臺灣博碩士論文加值系統

本研究旨在利用二甲基亞碸(dimethyl sulfoxide, DMSO)為氫氧自由基捕捉劑(radical capture)，量測液相光催化反應系統中，氫氧自由基的生成濃度。基於自由基定量的需要，本研究先自行研發自由基捕捉/螢光法量測技術後，再進一步比較不同反應環境因子，對光催化反應系統中氫氧自由基生成之影響，所測試的因子包括：捕捉劑濃度、溶液pH值、光觸媒劑量、光照強度、不同波長光源等。DMSO於液相光催化反應中與氫氧自由基反應產生甲醛後，經添加螢光試劑(1,3-cyclohexanedione and ammonia)產生具有螢光特性的甲醛衍生物後，再以螢光-HPLC量測之，並藉以計算氫氧自由基的生成濃度。
研究結果顯示：當光觸媒濃度為0.01 g/L時，DMSO之濃度須維持在4 mM以上，已確認自由基捕捉劑可有效地覆蓋二氧化鈦光觸媒表面上所有的活化位置，而過低濃度的DMSO，會低估氫氧自由基的生成濃度；研究結果也顯示，氫氧自由基的生成濃度隨水溶液酸鹼值增加而增加，而提高光照強度也有助於提升氫氧自由基的生成濃度，且氫氧自由基濃度隨光照強度呈指數增加的關係；此外，研究中也發現，雖然反應系統中氫氧自由基的總生成濃度隨光觸媒劑量的增加而增加，但單位重量光觸媒所產生的自由基數反而減少，其係因為過高的光觸媒懸浮顆粒所引起的「遮蔽效應」所致；另外，研究中發現當以波長為446 nm之醫療燈管為光源時，氫氧自由基產量相當低。而以波長為256 nm為光源時，其氫氧自由基生成量為以波長365 nm為光源的2.5倍，較高的光照強度，仍有利於氫氧自由基的生成。
本研究根據前述環境因子與自由基生成濃度關係，針對液相光催化反應系統，建立一氫氧自由基生成濃度的經驗模式。將此經驗式所推估氫氧自由基生成濃度，與甲醛光催化分解反應速率相互驗證，發現兩者有良好之正相關。此外，本研究利用所建立之自由基捕捉/螢光法量測技術，將其應用於光觸媒量較少的薄膜式光催化反應系統，也證實此方法即使在試片表面生成微量的氫氧自由基，亦可以此技術量測其生成濃度，同時也實驗證實二氧化鈦氫氧自由基生成量，與甲基藍光催化分解速率間，具有良好之正比關係。

The study employs dimethyl sulfoxide (DMSO) as a radical capture for quantifying formation concentration of hydroxyl radicals (·OH) in liquid-phase TiO2-photocatalytic reaction systems. In this study, a trapper/fluoresce technique has been developed to monitor formation concentration of formaldehyde which is the major reaction intermediate from reacting DMSO with hydroxyl radicals. The initial formation rate of formaldehyde is applied to calculate yield rate of the hydroxyl radicals formed onTiO2 surfaces. Several affecting factors including solution pH level, TiO2 dosage, irradiated light intensity and different wavelength light sources have been tested to investigate the capability of applying the developed technique for determining photocatalyst photocatalytic activities in various operation conditions.
Experimental results indicate that DMSO concentration should be higher than 4 mM for covering most part of active sites on TiO2 particles while TiO2 concentration equal to 0.01 g/L. Otherwise, underestimation of ·OH formation concentration will be observed. The results also show hydroxyl radicals concentration increases with pH level due to increasing reactions between hydroxyl ions (OH-) with electron holes. More formation of hydroxyl radicals are detected in higher illumination light intensity, too. For the effect of TiO2 dosage concentration on the radical formation, it is observed that the overall radical yield rate increases withTiO2 concentration initially and then approaches a flat maximal level as TiO2 concentration above 200 mg/L. But the radical yield rate is declining with TiO2 concentration if the rate is expressed by unit gram of TiO2, which results from receiving less irradiated light intensity by each TiO2 particle because TiO2 particle scatters each other in high-concentration conditions. Besides, the experimental results indicate a low yield rate of hydroxyl radicals by using 446-nm light sources. The radical yield rate by using 256-nm lamps is about 2.5 times higher than by using 365-nm lamps.
