., 1996. Biological treatment of dye wastewaters using an anaerobic-oxic system. Chemosphere. 33, 2533-2542.
I. Safarik, M. Safarikova and N. Vrchotova, 1995. Study of sorption of triphenylmethane dyes on a maganetic carrier bearing an immobilized copper phthalocyanine dye. Collect. Czech. Chem. Commun. 60, 34-42.
Jing, L., Xu, Z., Sun, X., Shang, J., Cai, W., 2001. The surface properties and photocatalytic activities of ZnO ultrafine particles. Appl. Surf. Sci. 180, 308-314.
Kang, S.-., Liao, C.-., Po, S.-., 2000. Decolorization of textile wastewater by photo-fenton oxidation technology. Chemosphere. 41, 1287-1294.
Kansal, S.K., Singh, M., Sud, D., 2007. Studies on photodegradation of two commercial dyes in aqueous phase using different photocatalysts. J. Hazard. Mater. 141, 581-590.
Kim, Y.-., Tai, W.-., Shu, S.-., 2005. Effect of preheating temperature on structural and optical properties of ZnO thin films by sol-gel process. Thin Solid Films. 491, 153-160.
Kobya, M., Can, O.T., Bayramoglu, M., 2003. Treatment of textile wastewaters by electrocoagulation using iron and aluminum electrodes. J. Hazard. Mater. 100, 163-178.
Liu, B., Hua, C.Z., 2004. Fabrication of ZnO "Dandelions" via a modified Kirkendall process. J. Am. Chem. Soc. 126, 16744-16746.
Liu, Y., Liu, Z., Wang, G., 2003. Synthesis and characterization of ZnO nanorods. J. Cryst. Growth. 252, 213-218.


Mai, F.D., Chen, C.C., Chen, J.L., Liu, S.C., 2008. Photodegradation of methyl green using visible irradiation in ZnO suspensions. Determination of the reaction pathway and identification of intermediates by a high-performance liquid chromatography-photodiode array-electrospray ionization-mass spectrometry method. Journal of Chromatography A. 1189, 355-365.
Martins, A.d.O., Canalli, V.M., Azevedo, C.M.N., Pires, M., 2006. Degradation of pararosaniline (C.I. Basic Red 9 monohydrochloride) dye by ozonation and sonolysis. Dyes and Pigments. 68, 227-234.
Mittal, A., Gajbe, V., Mittal, J., 2008. Removal and recovery of hazardous triphenylmethane dye, Methyl Violet through adsorption over granulated waste materials. J. Hazard. Mater. 150, 364-375.
Molinari, R., Pirillo, F., Falco, M., Loddo, V., Palmisano, L., 2004. Photocatalytic degradation of dyes by using a membrane reactor. Chemical Engineering and Processing: Process Intensification. 43, 1103-1114.
Mrowetz, M., Pirola, C., Selli, E., 2003. Degradation of organic water pollutants through sonophotocatalysis in the presence of TiO2. Ultrason. Sonochem. 10, 247-254.
Namasivayam, C., Arasi, D.J.S.E., 1997. Removal of congo red from wastewater by adsorption onto waste red mud. Chemosphere. 34, 401-417.
Namasivayam, C., Muniasamy, N., Gayatri, K., Rani, M., Ranganathan, K., 1996. Removal of dyes from aqueous solutions by cellulosic waste orange peel. Bioresour. Technol. 57, 37-43.
Noureddine Barka, Samir Qourzal, Ali Assabbane, Abederrahman Nounah and Yhya Ait-Ichou, 2008. Factors influencing the photocatalytic degradation of Rhodamine B by TiO2-coated non-woven paper. Journal of Photochemistry and Photobiology A: Chemistry. 195, 346-351.
Okudera, H., Yokogawa, Y., 2003. Fabrication of titania-coated silica fibers and effect of substrate shape on coating growth rate. Thin Solid Films. 423, 119-124.
Peternel, I.T., Koprivanac, N., Božić, A.M.L., Kušić, H.M., 2007. Comparative study of UV/TiO2, UV/ZnO and photo-Fenton processes for the organic reactive dye degradation in aqueous solution. J. Hazard. Mater. 148, 477-484.
Popiel, S., Witkiewicz, Z., Chrzanowski, M., 2008. Sulfur mustard destruction using ozone, UV, hydrogen peroxide and their combination. J. Hazard. Mater. 153, 37-43.
