揮發性有機化合物（VOCs）是重要的空氣污染物，他們會對人體的健康造成危害。含氯揮發性有機化合物已被廣泛地應用在各種工業生產和製藥程序上，主要作為溶劑，脫脂劑，以及各種清洗劑。1,2-二氯乙烷(1,2-dichloroethane, DCE)為工業上常用的有機溶劑，但如果在使用過程中排放到環境中，將對人體造成危害。另外，含硫揮發性有機硫化合物，由於其難聞的氣味與低嗅覺閾值引起了極大的關注。二甲基硫(DMS)和二甲基二硫(DMDS)皆含有非常低的嗅覺閾值。反覆接觸有氣味污染物，可能會引起慢性呼吸系統和心血管疾病，因此應極力消除此氣味污染物的排放，以改善人們生活居住的品質。
本研究利用溶膠凝膠法自行製備光觸媒，並藉由金屬/非金屬摻雜TiO2期望提高光觸媒在可見光下處理揮發性有機物的能力。首先以1,2-二氯乙烷篩選非金屬摻雜TiO2，實驗結果顯示硫摻雜具有較好之光催化效果。依上述結果，探討摻雜不同含硫比例之光觸媒光催化二甲基硫的能力。進一步在可見光下使用共摻雜光觸媒處理DMDS。同時利用各種輔助實驗，如TG/DTA、XRD、UV-Visible、FTIR、和XPS等儀器分析光觸媒晶相變化、粒徑分佈、吸光度、化學鍵結等物化特性。
對1,2-二氯乙烷進行光催化降解，結果顯示硫摻雜光觸媒比氮摻雜效果更好，主要由於其能隙較低與高表面積。依上述結果，接著以不同含硫比例摻雜光觸媒在可見光下處理二甲基硫，其結果顯示，經硫摻雜之光觸媒晶相已完全轉換為活性較佳的anatase晶相，且經硫摻雜的TiO2粒徑明顯變小。由XPS分析結果可知，S摻雜之光觸媒是以S6+型態存在，鍵結方式為Ti–O–S。在可見光的照射下，S0.05/TiO2顯示有較好之光催化效果，故選用S0.05/TiO2光觸媒作為後續研究。在操作參數實驗中，可知隨二甲基硫進流濃度(30、55、75和100 ppm)及相對濕度(10%、40%、80%)提高，轉化率隨之下降；隨進流溫度(25°C、35°C及45°C)上升二甲基硫之轉化率則會增加。此外，以Langmuir-Hinshelwood model模擬動力，結果顯示二甲基硫吸附常數KA大於H2O吸附常數KW，表示二甲基硫吸附能力大於H2O吸附能力。反應速率常數k隨溫度上升而提高，顯示整體反應受表面反應及吸附綜合影響，光催化反應之活化能為13.3 kJ mol–1。DMS光降解的主要氧化產物為SO2，CO2，二甲基二硫，二甲亞碸，二甲基碸，一氧化碳和甲磺酸。在乾燥條件下DMS的光催化降解主要有兩個反應途徑：C–S鍵的斷裂和超氧自由基對S的氧化；在潮濕的條件下光催化降解DMS主要包含兩個潛在反應途徑：氫氧自由基對S的氧化和C–S鍵的斷裂。
比較純TiO2和硫摻雜TiO2，可發現硫和金屬共摻雜的光觸媒具有更小的晶體，且利用可見光的能力更強。XPS的分析結果顯示：V4+，Fe3+，和S6+成功摻雜進入二氧化鈦的晶格，但是鋅離子卻是吸附在TiO2的表面上，形成複合光觸媒。S0.05Zn0.001/ TiO2顯示出對DMDS最佳之催化活性和對含硫揮發性有機化合物的抗毒性。DMDS的轉化率隨著相對濕度的提高而降低。另外，光催化效率亦隨著溫度的升高而增加，此現象主要可依碰撞理論而解釋之。Langmuir-Hinshelwood動力學第4型適合用於描述二甲基二硫的光催化降解特性。根據FT-IR和GC-MS的分析結果，光催化二甲基二硫後生成的含硫副產物包括SO2，C2H6S3（DMTS），C2H6O2S2（MMTS）和MSA，另外還可在氣相中測得CO2，CO，HCHO，和醋酸。二甲基二硫的光降解方式主要可分為：硫氧化，碳的氧化，以及S–S鍵斷裂。在乾燥與潮溼環境下，主要的關鍵影響因子分別是超氧自由基和•OH自由基。

Volatile organic compounds (VOCs) are important air pollutants with regard to their health implications and frequent occurrence. Chlorinated volatile organic compounds (Cl-VOCs) are widely used in industrial manufacture and pharmaceutical industries as solvents, degreasing agents, cleaning agents, and a variety of commercial products. 1,2-Dichloroethane (1,2-DCE), a widely used as one of organic solvents in the industry, can damage the human when it releases. Besides, Volatile organic sulfur compounds (VOSCs) have caused great concern due to their offensive odor, low odor thresholds value (OTV). Dimethyl sulfide (DMS) and dimethyl disulfide (DMDS) have an offensive smells with a very low odor threshold value (OTV). The anthropogenic source can easily result in local concentrations strongly exceeding OTV. Repeated exposure to odorous pollution can cause chronic respiratory and cardiovascular diseases. Eliminating pollutant emissions is achievable to improve the quality of life for people living.