Finally, according to the achieved relationships among hydroxyl radical yield rates and the experimental parameters, a semi-empirical model for predicting formation rate of hydroxyl radicals is proposed in this study based on the variables including proton concentration, TiO2 concentration and irradiated light intensity. The prediction model demonstrates well correlations between radical concentrations and photocatalytic reaction rates assisted by TiO2, which not only shows the developed radical measurement technique being a good indicator representing photocatalytic activities of photocatalysts, but also indicates the formation of hydroxyl radical is the key reaction mechanism for fast degradation of organic compounds.

誌謝……………………………………………………………… i
中文摘要………………………………………………………… ii
英文摘要………………………………………………………… iv
目錄……………………………………………………………… vi
表目錄…………………………………………………………… ix
圖目錄…………………………………………………………… x
第一章、緒論…………………………………………………… 1
1-1 研究源起…………………………………………………… 1
1-2 研究目的…………………………………………………… 4
第二章、文獻回顧……………………………………………… 5
2-1 二氧化鈦液相光催化反應………………………………… 5
2-1-1半導體光觸媒性質……………………………………… 5
2-1-2半導體光催化反應基本原理……………………………… 8
2-1-3半導體光觸媒的選擇……………………………………… 11
2-2 光催化氧化程序之反應動力………………………………… 16
2-2-1 光催化反應步驟…………………………………………… 16
2-2-2 光催化反應動力模式……………………………………… 18
2-3 氫氧自由基特性與量測……………………………………… 20
2-3-1 氫氧自由基特性…………………………………………… 20
2-3-2 氫氧自由基的生成………………………………………… 21
2-3-3 氫氧自由基的量測方法…………………………………… 24
2-3-4 氫氧自由基濃度之估算方式……………………………… 31
2-4 影響光催化反應速率的環境因子…………………………… 33
2-4-1 pH值………………………………………………………… 33
2-4-2 光觸媒劑量與反應物濃度之影響………………………… 35
2-4-3 光源與光強………………………………………………… 37
2-4-4 水溶液中離子成分………………………………………… 39
第三章、研究方法………………………………………………… 41
3-1 實驗材料與設備……………………………………………… 45
3-1-1 實驗材料…………………………………………………… 45
3-1-2 實驗設備…………………………………………………… 46
3-2 實驗方法與分析……………………………………………… 46
3-2-1 實驗方法…………………………………………………… 46
3-2-2 甲醛分析…………………………………………………… 47
3-3 初步分析……………………………………………………… 49
3-3-1 試劑溶液pH對樣品螢光強度之影響……………………… 49
3-3-2 甲醛生成速率之選定……………………………………… 52
3-4 甲醛量測方法之QA/QC檢測………………………………… 54
3-4-1 空白實驗…………………………………………………… 54
3-4-2 甲醛檢量線………………………………………………… 54
3-4-3 重複性及穩定性之測試…………………………………… 55
3-5 DMSO捕捉劑濃度的影響……………………………………… 57
3-6 實驗設計……………………………………………………… 63
3-5-1 甲醛生成確認實驗………………………………………… 63
3-5-2 溶液pH對氫氧自由基生成量之影響……………………… 63
3-5-3 光觸媒濃度對氫氧自由基生成量之影響………………… 63
3-5-3-1 光觸媒濃度對光強度之影響…………………………… 64
3-5-4 UV光照強度對氫氧自由基生成量之影響………………… 64
3-5-5 微量氫氧自由基檢測分析之測試………………………… 66
第四章、結果與討論……………………………………………… 68
4-1甲醛生成確認實驗…………………………………………… 68
4-2 環境因子對氫氧自由基生成之影響………………………… 70
4-2-1 pH值之影響………………………………………………… 70
4-2-2 光觸媒濃度之影響………………………………………… 76
4-2-3 光照強度之影響…………………………………………… 82
4-2-4 不同波長光源之影響……………………………………… 85
4-3 氫氧自由基生成經驗式……………………………………… 89
4-4 氫氧自由基生成量與污染物降解速率之相關性…………… 92
4-5 微量氫氧自由基檢測分析之測試…………………………… 95
第五章、結論與建議……………………………………………… 101
5-1 結論…………………………………………………………… 101
5-2 建議…………………………………………………………… 102
參考文獻…………………………………………………………… 104
附錄A……………………………………………………………… A-1
附錄B……………………………………………………………… B-1
附錄C……………………………………………………………… C-1

1.Agustina T.-E.; Ang H.-M.; Vareek V.-K. (2005). "A review of synergistic effect of photocatalysis and ozonation on wastewater treatment." Journal of Photochemistry and Photobiology C: Phorochemistry Reviews 6: 264-273.
