利用水热法合成钛酸盐奈米管及其性质研究-国立高雄科技大学化学工程

中文摘要本研究利用水熱法(Hydrothermal Method)分別合成二氧化鈦和鈦酸鹽奈米管，將商業用二氧化鈦粉末與10 M 的氫氧化鈉水溶液均勻攪拌後置入壓力釜內進行水熱處理，在不同水熱反應溫度(110、130、150、180 ℃)、反應時間(12、24、48 hr)條件下製備鈦酸鹽奈米管，並藉由表面質子化製備二氧化鈦奈米管。

經FE-SEM 及TEM 觀察發現，鈦酸鹽奈米管管長約50 ~ 100 nm，管徑約10 ~ 15 nm，經XRD 可得知其組成具有氫/鈉鈦酸鹽的晶相(例如NaHTi3O7•xH2O)，且隨著水熱處理溫度增加原先氫/鈉鈦酸鹽的晶相將轉變成Na2Ti6O13 棒狀結構。

二氧化鈦奈米管經TEM 觀察發現，二氧化鈦奈米管管長與管徑都與鈦酸鹽奈米管差不多，經XRD 可得知其組成具有二氧化鈦銳鈦礦及鈦酸鹽化合物的晶相。

BET 分析結果顯示，二氧化鈦奈米管比表面積高達316 m2/g，高於鈦酸鹽奈米管之比表面積184 m2/g。

以水熱法所製備得奈米管光催化活性試驗結果顯示，鈦酸鹽奈米管在紫外光照射下，吸附率高於光降解效率。

二氧化鈦奈米管在紫外光照射下，其降解亞甲基藍效率優於鈦酸鹽奈米管。

於光催化有機酸廢水部分，以水熱處理溫度為110 ℃於500 ℃煅燒後所得之二氧化鈦奈米管粉末為最佳光觸媒，對草酸及矽酸有機廢水之光催化降解率分別為78％及64％。

英文摘要Titanate and titanium dioxide nanotubes were prepared via a hydrothermal method by using commercially available TiO2 powders in a 10 M NaOH solution at various temperatures (110 oC, 130 oC, 150 oC and 180 oC) for 12-48 hours, respectively. The specific surface areas of the as-prepared nanotubes before and after protonating, respectively, were characterized by FTIR, XRD, BET, Raman and TEM. The results showed that the as-prepared titanate nanotubes exhibit an average diameters of around 10-15 nm with 50-100 nm in lengths. The XRD patterns indicated that titanate nanotubes are sodium/hydrogen titanate structures (e.g. NaHTi3O7xH2O). The nanotubes were transferred into Na2Ti6O13 nanorod structures as the reaction temperature above 180 oC during the hydrothermal process. The BET surface areas of the titanium dioxide nanotubes treated by protonating the surface are 316 m2/g, which is much higher than the surface areas of titanate nanotubes’ at 184 m2/g.It was found that the absorption effect is better than the photo-decomposition effect in titanate nanotubes was the methylene blue solution irradiated by UV light. In contrast, the degradation experiments of methyl blue solution showed that the titanium dioxide nanotube is much more effective than the titanate nanotube. Hydrothermal process was adopted for the synthesis of TiO2 nanotubes and was used as photocatalyst. The catalysts were prepared at 110 oC in an autoclave and calcined at 500 oC exhibited the best performance of photocatalytic properties. The synthesized TiO2 nanotubes were implemented for the best photocatalytic degradation of organic dye, methyl blue(MB) than titanate nanotubes by UV irradiation from aqueous media. The photocatalytic degradation of oxalic acid and silicic acid solutions are 78 % and 64 %, respectively.目錄中文摘要I英文摘要Ⅱ目錄Ⅲ表目錄Ⅵ圖目錄Ⅶ第一章緒論 11.1前言11.2 研究動機 3第二章文獻回顧 52.1 二氧化鈦基本性質 52.2 二氧化鈦奈米管的製備 112.2.1 水熱法(Hydrothermal Method) 112.2.2 溶膠凝膠法(Sol-Gel Method) 122.2.3 模板製造法(Template Replica Process) 132.2.4 自組裝法(Self-assembly Process) 142.3 水熱法文獻回顧152.4 水熱法影響鈦酸鹽奈米管形狀之因素182.5 煅燒改質文獻回顧232.6 鈦酸鹽奈米管之文獻回顧242.7 染料之種類與特性272.8 染料之發射原理292.9 二氧化鈦的光催化機制30第三章實驗方法與步驟323.1 實驗藥品323.2 分析儀器353.3 實驗程序383.3.1 氧化鈦奈米管之製備程序383.3.1.1 鈦酸鹽奈米管之製備程序383.3.1.2 氮摻雜二氧化鈦奈米管之製備程序383.3.2 實驗設計423.4 光催化系統433.4.1 鈦酸鹽及二氧化鈦奈米管降解染料廢水實驗443.4.2 二氧化鈦奈米管降解草酸有機廢水實驗463.4.3 二氧化鈦奈米管降解矽酸有機廢水實驗49第四章結果與討論504.1 鈦酸鹽奈米管之物性分析504.1.1 傅立葉轉換紅外光譜儀分析(FTIR) 504.1.2 熱重量測儀(TGA) 524.1.3 X-光繞射儀分析(XRD) 544.1.4 拉曼散射光譜儀(RAMAN) 564.1.5 比表面積分析與孔徑分析(BET) 584.1.6 穿透式電子顯微鏡(TEM) 604.2 二氧化鈦奈米管之物性分析634.2.1 傅立葉轉換紅外光譜儀分析(FTIR) 634.2.2 熱重量測儀(TGA) 654.2.3 X-光繞射儀分析(XRD) 684.2.4 拉曼散射光譜儀(RAMAN) 724.2.5 比表面積分析與孔徑分析(BET) 744.2.6 穿透式電子顯微鏡分析(TEM) 764.27. 能量分散分析儀(EDS) 814.3 奈米管降解亞甲基藍之檢測854.3.1 未照光實驗854.3.2 紫外光波長(254nm)之光催化實驗874.4 二氧化鈦奈米管降解偶氮染料之檢測904.5 二氧化鈦奈米管降解草酸有機廢水之檢測924.6 二氧化鈦奈米管降解矽酸有機廢水之檢測94第五章結論97參考文獻1. 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