Prevot, A. B., Baiocchi, C., Brussino , M. C., Pramauro,E., Savarino, P., Augugliaro, V., Marci, G., and Palmisano, L., 2001. Photocatalytic Degradation of Acid Blue 80 in Aqueous Solution Containg TiO2 Suspension. Environ. Sci. Technol. 35, 971-975.
Ruppert, G., Bauer, R., Heisler, G., 1994. UV-O3, UV-H2O2, UV-TiO2 and the photo-Fenton reaction comparison of advanced oxidation processes for wastewater treatment. Chemosphere. 28, 1447-1454.
Sakthivel, S., Neppolian, B., Shankar, M.V., Arabindoo, B., Palanichamy, M., Murugesan, V., 2003. Solar photocatalytic degradation of azo dye: Comparison of photocatalytic efficiency of ZnO and TiO2. Solar Energy Mater. Solar Cells. 77, 65-82.
Sani, R.K., Banerjee, U.C., 1999. Decolorization of triphenylmethane dyes and textile and dye-stuff effluent by Kurthia sp. Enzyme Microb. Technol. 24, 433-437.
Sasaki, Y.F., Kawaguchi, S., Kamaya, A., Ohshita, M., Kabasawa, K., Iwama, K., Taniguchi, K., Tsuda, S., 2002. The comet assay with 8 mouse organs: Results with 39 currently used food additives. Mutation Research - Genetic Toxicology and Environmental Mutagenesis. 519, 103-119.
Selcuk, H., 2005. Decolorization and detoxification of textile wastewater by ozonation and coagulation processes. Dyes and Pigments. 64, 217-222.
Selva Roselin, L., Rajarajeswari, G.R., Selvin, R., Sadasivam, V., Sivasankar, B., Rengaraj, K., 2002. Sunlight/ZnO-Mediated photocatalytic degradation of reactive red 22 using thin film flat bed flow photoreactor. Solar Energy. 73, 281-285.
Shu, H.-., Chang, M.-., 2005. Decolorization effects of six azo dyes by O3, UV/O3 and UV/H2O2 processes. Dyes and Pigments. 65, 25-31.
Smith, A., Rodriguez-Clemente, R., 1999. Morphological differences in ZnO films deposited by the pyrosol technique: Effect of HCl. Thin Solid Films. 345, 192-196.
Srivastava, S., Sinha, R., Roy, D., 2004. Toxicological effects of malachite green. Aquatic Toxicology. 66, 319-329.
T.Gessner, U. Mayer, B. aktiengesellschaft., 1996. Triarylmethane and Diarylmethane Dyes. . Industrial Chemistry A. 27, 179-227.
Tonto, P., Mekasuwandumrong, O., Phatanasri, S., Pavarajarn, V., Praserthdam, P., 2008. Preparation of ZnO nanorod by solvothermal reaction of zinc acetate in various alcohols. Ceram. Int. 34, 57-62.
Walker, G.M., Weatherley, L.R., 1997. Adsorption of acid dyes on to granular activated carbon in fixed beds. Water Res. 31, 2093-2101.
Wang, H., Xie, C., 2008. The effects of oxygen partial pressure on the microstructures and photocatalytic property of ZnO nanoparticles. Physica E: Low-Dimensional Systems and Nanostructures. 40, 2724-2729.
Wanpeng, Z., Zhihua, Y., Li, W., 1996. Application of ferrous-hydrogen peroxide for the treatment of H-acid manufacturing process wastewater. Water Res. 30, 2949-2954.
Wert, E.C., Rosario-Ortiz, F.L., Drury, D.D., Snyder, S.A., 2007. Formation of oxidation byproducts from ozonation of wastewater. Water Res. 41, 1481-1490.
Wojnárovits, L., Takács, E., 2008. Irradiation treatment of azo dye containing wastewater: An overview. Radiat. Phys. Chem. 77, 225-244.
Zollinger H., 1992. Color chemistry: syntheses, properties, and applications of organic dyes and pigments. Journal of Photochemistry and Photobiology A: Chemistry. , 385-386.


張有諒，2005，「利用費頓試劑來氧化Reactive Black 5染料
的可行性及動力學之研究」，碩士論文，國立高雄師範大學化
學系，高雄。
藤島昭,橋本和仁,渡部俊也,譯：王政友,世茂出版有限公
司,2006/04/27圖解光觸媒.