2.Anpo M.; Takeuchi M.; Ikeue K.; Dohshi S. (2002). "Design and development of titanium oxide photocatalysts operating under visible and UV light irradiation : the applications of metal ion-implantation techniques to semiconducting TiO2 and Ti/zeolite catalysts." Curr. Opin. Solid State Mater. Sci. 6: 381-388.
3.Ao C.-H.; Zou S.-C.; Mak C.-L. (2004). "Inhibition effect of SO2 on NOx and VOCs during the photogradation of synchronous indoor air pollutants at part per billion (ppb) level by TiO2." Applied Catalysis B:Environmental 49: 187-193.
4.Bardouki H.; Barcellos da Rosa M.; Mihalopoulos N.; Palm W.-U.; Zetzsch C. (2002). "Kinetics and mechanism of the oxidation of dimethylsulfoxide (DMSO) and methanesulfinate(MSI-) by OH radicals in aqueous medium." Atmospheric Environment 36: 4627–4634.
5.Benitez N.; Sarria V.; Parra S.; Adler N.; Péringer P.; Pulgarin C. (2002). "Recent developments in the coupling of photoassisted and aerobic biological processes for the treatment of biorecalcitrant compounds." Catalysis Today 76: 301–315.
6.Billany M.-R.; Khatib K.; Gordon M.; Sugden J.-K. (1996). "Alcohols and ethanolamines as hydroxyl radical scavengers." International Journal of Pharmaceurics 137: 143-147.
7.Cheng S.; Tsai S.-J.; Lee Y.-F. (1995). "Photocatalytic decomposition of phenol over titanium oxide of various structures." Catalysis Today 26: 87-96.
8.Coudray C.; Talla M.; Martin S.; Fatome M.; Favier A. (1995). "High-performance liquid chromatography-electrochemical determination of salicylate hydroxylation products as an in vivo marker of oxidative stress." Analyticl biochemistry 227: 101-111.
9.Datye A.-K.; Riegel G.; Bolton J.-R.; Huang M.; Prairie M.-R. (1995). "Microstructural characterization of a fumed titanium dioxide photocatalyst." Journal of Solid State Chemistry 115: 236-239.
10.Doong R.-A.; Chen C.-H.; Maithreepala R.-A.; Chang S.-M. (2001). "The influence of pH and cadmiun sulfide on the photocatalytic degradation of 2-chlorophenol in titanium dioxide suspensions." Water Research 35(12): 2873-2880.
11.Emeline A.-V.; Smirnova L.-G.; Kuzmin G.-N.; Basov L.-L.; Serpone N. (2002). "Spectral dependence of quantum yields in gas-solid heterogeneous photosysems influence of anatase/rutile content on the photostimulated adsorption of dioxygen and dihydrogen on titania." Journal of Photochemistry and Photobiology A: Chemistry 148: 97-102.
12.Farnood R.; Zang Y. (2005). "Photocatalytic decomposition of methyl tert-butyl ether in aqueous slurry of titanium dioxide." Applied Catalysis B: Environmental 57: 275-282.
13.Fang Y.; Wang Q.; Ding F.; Zhu N.; Li H.; He P. (2003). "Determination of hydroxyl radical by capillary zone electrophoresis with amperometric detection." Journal of Chromatography A 1016: 123-128.
14.Gomes A.; Fernandes E.; Lima J.-L.-F.-C. (2005). "Fluorescence probes used for detection of reactive oxygen species." J. Biochem. Biophys. Methods 65: 45-80.
