臺灣博碩士論文加值系統

二氧化鈦 (TiO2)為良好之光催化材料，對工業廢水中之染料有光降解作用，而在TiO2中摻雜氧化銦 (In2O3)形成之二氧化鈦-氧化銦 (TiO2-In2O3, Ti-In) 複合材料，可縮小TiO2能隙提高光催化活性。故本研究利用溶膠-凝膠法製備Ti-In複合材料，Ti-In再分別與碳-氮 (C-N)和硫-氮 (S-N)共摻雜以形成新之Ti-In-C-N和Ti-In-S-N複合觸媒，希望提高Ti-In光降解之效率。TiO2與In2O3的前驅物分別是四氯化鈦及氯化銦，C、N和S摻雜劑之來源分別是粉末活性碳、尿素和硫代硫酸鈉，一步驟進行SN改質則以L-半胱胺酸為前驅物。本研究製備Ti-In-S-N複合觸媒時需兩個步驟，先製備出Ti-In-S再與尿素合成Ti-In-S-N；另本研究以一個步驟改質Ti-In為Ti-In-SN，以比較Ti-In-S-N及Ti-In-SN之光催化活性。
由XRD分析顯示，Ti-In-SN、Ti-In-S-N與Ti-In-C-N之Anatase晶相比例分別為100%、64%和63%，均高於Ti-In之30%；Ti-In-C-N、Ti-In-S-N及Ti-In-SN複合觸媒之顆粒直徑分別為33 nm、33 nm及13 nm，均小於Ti-In 之57 nm；Ti-In、Ti-In-C-N、Ti-In-S-N及Ti-In-SN之能隙值分別為2.97 eV、2.86 eV、2.82 eV與2.75 eV，以C-N、S-N和SN共摻雜Ti-In均達到降低Ti-In能隙之目的。Ti-In-C-N、Ti-In-S-N和Ti-In-SN之SEM圖像均呈現高凝聚傾向且具有多孔結構和片狀結構，TEM圖像顯示Ti-In-C-N、Ti-In-S-N和Ti-In-SN之顆粒尺寸分別為25-50 nm、20-50 nm和15-80 nm；XPS分析顯示，Ti-In-C-N具有Ti-O-N，Ti-N-O和Ti-O-C之鍵結，在Ti-In-S-N中發現Ti-O-N、Ti-N-O和Ti-O-S鍵結，在Ti-In-SN證實有Ti-N-O、Ti-O-N和Ti-O-S鍵結形成。BET分析Ti-In、Ti-In-C-N、Ti-In-S-N及Ti-In-SN之比表面積，其值分別為35.7、35.6、42.3及48.6 m2/g。
本研究以染料C.I. Reactive red 2 (RR2)作為目標污染物，在光催化反應中比較各觸媒之光催化活性，光催化實驗使用254 nm紫外燈為光源，在pH 3及25 ℃下測試，UV/Ti-In、UV/Ti-In-C-N、UV/Ti-In-S-N和UV/Ti-In-SN中光催化降解反應均遵循擬一階動力式，去除RR2之擬一階反應速率常數分別為0.43、1.68、1.70及0.68 h-1。UV/Ti-In，UV/Ti-In-C-N和UV/Ti-In-S-N中RR2之比攝氧率分別為4.4、7.3及5.3 mg O2/g-MLVSS-h。本研究發現Ti-In共摻雜後所得之Ti-In-C-N、Ti-In-S-N和Ti-In-SN複合觸媒之光活性均較Ti-In為高，且處理後出流水之毒性較低，兩步驟合成之Ti-In-S-N光催化活性雖高於一步驟合成之Ti-In-SN，但合成過程相對耗時。

