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研究生： 庄美志
Chong, Mei-Chi
論文名稱： 以鋅和還原石墨烯改質二氧化鈦於可見光下降解空氣污染物二甲基硫之研究
ZnxTiO2/rGO nanocomposites for photocatalytic degradation of dimethyl sulfide (DMS) by visible-light irradiation
指導教授： 朱信
Chu, Hsin
學位類別： 碩士
Master
系所名稱： 工學院 - 環境工程學系
Department of Environmental Engineering
論文出版年： 2020
畢業學年度： 108
語文別： 英文
論文頁數： 162
中文關鍵詞： 光催化劑 、二氧化鈦 、含硫揮發性有機化合物 、表面氧空位
外文關鍵詞： Photocatalysts, Titanium dioxide, sulphide-containing volatile organic compounds, surface oxygen vacancy
相關次數： 點閱：108  下載：0 
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    • 揮發性有機化合物(VOCs)是造成空氣污染的主要原因之一，並可能導致霧霾、臭氧層損耗和温室效應等問題，其主要排放來自石油、化工、溶劑工業及自然界中生物質的降解等。在眾多類別的揮發性有機化合物中，含硫揮發性有機化合物被認為是日常生活中臭味的主要源頭。由於此類揮發性有機化合物對日常生活品質、人體健康和環境皆有危害，多項相關法項已被訂定用以監管和限制其排放和室內濃度。此外，硫中毒導致的催化劑老化問題一直是催化領域上的一大難題。因此，尋找合適的技術控制並減少含硫揮發性有機化合物的排放是現今重要的議題。
    光催化是一種有效、合乎經濟效益且十分具前景的去除揮發性有機化合物的技術，特別適用於低濃度的室內污染物，這是由於光催化劑由相對便宜的半導體組成，可在常温常壓下進行反應，且適用於各種不同類型的有機化合物。在過去的十多年間，二氧化鈦一直被視為十分具有潛力的光催化劑而被廣泛研究，雖然二氧化鈦具有安全無害、低成本、穩定和易製備等優點，但其快速的電子空穴對再結合率和寬能帶間隙所導致的低效光利用率大大限制其光催化能力和實際應用。眾多研究表示金屬或非金屬摻雜可以有效地降低二氧化鈦的能隙和電子空穴再結合率，從而提高其在可見光下的活性。然而，由於摻雜可能造成兩種截然相反的效果，摻雜物的種類和數量都需要經過仔細的研究和分析。在理想的摻雜條件下，摻雜分子可提高電子和空穴的分離；當摻雜量過多時，摻雜分子則會造成大量的體相缺陷並成為電子空穴再結合的位點，導致活性降低。
    本研究通過溶劑熱法製備二氧化鈦，同時利用還原氧化石墨烯和鋅改質以提高其在可見光條件下的光催化能力，二甲基硫用於模擬含硫揮發性有機化合物作為本研究中的降解目標。本研究闡釋了利用還原氧化石墨烯和鋅改質後二氧化鈦的相關材料表徴和動力學研究。XRD數據表明所製得的光催化劑主要由銳鈦礦和板鈦礦兩相組成。二氧化鈦成功摻入還原氧化石墨烯和鋅，且鋅主要以氧化鋅的形態生長在二氧化鈦晶界或團簇的邊界中；通過SEM和TEM圖譜可以看到光催化劑的顆粒大小約為10 nm；BET結果顯示加入還原氧化石墨烯和鋅後材料的比表面積有所增加；TGA和FTIR圖譜表示0.1rGO/Zn1TiO2 上具有較少的吸附水分子，這是由於其表面具有較多的氧空位所致；拉曼數據進一步證明了板鈦礦和還原氧化石墨烯的存在，以及通過鋅改質後出現的表面氧空位；UV-Vis光譜顯示加入還原氧化石墨烯和鋅後二氧化鈦的能隙有所降低；通過XPS數據可以對材料表面的價態進行半定量分析，Ti3+和表面氧空位皆隨鋅含量的增加而增加；PL圖譜表現出在0.1rGO/Zn1TiO2 中具有較多的電子遷移，這是由於結構缺陷(包括氧空位和Ti3+)在禁帶間形成的副能帶所導致。
    表面氧空位和Ti3+對光催化性能有着十分重要的影響，其可在價帶和導帶間形成的副能帶降低了把電子從價帶激活至導帶所需的能量，藉此提高了二氧化鈦在可見光下的利用率和催化活性。此外，表面氧空位也提高了催化劑的氧吸附能力，亦可以作為反應物和超氧活性基的反應位點，從而提高光催化效率。

    Volatile organic compounds (VOC) is one of the major contributors of air pollution which may cause the formation of urban smog, stratospheric ozone depletion and greenhouse effects. The main emission of VOCs is from petroleum refineries, chemical industries, solvent processes and decomposition of biosphere and biomass, etc. Among different classifications of VOCs, sulphur-containing VOCs (SVOCs) are always considered as the major resources of malodor and toxic. Owing to its influence on life quality, human health and environment, many stringent regulations are imposed to restrict the emission and indoor concentration of VOCs. Besides, sulphur poisoning is known as a difficult problem leading to rapid deactivation in the catalysis field. Therefore, it is necessary to control and reduce the emission of SVOCs.