15.Herrmann J.-M. (1999). "Heterogeneous photocatalysis: fundamentals and applications to the removal of various types of aqueous pollutants." Catal. Today: 115-129.
16.Hidalgo M.-C.; Colon G.; Navi o J.-A. (2002). "Modification of the physicochenical properties of commercial TiO2 samples by soft mechanical activation." Journal of Photochemistry and Photobiology A: Chemistry 148: 341-348.
17.Hoffmann M.-R.; Marti`n S.-T.; Choi W.; Bahnemann D.-W. (1995). "Environmental applications of semiconductor photocatalysis." Chemical Reviews 95: 69-96.
18.Hurum D.-C.; Agrios A.-G.; Crist S.-E.; Gray K.-A.; Rajh T.; Thurnauer M.-C. (2006). "Probing reaction mechanisms in mixed phase TiO2 by EPR." Journal of Electron Spectroscopy and Related Phenomena 150: 155-163.
19.Ichiura H.; Kitaoka T.; Tanaka H. (2003). "Removal of indoor pollutants under UV irradiation by a composite TiO2–zeolite sheet prepared using a papermaking technique." Chemosphere 50(1).
20.Ishibashi K.-I.; Fujishima A.; Watanabe T.; Hashimoto K. (2000). "Detection of active oxidative species in TiO2 photocatalysis using the fluorescence technique." Electrochemistry Communication 2: 207-210.
21.Ishibashi K.-I.; Fujishima A.; Watanabe T.; Hashimoto K. et al. (2000). "Quantum yields of active oxidative species formed on TiO2 photocatalyst." Journal of Photochemistry and Photobiology A: Chemistry 134: 139–142.
22.Jen J.-F.; Leu M.-F.; Yang T.-C. (1998). "Determination of hydroxyl radicals in an advanced oxidation process with salicylic acid trapping and liquid chromatography." Journal of Chromatography A 796: 283-288.
23.Kawahara T.; Konishi Y.; Tada H.; Tohge N.; Ito S. (2001). "Patterned TiO2/SnO2 bilayer type photocatalyst. 2. Efficient dehydrogenation of methanol." Langmuir 17: 7442-7445.
24.Kevin E.; O''Shea C.-C. (1995). "The reactivity of phenol in irradiated aqueous suspensions of TiO2. Mechanistic changes as a function of solution pH." Journal of Photochemistry and Photobiology A:Chemistry 91: 67-72.
25.Kiriakidou F.; Kondarides D.-I.; Verykios X.-E. (1999). "The effect of operational parameters and TiO2-doping on the photocatalytic degradation of azo-dyes." Catalysis Today 54: 119-130.
26.Koelsch M.; Cassaignon S.; Guillemoles J.-F.; Jolivet J.-P. (2002). "Comparison of optical and electrochemical properties of anatase and brookite TiO2 synthesized by the sol-gel method." Thin Solid Films 312: 403-404.
27.Kolar J.; Strlic M.; Pihlar B. (2001). "New colourimetric method for determination of hydroxyl radicals during ageing of cellulose." Analytica Chimica Acta 431: 313-319.
28.Konstantinou I.-K.; Sallas V.-A.; Albanis T.-A. (2002). "Photocatalytic degradation of propachlor in aqueous TiO2 suspensions. Determination of the reaction pathway and identification of intermediate products by various analytical methods." Water Research 36: 2733-2742.
29.Kormann C.; Bahnemann D.-W.; Hoffmann M.-R. (1991). "Photolysis of chloroform and other organic molecules in aqueous TiO2 suspensions." Environ. Sci. Technol. 25: 494-500.
30.Kuo W.-S.; Ho P.-H. (2006). "Solar photocatalytic decolorization of dyes in solution with TiO2 film." Dyes and Pigments 71: 212-217.
31.Lee Y.; Lee C.; Yoon J. (2004). "Kinetics and mechanisms of DMSO (dimethylsulfoxide) degradation by UV/H2O2 process." Water Research 38: 2579-2588.