TiO2 is a good photocatalyst and plays a role in the photodegradation of dyes in industrial wastewater. When TiO2 is doped with In2O3, a TiO2-In2O3 (Ti-In) composite material is formed, which can decrease the band gap in TiO2 and increase its photocatalytic activity. This study employed the sol-gel method to prepare Ti-In composite materials. Ti-In was then co-doped with carbon-nitrogen (C-N) and sulfur-nitrogen (S-N) to form new Ti-In-C-N and Ti-In-S-N composite catalysts, respectively, with the aim of increasing the photocatalytic efficiency of Ti-In. The precursors of TiO2 and In2O3 were titanium tetrachloride and indium chloride, respectively. The sources of the C, N, and S dopants were activated carbon powder, urea, and sodium thiosulfate, respectively. L-cysteine was used as a precursor for the modification of SN. The study employed a 2-step process to prepare the Ti-In-S-N composite catalysts. The first step was to prepare the Ti-In-S, before the Ti-In-S-N was synthesized with urea. During the preparation of the Ti-In-SN catalyst by doping L-cysteine, the Ti-In was modified to Ti-In-SN, in order to compare the photocatalytic activity of the two catalysts (Ti-In-S-N and Ti-In-SN).
XRD analysis showed that the anatase crystalline phase ratios in Ti-In-SN, Ti-In-S-N, and Ti-In-C-N were 100 %, 64 %, and 63 %, respectively; they were all higher than Ti-In (30 %). The particle sizes of Ti-In-C-N, Ti-In-S-N, and Ti-In-SN were 33, 33, and 13 nm, respectively, all lower than Ti-In (57 nm). The band gap values of Ti-In, Ti-In-C-N, Ti-In-S-N, and Ti-In-SN were 2.97, 2.86, 2.82, and 2.75 eV, respectively, showing that co-doping Ti-In with C-N, S-N, and SN achieved the aim of decreasing the band gap of Ti-In. SEM images of Ti-In-C-N, Ti-In-S-N, and Ti-In-SN all showed a high tendency to agglomerate and all have a lamellar porous structure. TEM images showed that the particle dimensions of Ti-In-C-N, Ti-In-S-N, and Ti-In-SN were 25-50 nm, 20-50 nm, and 15-80 nm, respectively. The XPS analysis showed that Ti-In-C-N contains Ti-O-N, Ti-N-O, and Ti-O-C bonds; Ti-In-S-N contains Ti-O-N, Ti-N-O, and Ti-O-S bonds; and Ti-In-SN was verified to be formed Ti-N-O, Ti-O-N, and Ti-O-S bonds. A Brunauer-Emmett-Teller (BET) analysis was used to quantitate the specific surface areas of Ti-In, Ti-In-C-N, Ti-In-S-N, and Ti-In-SN. The resulting values were 35.7, 35.6, 42.3, and 48.6 m2/g, respectively.
C.I. Reactive red 2 (RR2) was used as a target pollutant for photocatalysis reactions to compare the photocatalytic activity of various catalysts. A 254 nm UV lamp was used as a light source and the experiment was carried out at pH 3 and 25 °C. The photodegradation reactions of the prepared Ti-In, Ti-In-C-N, Ti-In-S-N, and Ti-In-SN composite catalysts were observed to obey pseudo-first-order kinetics, with rate constants of 0.43, 1.68, 1.70, and 0.68 h-1, respectively. The specific oxygen uptake rates of RR2 photodegradation were 4.4, 7.3, and 5.3 mg O2/g-MLVSS-h, respectively. The results showed that the photoactivity of the Ti-In-C-N, Ti-In-S-N, and Ti-In-SN composite catalysts, obtained from the co-doping of Ti-In, were all higher than Ti-In, and the toxicities of the treated effluent were all lower than Ti-In. Although the photocatalytic activity of Ti-In-S-N based on a two-step synthesis was higher than Ti-In-SN, the synthesis process was relatively time-consuming.

中文摘要
ABSTRACT
致 謝
目 錄
表目錄
圖目錄
第一章、緒論
1-1研究動機
1-2研究目的
第二章、文獻回顧
2-1廢水處理簡介
2-2 高級氧化程序
2-2-1 臭氧氧化
2-2-2 過氧化氫氧化
2-2-3 Fenton 法
2-2-4 異相光催化
2-2-5 濕式氧化
2-3金屬氧化物半導體光催化
2-3-1 二氧化鈦 (TiO2)及氧化銦 (In2O3)
2-3-2 TiO2摻雜In2O3 (TiO2-In2O3, Ti-In)
2-3-3 Ti-In表面改質
第三章、實驗方法
3-1研究架構
3-2實驗藥品與儀器
3-3 偶氮染料
3-4觸媒合成
3-4-1 銦鈦複合觸媒之製備
3-4-2 硫改質銦鈦複合觸媒之製備
3-4-3 氮改質銦鈦複合觸媒之製備
3-3-4 碳氮共存改質鈦銦複合觸媒
3-4-5 硫氮共存改質鈦銦複合觸媒
3-4-6 L-半胱胺酸一步驟改質銦鈦複合觸媒
3-5觸媒表面特性分析
3-5-1 X光繞射光譜
3-5-2 掃描式電子顯微鏡
3-5-3 穿透式電子顯微鏡
3-5-4 比表面積分析儀 (BET)
3-5-5 X射線光電子能譜
3-5-6 紫外-可見光光譜儀 (分光光度計)
3-6 光催化降解實驗
3-7 比攝氧率試驗
3-8 混合液揮發性固體含量測定
3-9 反應動力學模擬
第四章、結果與討論
4-1 觸媒表面特性鑑定
4-1-1 XRD圖譜分析
4-1-2 SEM與TEM 圖像分析
4-1-3 XPS圖譜分析
4-2 觸媒光催化活性比較
4-2-1 Ti-In、Ti-In-C-N和Ti-In-S-N之光催化活性比較
4-2-2 Ti-In、Ti-In-S、Ti-In-N和Ti-In-SN之吸附及光催化活性比較
第五章、結論與建議
5-1 結論
5-2 建議
參考文獻
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