本研究以正丁氧基鈦為前驅物，三嵌段高分子P123為模板，鎢酸銨與尿素為鎢氮來源，採溶凝膠法一次共水熱的方式合成鎢與氮共摻雜的二氧化鈦。掃描式電子顯微鏡觀察摻雜鎢之前含氮二氧化鈦及摻雜之粉末為1 - 5μm實心圓球體，摻雜鎢後則外形受鎢酸銨影響較不規則。由氮氣吸脫附檢驗顯示其結構屬中孔洞結構。可見光催化檢驗中，摻雜鎢氮的二氧化鈦，對羅丹明B染料的降解效果均優於未摻雜的二氧化鈦與商用二氧化鈦P25，其反應機構為摻雜鎢可促使電子電洞有效分離，羅丹明B染料與粉體照光後產生發色團分解反應及脫乙基反應達降解效果。由XPS圖譜分析，氮以γ-N型鍵結，為Ti-N-O或Ti-O-N的鍵結方式與二氧化鈦結合。添加鎢酸銨後，O 1s、Ti 2p結合能往正向偏移。本研究已成功的以溶凝膠法合成具良好可見光催化效果的鎢與氮共摻雜的二氧化鈦。

The sphere-like W,N-codoped TiO2 photocatalysts were prepared by a simple one-pot hydrothermal synthesis route, using tetrabutyl titanate as the TiO2 precursor through sol-gel process, urea and ammonium tungstate as the nitrogen and tungsten sources, and the triblock copolymer Pluronic P123 as the template. The morphology and microstructure characteristics of W,N-codoped titania photocatalysts with different amount of tungsten doping were characterized by means of XRD, BET, SEM, XPS, DRS and UV-Vis. The metal and nonmetal codoped W,N-TiO2 shows a much superior photocatalytic activity to the commercial titania P25 and undoped titania under visible light irradiation. A plausible mechanism of codoping is proposed. It is presumed that incorporation of nitrogen and tungsten leads to the formation of new mid-gap states and effectively narrow the band gap between the valence band and the conduction band; this greatly improves the photocatalytic activity in the visible light region. On the other hand, the tungsten ions with changing valences in the W,N-TiO2 are considered to act as trapping sites, which effectively decrease the recombination rate of photo-induced electrons and holes, thereby increasing the photo-oxidation efficiency of the catalysts.

論文審定書 i
誌謝 ii
摘要 iii
Abstract iv
圖目錄 viii
表目錄 x
第一章 緒論 1
1.1 前言 1
1.2 研究動機與目的 1
第二章 文獻回顧 4
2.1 光觸媒簡介 4
2.1.1 半導體材料 4
2.1.2光催化反應原理 4
2.2 影響光催化因素 6
2.2.1光的強度 6
2.2.2 pH值 6
2.2.3 反應溫度 7
2.2.4 有機物濃度 7
2.2.5 光觸媒性質 8
2.3 金屬氧化物 8
2.3.1 二氧化鈦基本性質與結構 8
2.3.2 三氧化鎢基本性質與結構 9
2.4 溶膠凝膠之發展與反應過程 10
2.5 孔洞結構 11
2.5.1吸脫附曲線 12
2.5.2中孔洞材料 15
2.6 二氧化鈦的改質 16
2.6.1 金屬離子摻雜 16
2.6.2 非金屬離子摻雜 16
2.6.3 鎢的摻雜 16
第三章 實驗方法 19
3.1 實驗藥品 19
3.2 實驗流程 19
3.3 樣品代號 21
3.4 實驗儀器分析方法 21
3.4.1 X光繞射儀( X-ray Diffractometer，XRD ) 21
3.4.2比表面積分析儀 ( Surface Area and Porosimetry Analyzer ) 22
3.4.3場發射掃描式電子顯微鏡( Field Emission Scanning Electron Microscope，SEM ) 22
3.4.4可見光光催化實驗 22
3.4.5 X射線光電子能譜儀( X-ray Photoelectron Spectrometer，XPS ) 23
3.4.6 紫外-可見光漫反射光譜分析( Diffuse Reflectance spectroscopic，DRS ) 23
第四章 結果與討論 24
4.1不同的鎢酸銨添加量對性質的影響 24
4.1.1 X光繞射分析 24
4.1.2紫外-可見光漫反射光譜分析 25
4.1.3 可見光降解分析 26
4.1.4 BET比表面積與孔洞結構分析 29
4.1.5 SEM電子顯微鏡分析 31
4.2不同煅燒溫度對於光觸媒粉末之影響 33
4.2.1 X光繞射分析 33
4.2.2 可見光降解分析 35
4.2.3 BET比表面積與孔洞結構分析 39
4.2.4 紫外-可見光漫反射光譜分析 41
4.2.5 SEM電子顯微鏡分析 42
4.3 TW-3的電子能譜儀特性分析 44
4.4 TW-3對於不同染劑Rh B、MB的降解差異分析 49
4.5 鎢氮共摻雜二氧化鈦於可見光光催化降解機制 50
第五章 結論 52
第六章 建議未來工作 53
參考文獻 54

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