32.Lin C.-Y.; Li C.-S. (2003). "Effectiveness of titanium dioxide photocatalyst filters for controlling bioaerosols." Aerosol Science and Technology 37: 162-170.
33.Linsebigler A.-L.; Lu G.; Yates Jr J.-T. (1995). "Photocatalysis on TiO2 surface: Principles, mechanism, and selected results." Chemical Reviews 95: 735-758.
34.Luo X.; Lehotay D.-C. (1997). "Determination of hydroxyl radical using salicylate as a trapping agent by gas chromatography-mass spectrometry." Clinical Biochemistry 30: 41-46.
35.Mohseni M. (2005). "Gas phase trichloroethylene(TCE) photooxidation and byproduct formation: photolysis vis titania/silica based photocatalysis." Chemosphere 59: 356-342.
36.Muruganandham M.; Swaminathan M. (2006). "Photocatalytic decolourisation and degradation of reactive Orange 4 by TiO2 -UV process." Dyes and Pigments 68: 133-142.
37.Newton G.-L.; Milligan J.-R. (2006). "Fluorescence detection of hydroxyl radicals." Radiation Physics and Chemistry 75: 473–478.
38.Ning P.; Bart H.-J.; Jiang Y.; Haan A.-D.; Tien C. (2005). "Treatment of organic pollutants in coke plant wastewater by the method of ultrasonic irradiation, catalytic oxidation and activated sludge." Separation and Purification Technology 41: 133–139.
39.Ohno T.; Sarukawa K.; Tokieda K.; Matsumura M. (2001). "Morphology of a TiO2 photocatalyst (Degussa P-25) consisting of anatase and rutile crystalline phases." Journal of Physical Chemistry B 203: 82-86.
40.Ohtani B.; Ogawa Y.; Nishimoto S. (1997). "Photocatalytic activity of amorphous-anatase mixture of Titanium(IV) Oxide particles suspended in aqueous solutions." Journal of Physical Chemistry B 101: 3746-3752.
41.Ozaki S.; Zhao L.-H.; Amemiya T.; Itoh K.; Murabayashi M. (2004). "Gas-phase photocatalytic degradation of cis-1,2-dichloroethylene using titanium dioxide under near-UV-illumination." Applied Catalysis B: Environmental 52: 81-89.
42.Sakai H.; Kawahara H.; Shimazaki M.; Abe M. (1998). "Preparation of ultrafine titanium dioxide particles using hydrolysis and condensation reactions in the inner aqueous phase of reversed micelles: Effect of alcohol addition " Langmuir 14: 2208 -2212.
43.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 Materials & Solar Cells 77: 65-82.
44.San N.; Hatipoglu A.; Kocturk G.; Cinar Z. (2002). "Photocatalytic degradation of 4-nitrophenol in aqueous TiO2 suspensions: Theoretical prediction of the intermediates." Journal of Photochemistry and Photobiology A:Chemistry 146: 189-197.
45.San N.; Hatipoglu A.; Kocturk G.; Cinar Z. (2001). "Prediction of primary intermediates and the photodegradation kinetics of 3-aminophenol in aqueous TiO2 suspensions." Journal of Photochemistry and Photobiology A: Chemistry 139: 225-232.
46.Sato T.; Tayta M. (2006). "Enhancement of phage inactivation using photocatalytic titanium dioxide particles with different crystalline structures." Biochemical Engineering Journal 28: 303-308.
47.Sclafani A.; Palmisano L.; Schiavello M. (1990). "Influence of the preparation methods of TiO2 on the photocatalytic degradation of phenol in aqueous dispersion." The Journal of Physical Chemistry(94): 829-832.
48.Singhal B.; Porwal A.; Sharma A.; Ameta R.; Ameta S.-C. (1997). "Photocatalytic degradation of cetylpyridinium chloride over titanium dioxide powder." Journal of Photochemistry and Photobiology A: Chemistry 108: 85-88.
49.Sumita T.; Yamaki T.; Yamamoto S.; Miyashita A. (2002). "Photo-induced surface charge separation of highly oriented TiO2 anatase and rutile thin films." Applied Surface Science 200: 21-26.