    Photocatalysis is an efficient, promising and cost-effective technique to remove VOCs, especially for low concentration indoor pollutants. These behaviors are because photocatalysis can be operated at ambient temperature and pressure and is suitable for wide range of pollutants by using inexpensive semiconductors. TiO2 has received considerable attention for its well potential as photocatalysts in the past few decades. Although TiO2 is safe, relatively low-cost, stability, ease of synthesis and nontoxicity, the high recombination rate of photoinduced carriers and low light utilization given by its wide band gap limited its photocatalytic activity and practical application. Numerous researches reported metal or non-metal doping can extend the light adsorption of TiO2 to visible light by reducing band gap and decreasing electron and hole recombination. However, the type and amount of dopant require detailed study on accounting of it two contrasting effect. At the optimal amount of dopant, it acts as charge carrier bridge and improve the separation of e--h+, remarkably increasing the photocatalytic efficiency. Beyond the optimal amount, dopant induce immoderate bulk defects and serve as recombination center, leads to decreasing the photocatalytic efficiency.
    In this study, TiO2 are modified by rGO and Zn via solvothemal in order to improve its photocatalytic efficiency under visible light irradiation. Dimethyl sulfide (DMS) are chosen as simulated pollutants of SVOCs. A series of characterization and kinetic study were comprehensively presented. XRD results show that the synthesized photocatalysts are mainly consisted of anatase and brookite phase. TiO2 are successfully fabricated with rGO and Zn are grown on the boundary of TiO2 agglomeration in the form of ZnO. SEM and TEM images display the average particle sizes range are 10 nm. BET data indicate the specific surface area increases by the addition of rGO and Zn. TGA and FTIR reveal that 0.1rGO/Zn1TiO2 has less adsorbed water molecules on the surface because of the higher content of surface oxygen vacancy. Raman spectra further evidence that the presence of brookite phase and rGO and the advent of surface oxygen vacancy owing to the modification of Zn. UV-Vis spectra demonstrate the band gap of TiO2 slightly decreases due to the addition of rGO and Zn. XPS results give quantitative analysis of surface chemical state. The amount of oxygen defects and Ti3+ are increased with the increasing amount of Zn. PL spectra illustrate more electron transition are provoked in 0.1rGO/Zn1TiO2, in the results of the advent of deep level band within the forbidden band caused by structural defects (including surface oxygen vacancy and Ti3+).
    Surface oxygen vacancy and Ti3+ are crucial impact factors of photocatalytic performance. The formation of deep level band between VB and CB significantly reduce the energy required for excitation of electron from VB to CB, resulting in higher light utilization and remarkably promoting the photocatalytic activity under visible light. Besides, surface oxygen vacancies can enhance the adsorption of exoteric oxygen and act as active sites for the reaction of superoxide and pollutants, therefore, increasing the photocatalytic efficiency.