In this study, photocatalysts were prepared by a sol-gel method. The photocatalytic performance of several nonmetal-doped TiO2 was evaluated for the degradation of 1, 2-DCE under visible light irradiation. Based on the result of 1, 2-DCE photodegradation, sulfur doped TiO2 for photocatalytic degradation of gaseous DMS was attempted. Soon afterwards, the photocatalysis performance of S,M (M = iron, vanadium, and zinc) co-doped TiO2 for photocatalytic degradation of gaseous DMDS under visible light irradiation was further conducted. The physical and chemical characteristics of photocatalysts were analyzed by thermo-gravimetric/differential-thermal analysis, X-ray diffraction, Fourier transform-infrared spectroscopy, UV-Visible spectroscopy, and XPS, respectively. The photocatalytic degradation of VOCs, kinetics of the reaction, and pathway of SVOCs photooxidation has been investigated under visible irradiation.
The results show the degradation rate of 1,2-DCE by S0.15/TiO2 is faster than that by N0.15/TiO2 because of its narrower band gap and the larger specific surface area. Therefore, the photocatalytic decomposition rate of dimethyl sulfide under visible light was expected to increase by doping sulfur. The result shows S-doped can reduce the crystalline size of TiO2 and all photocatalysts are anatase phase structure. The XPS results of S-doped TiO2 indicate that S exists as S6+ on the surface crystal lattices and leads to the formation of Ti–O–S in the TiO2 lattice. The activity of S-doped TiO2 was determined by the measurement of DMS degradation under visible light. According to the result of activity test, S0.05/TiO2 was chosen for further parameter studies. The conversion of DMS increases with the decreasing DMS concentration. The decomposition efficiency of DMS increases with decreasing relative humidity, and with increasing temperature. The presence of water vapor in air with DMS significantly impacts the photocatalytic activity. The phenomenon is ascribed to the competitive adsorption of water vapor and DMS on the active sites of the photocatalysts. By fitting the Langmuir-Hinshelwood model, the result shows that KA is larger than KW and it also represents that adsorption ability of DMS is greater than H2O. The value of k rises with the increasing temperature. The photocatalytic activation energy of the degradation of DMS by S0.05/TiO2 is 13.3 kJ mol–1. The main oxidation products of DMS photodegradation are SO2, CO2, DMDS, DMSO, DMSO2, CO, and MSA. There are two main reactions for photocatalytic degradation of DMS in dry condition: S oxidation by superoxide radicals and C-S bond cleavage. In the case of the wet condition, there are two potential reaction pathways for photocatalytic degradation of DMS: S oxidation by •OH radical and C-S bond cleavage.
Compared to S/TiO2, sulfur and transition metal co-doped TiO2 photocatalysts have smaller crystal sizes and shift further to visible-light absorption region. The XPS spectra confirm that V4+, Fe3+, and S6+ are successfully doped into the lattice of TiO2, but Zn2+ is adsorbed on the surface of TiO2. S0.05Zn0.001/TiO2 shows the best photocatalytic activity and S-VOCs tolerance for the degradation of DMDS under visible irradiation among all co-doped TiO2 photocatalysts. The conversion of DMDS decreases with increasing relative humidity. Besides, photocatalytic efficiency of DMDS increases with increasing temperature, which can be described by the rate law and explained by collision theory. The Langmuir-Hinshelwood model 4 is a feasible way to describe the photocatalytic degradation of DMDS by S0.05Zn0.001/TiO2 in this study. Based on the FT-IR and GC-MS characterization results, SO2, C2H6S3 (DMTS), C2H6O2S2 (MMTS), and MSA are the major sulfur-containing products of the photocatalytic degradation of gaseous DMDS, and CO2, CO, HCHO, CH3OOH, and H2O are also presented in the gas phase. Several organic products have been detected in the degradation of DMDS, which show the presence of different types of reaction: (1) oxidation of sulfur, (2) oxidation of carbon, and (3) cleavage of S–S bond. Superoxide radicals and •OH radical are considered the key species for the dry and wet reaction process, respectively.

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