50.Sun B.; Vorontsov A.-V.; Smirniotis P.-G. (2003). "Role of platinum deposited on TiO2 in phenol photocatalytic oxidation." Langmuir 19: 3151-3156.
51.Sun L.; Bolton J.-R. (1996). "Determination of the quantum yield for the photochemical generation of hydroxyl radicals in TiO2 suspensions." The Journal of Physical Chemistry(100): 4127-4134.
52.Tai C.; Gu X.; Zou H.; Guo Q. (2002). "A new simple and sensitive fluorometric method for the determination of hydroxyl radical and its application." Talanta 58: 661-667.
53.Tai C.; Peng J.F.; Liu J.F.; Jiang G.B.; Zoub H. (2004). "Determination of hydroxyl radicals in advanced oxidation processes with dimethyl sulfoxide trapping and liquid chromatography" Analytica Chimica Acta 527: 73–80.
54.Wong C.-C.; Chu* W. (2003). "The direct photolysis and photocatalytic degradation of alachlor at different TiO2 and UV sources." Chemosphere 50: 981-987.
55.Wu J.-F.; Hung C.-H.; Yuan C.-S. (2005). "Kinetic modeling of promotion and inhibition of temperature on photocatalytic degradation of benzene vapor." Journal of Photochemistry and Photobiology, A: Chemistry 170: 299–306.
56.Wu K-R.; Hung C.-H.; Liu W.-C. (2006). "Effect of several sputtering parameters on structural and photocatalytic properties of nitrogen-doped titanium oxide films." Elsevier Editorial System for surface and Coatings Technology.
57.Yang X.-F.; Guo X.-Q. (2001). "Investigation of the anthracene-nitroxide hybrid molecule as a probe for hydroxyl radicals."
58.Yoneyama H.; Torimoto T. (2000). "Titanium dioxide / adsorbent hybrid photocatalysts for photodestruction of organic substances of dilute concentrations." Catalysis Today 58: 133-140.
59.Zhang Q.; Gao L.; Guo J. (2000). "Effects of calcination on the photocatalytic properties of nanosized TiO2 powders prepared by TiCl4 hydrolysis." Applied Catalysis B:Environmental 26: 207-215.
60.Zhang Z.; Wang C.-C.; Zakaria R.; Ying J.-Y. (1998). "Role of particle size in nanocrystalline TiO2-based photocatalysts." Journal of Physical Chemistry B 102: 10871-10878.
61.洪崇軒、鄭佳倩，“建立以自由基捕捉/螢光法測定光催化系統中氫氧自由基之生成”, 高科大工學院2007年教師研發成果研討會, 高雄, Taiwan, May 3 (2007).
62.吳致誠，“UV/TiO2程序中氫氧自由基之生成研究”，碩士論文，國立中興大學環境工程研究所，台中，1999。
63.黃欣栩、曾迪華、莊連春，“UV/TiO2系統中氫氧自由基產生與單氯苯降解效果之相關性”，第二十九屆廢水處理技術研討會，2004。
64.邱琬婷、謝永旭、劉謹銓、高肈郎、李佳欣、張名毅，“以銀、鉑改質二氧化鈦薄膜反應器之光催化活性研究”，廢水處理技術研討會，2006。
65.宋衛鋒,倪亞明,何德文，“電解法水處理技術的研究進展”，化工環保期刊，第21卷第一期，p11-12，2001。
66.汪涵，“電化學技術在環保領域的應用”，化工環保期刊，第25卷第5期，2005。
67.林有銘，“奈米光觸媒環境大氣淨化應用技術”，化工技術，Vol. 14，4月號，2006。
68.鄭正垣，“水中甲醛之二氧化鈦光催化分解研究”，國立高雄第一科技大學環境與安全衛生工程系，碩士論文，2006。
69.楊蘭芳，“液相光催化反應之氫氧自由基生成量測-以二甲基亞碸為自由基捕捉劑”，國立高雄第一科技大學環境與安全衛生工程系，碩士論文，2006。
70.魏慶華、呂金塗、蘇武忠、陳君閣、張景閔，“濺鍍TiO2薄膜受紫外光照射之親水性分析”，南台科技大學機械工程系，2006。