    CONTENT 摘要 I Abstract III 致謝 V Content VI List of Table IX List of Figure XI CHAPTER 1 Introduction 1 1-1 Motivation 1 1-2 Objectives 3 CHAPTER 2 Literature survey 5 2-1 Introduction of air pollutants 5 2-1.1 Volatile Organic Compounds (VOCs) 6 2-1.2 Chlorinated Volatile Organic Compounds (CVOCs) 8 2-1.3 Sulphide-containing Volatile Organic Compounds (SVOCs) 9 2-1.4 Dimethyl sulfide 10 2-2 Control method of VOCs 13 2-3 Photocatalysis 17 2-3.1 Photocatalysts 17 2-3.2 Mechanism of photocatalysis 18 2-3.3 Impact factors of photocatalytic activity 21 2-3.4 Synthesis method of photocatalysts 22 2-4 TiO2 for photocatalysis 26 2-4.1 TiO2 26 2-4.2 Modification of TiO2 27 2-5 Heterojunction semiconductor 29 2-6 Graphene-based photocatalysts 30 2-7 Chemical reaction mechanism 33 2-7.1 Impact factor of photocatalytic performance 34 2-7.2 Plug flow reactor 36 2-8 Catalytic kinetic model 39 2-9 Arrhenius equation 43 2-10 Van’t Hoff equation 43 CHAPTER 3 Material and methods 45 3-1 Research scope 45 3-2 Experimental materials and equipment 46 3-3 Photocatalysts Preparation 48 3-3.1 Synthesis of reduced graphene oxide 48 3-3.2 Synthesis of Photocatalysts 51 3-3.3 Preparation of immobilized photocatalyst film 55 3-4 Photocatalytic reactor 56 3-4.1 The stability and photolysis of simulated DMS gas system 57 3-4.2 Calibration curve 59 3-5 Photocatalysts characterization 59 3-5.1 Thermogravimetric / differential thermal analysis (TG/DTA) 59 3-5.2 X-ray powder diffraction spectroscopy (XRD) 60 3-5.3 Scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) 60 3-5.4 Transmission electron microscopy (TEM) 60 3-5.5 Fourier transform infrared spectroscopy (FTIR) 61 3-5.6 Diffuse reflectance spectra (DRS) 61 3-5.7 X-ray photoelectron spectroscopy (XPS) 62 3-5.8 Brunauer-Emmett-Teller (BET) surface area analysis 62 3-5.9 Raman spectroscopy 65 3-5.10 Photoluminescence (PL) 65 3-5.11 Inductively coupled plasma optical microscopy (ICP-OES) 65 CHAPTER 4 Results and Discussion 66 4-1 Photocatalysts Characterization 66 4-1.1 XRD 66 4-1.2 ICP-OES 69 4-1.3 SEM Image 70 4-1.4 TEM Image 73 4-1.5 BET 80 4-1.6 TGA 83 4-1.7 FTIR 87 4-1.8 Raman 89 4-1.9 UV–Vis spectroscopy 93 4-1.10 XPS 96 4-1.11 Photoluminescence 109 4-2 Photocatalytic activity tests 112 4-2.1 Photocatalytic performance of various photocatalysts 112 4-2.2 Photocatalytic performance under various conditions 115 4-3 Mechanism of photocatalytic reaction 116 4-3.1 Intermediate study by FTIR 116 4-3.2 Mineralization study 119 4-3.3 Reaction pathway 120 4-4 Parameters Test 125 4-4.1 Effect of initial concentration 125 4-4.2 Effect of temperature 127 4-4.3 Effect of retention time 129 4-4.4 Effect of humidity 131 4-5 Kinetic study 134 CHAPTER 5 Conclusion and suggestion 140 5-1 Conclusion 140 5-2 Suggestion 141 Reference 142   LIST OF TABLE Table 2 1 Diverse definition of VOCs in different countries/ organizations 7 Table 2 2 Physical properties of CVOCs and relevant regulations. a 8 Table 2 3 Physical properties of SVOCs and relevant regulations. a 9 Table 2 4 Material safety data sheet of dimethyl sufides. 12 Table 2 5 Characteristics, advantages and limitation of the technologies for VOC elimination (Referred from (Delhoménie et al., 2005; Huang et al., 2016a; Kumar et al., 2011b; Sudnick et al., 1994; Thevenet et al., 2014)). 15 Table 2 6 The benefits and drawbacks comparison between a variety of synthesis routine (Referred from (Asim et al., 2014; Athar, 2015; Carter et al., 2013; Grabowska et al., 2018; Makhlouf, 2011; Mu et al., 2019; Najafpour et al., 2007; Rane et al., 2018; Riikonen, 2016; Zhang et al., 2016b)). 24 Table 2 7 The structural parameters and band gap Four main polymorphs of TiO2 (Referred from (Lance, 2018; Ma et al., 2014)). 27 Table 2 8 The reaction rate expressions in various reaction models. 42 Table 3 1 The contents of dopants and doping ratio. 52 Table 4 1 Structural properties of bare TiO2 and rGO/Zn co-modified TiO2. 69 Table 4 2 Estimation of Zn and Ti content by ICP-OES. 69 Table 4 3 BET specific surface area and porous properties of various photocatalysts. 80 Table 4 4 Intensity ratio of D/G and 2D/G bands in graphite, its derivative compounds and 0.1rGO/ZnXTiO2. 91 Table 4 5 The position and full width at half maximum (FWHM) of Raman Eg mode of anatase. 93 Table 4 6 Band gap and Band edge wavelength of various photocatalysts. 94 Table 4 7 XPS results for the Ti 2p region: binding energy, full widths at half-maximum, area and proportion. 103 Table 4 8 XPS results for the O 1s region: binding energy, full widths at half-maximum, area and proportion. 106 Table 4 9 The conversion and reaction rate of DMS by 0.1rGO/Zn1TiO2 under various initial DMS concentrations. 126 Table 4 10 The conversion and reaction rate of DMS by 0.1rGO/Zn1TiO2 at various reaction temperatures. 128 Table 4 11 The conversion and reaction rate of DMS by 0.1rGO/Zn1TiO2 with various retention times. 130 Table 4 12 The conversion and reaction rate of DMS by 0.1rGO/Zn1TiO2 with various relative humidities. 132 Table 4 13 Parameters design and the experimental reaction rate of kinetic study. 135 Table 4 14 Results of kinetic model fitting: reaction rate constant (k), adsorption equilibrium constants of DMS and water (KA, KW), and R2. 136 Table 4 15 Fitting results of parameters in Arrhenius equation and Van’t Hoff equation. 139   LIST OF FIGURE Figure 1 1 Research procedure flow charts. 4 Figure 2 1 Overview of VOC chemistry in nature (Adapted from (Vandenbroucke, 2015)). 6 Figure 2 2 Atomic structure of DMS. 11 Figure 2 3 VOCs control technology for scope of application (Adapted from (Revah et al., 2005; Shareefdeen, 2005)). 14 Figure 2 4 Electrochemical potentials of the band edges of some semiconductors (interfaced with a pH 7 electrolyte solution) (Referred from (Belver et al., 2019; Di Paola et al., 2013; Tay et al., 2016; Yao, 2018)). 17 Figure 2 5 Thermodynamic requirements for a) photocatalytic water splitting, b) degradation of pollutants and c) CO2 reduction over a given semiconductor. OER; oxygen evolution reaction, HER; hydrogen evolution reaction, WOR; water oxidation to radicals of hydroxyl(ˑOH), ORR; oxygen reduction reaction and CRR: CO2 reduction reaction. 19 Figure 2 6 Schematic illustration of an irradiated photocatalyst particle (Reprinted from (Belver et al., 2019)). 19 Figure 2 7 Photoinduced reactions in TiO2 photocatalysis and the corresponding time scales (Reprinted from (Schneider et al., 2014)). 21 Figure 2 8 Crystalline structures of TiO2 in different phase: (a) anatase, (b) rutile, (c) brookite and (d) TiO2 (B) (Reprinted from (Ma et al., 2014)). 27 Figure 2 9 A schematic of (a) Schottky junction, (b) p-n heterojunction between two semiconductors, (c) p-n heterojunction with Ohmic Layer, and (d) bulk heterojunction (Reprinted from (Jang et al., 2012)). 30 Figure 2 10 Different structure of graphite family. 32 Figure 2 11 Steps in a heterogeneos catalytic reaction (Reprinted from (Fogler, 2006) Chapter 9). 33 Figure 2 12 Plug flow reactor. 39 Figure 3 1 Flow chart of photocatalytic research method. 46 Figure 3 2 Schematic of preparation of graphite oxide. 49 Figure 3 3 Flowchart of preparation of graphite oxide. 50 Figure 3 4 Flowchart of preparation of graphene oxide and reduced graphene oxide. 51 Figure 3 5 Schematic of preparation of photocatalysts. 53 Figure 3 6 Flowchart of preparation of photocatalysts. 54 Figure 3 7 Graphical illustration for the synthesis of rGO/ZnxTiO2 nanocomposite. (Referred to (Wang et al., 2013a)). 55 Figure 3 8 The photocatalytic experiments structure. 57 Figure 3 9 Photocatalytic reactor 57 Figure 3 10 The optical degradation of DMS under visible light. 58 Figure 3 11 The photocatalytic performance of TiO2 under UV-Vis and visible light (with filter) only irradiation. 58 Figure 3 12 The calibration curve of DMS concentration for GC-MS. 59 Figure 3 13 The IUPAC classification of adsorption isotherms (Cited from (Thommes et al., 2015)). 63 Figure 3 14 Classification of hysteresis loops and their related pore shapes (Adapted from (Thommes et al., 2015)). 64 Figure 4 1 XRD Pattern of graphite and its derivative compounds. 67 Figure 4 2 XRD Pattern of bare TiO2 and rGO/Zn co-modified TiO2. 68 Figure 4 3 SEM images of (a-b) graphite flake, (c-d) graphite oxide, (e-f) GO, (g-h) rGO. 71 Figure 4 4 SEM images of bare TiO2 and rGO/Zn co-modified TiO2. 72 Figure 4 5 TEM micrograph of GO: (a) magnification × 3,000, (b) × 25,000, (c) × 25,000 and (d) SAED pattern. 74 Figure 4 6 TEM micrograph of rGO: (a) magnification × 10,000, (b) × 50,000, (c) × 100,000 and (d) SAED pattern. 75 Figure 4 7 TEM micrograph of bare TiO2: (a) magnification × 50,000, (b) × 100,000, (c) × 150,000; High-resolution TEM micrograph of TiO2: (d-e) magnification × 800,000 and (f) SAED pattern. 76 Figure 4 8 TEM micrograph of 0.1rGO/TiO2: (a-b) magnification × 100,000, (c) × 150,000; High-resolution TEM micrograph of 0.1rGO/TiO2: (d) magnification × 500,000, (e) × 800,000 and (f) Fast Fourier transform (FFT) generated SAED pattern. 77 Figure 4 9 TEM micrograph of 0.1rGO/Zn1TiO2: (a) magnification × 100,000, (b-c) × 150,000; High-resolution TEM micrograph of 0.1rGO/Zn1TiO2: (d-e) magnification × 500,000 and (f) Fast Fourier transform (FFT) generated SAED pattern. 78 Figure 4 10 TEM micrograph of 0.1rGO/Zn5TiO2: (a) magnification × 150,000, (b) × 100,000, (c) × 150,000; High-resolution TEM micrograph of 0.1rGO/Zn5TiO2: (d-e) magnification × 500,000 and (f) SAED pattern. 79 Figure 4 11 Nitrogen adsorption-desorption curves of various photocatalysts. 81 Figure 4 12 Pore size ratio of various photocatalysts. 82 Figure 4 13 The size distribution of pores for various photocatalysts. 82 Figure 4 14 DSC-TGA curves of graphite and its derivative compounds. 84 Figure 4 15 DSC-TGA curves of TiO2, 0.1rGO/TiO2 and 0.1rGO/Zn0.01TiO2. 85 Figure 4 16 DSC-TGA curves of 0.1rGO/Zn0.1TiO2, 0.1rGO/Zn1TiO2 and 0.1rGO/Zn5TiO2. 86 Figure 4 17 FTIR spectra of graphite and its derivative compounds. 88 Figure 4 18 FTIR spectra of bare TiO2 and rGO/Zn co-modified TiO2. 89 Figure 4 19 Raman spectra of graphite and its derivative compounds. 90 Figure 4 20 Raman spectra of bare TiO2 and rGO/Zn co-modified TiO2. 92 Figure 4 21 UV-Vis absorption spectra of bare TiO2 and rGO/Zn co-modified TiO2. 94 Figure 4 22 Band gap energy of bare TiO2 and rGO/Zn co-modified TiO2 from UV-Vis absorption spectra. 95 Figure 4 23 Diffuse reflectance UV-Vis spectra of bare TiO2 and rGO/Zn co-modified TiO2. 95 Figure 4 24 Band gap energy of bare TiO2 and rGO/Zn co-modified TiO2 from Diffuse reflectance UV-Vis spectra. 96 Figure 4 25 High-resolution XPS spectra in C 1s region of graphite and its derivative compounds. 98 Figure 4 26 High-resolution XPS spectra in O 1s region of graphite and its derivative compounds. 99 Figure 4 27 High-resolution XPS survey spectra of graphite and its derivative compounds. 100 Figure 4 28 High-resolution XPS survey spectra of (a) bare TiO2, (b) 0.1rGO/TiO2, (c) 0.1rGO/Zn0.01TiO2, (d) 0.1rGO/Zn0.1TiO2, (e) 0.1rGO/Zn1TiO2 and , (c) 0.1rGO/Zn5TiO2. 102 Figure 4 29 High-resolution XPS survey spectra in Zn 2p region of 0.1rGO/Zn1TiO2 and 0.1rGO/Zn5TiO2. 102 Figure 4 30 High-resolution XPS survey spectra in Ti 2p region of bare TiO2 and rGO/Zn co-modified TiO2. 104 Figure 4 31 High-resolution XPS survey spectra in O1s region of bare TiO2 and rGO/Zn co-modified TiO2. 107 Figure 4 32 High-resolution XPS survey spectra in C1s region of bare TiO2 and rGO/Zn co-modified TiO2. 108 Figure 4 33 Photoluminescence spectra of bare TiO2 and rGO/Zn co-modified TiO2. 111 Figure 4 34 Schematic diagram of the band structure for different PL emission mechanisms (Referred to (Aguilar et al., 2017; Lin et al., 2014a; Liqiang et al., 2004)) 111 Figure 4 35 Photocatalytic activity of gaseous DMS over bare TiO2 and rGO/Zn co-modified TiO2 under visible light irradiation. 113 Figure 4 36 Conversion and reaction rates of DMS by various photocatalysts under room temperature, 60% relative humidity and RT = 30 s. 114 Figure 4 37 Schematic of the charge migration and separation on rGO/Zn co-modified TiO2. 114 Figure 4 38 Photocatalytic activity of gaseous DMS over 0.1rGO/Zn1TiO2 under various conditions with visible light irradiation (conditions: initial DMS concentration 2 ppm, 25°C and RT = 30 s). 115 Figure 4 39 The FTIR spectra of the exhaust gas by photocatalytic degradation process with 4 ppm DMS, 60% relative humidity, and 30 s retention time at 25 °C. 117 Figure 4 40 The FTIR spectra of the exhaust gas by photocatalytic degradation process with 2 ppm DMS, 60% relative humidity (N2 only), and 30 s retention time at 25 °C. 118 Figure 4 41 The FTIR spectra of the exhaust gas by photocatalytic degradation process with 2 ppm DMS, 0% relative humidity, and 30 s retention time at 25 °C. 118 Figure 4 42 The conversion and mineralization of DMS by 0.1rGO/Zn1TiO2 under various conditions. 120 Figure 4 43 Proposed pathway of photocatalytic degradation of DMS by rGO/Zn co-modified TiO2 under visible light irradiation. 123 Figure 4 44 Photocatalytic activity of DMS by 0.1rGO/Zn1TiO2 at various initial DMS concentrations. 126 Figure 4 45 Conversion and reaction rate of DMS by 0.1rGO/Zn1TiO2 at various concentrations under room temperature, 60% relative humidity, and RT = 30 s. 127 Figure 4 46 Photocatalytic conversion of DMS by 0.1rGO/Zn1TiO2 at various reaction temperatures. 128 Figure 4 47 Conversion and reaction rate of DMS by 0.1rGO/Zn1TiO2 at various reaction temperatures with 2 ppm initial DMS concentration, 60% relative humidity, and RT = 30 s. 129 Figure 4 48 Photocatalytic conversion of DMS over 0.1rGO/Zn1TiO2 with various retention times. 130 Figure 4 49 Conversion and reaction rate of DMS by 0.1rGO/Zn1TiO2 at various retention times with 2 ppm initial DMS concentration, 60% relative humidity, and temperature = 25°C. 131 Figure 4 50 Photocatalytic conversion of DMS by 0.1rGO/Zn1TiO2 at various relative humidities. 133 Figure 4 51 Conversion and reaction rate of DMS by 0.1rGO/Zn1TiO2 at various relative humidities with 2 ppm initial DMS concentration, 30 s retention time, and temperature = 25°C. 133 Figure 4 52 The predicted reaction rates from model 4 and the experimental values at (a) 298 K, (b) 308 K, and (c) 318 K. 137 Figure 4 53 Plot comparing the experimental reaction rates with the predicted reaction rates at various temperatures. 138 Figure 4 54 Regression of (a) reaction rate constant k with 1/T by Arrhenius equation, (b) adsorption equilibrium constant of DMS KA and (c) adsorption equilibrium constant of water KW with 1/T by Van’t Hoff equation. 138

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