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研究生： 鍾宜軒
Chung, Yi-Hsuan
論文名稱： 以鉑修飾之高分散二氧化鈦奈米管進行光催化產氫研究
Photocatalytic Hydrogen Production by Highly Dispersed Pt-Decorated Titania Nanotubes
指導教授： 楊家銘
Yang, Chia-Min
口試委員: 洪嘉呈
Horng, Jia-Cherng
張淑閔
Chang, Sue-Min
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2018
畢業學年度： 107
語文別： 中文
論文頁數： 119
中文關鍵詞： 二氧化鈦 、奈米管 、鉑修飾 、光催化產氫反應 、形貌調控
外文關鍵詞： titanate nanotube, titania nanorod, Pt-decorated
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    • 本研究利用水熱法合成鈦酸鹽奈米管以及二氧化鈦材料，並藉由SEM和XRD觀察其在不同pH值下的形貌與結構。發現將水熱24小時後的合成液在35 ℃下攪拌三天並搭配透析的方法，可製備出長度較短且整體較分散的奈米管。
    為觀察短奈米管在光催化產氫活性上的表現，我們將短奈米管鍛燒後，以光沉積的方式負載1 wt%的金屬鉑於表面，並將其結果與一般合成方式製備之奈米管作比較。我們發現材料中的鈉對於活性有很大的影響，且依據XPS的結果，不同製備方法所合成的材料其表面鉑的價態會隨著反應而改變，因此在穩定性上有差異。
    除了以後修飾的方式調控奈米管之外，我們研發出以一步驟合成法製備的鉑修飾二氧化鈦材料，並製備不同鉑含量的材料應用於光催化產氫反應中，找到最優化的條件。最後在本研究的結果中，發現在pH=2且含有1 wt%的鉑擁有最高的產氫活性。

    In this study, titanate and titania nanotubes (TNTs) were prepared under different pH values via hydrothermal treatment, and their morphologies and structures were analyzed using SEM and XRD. We found that nanotubes with much shorter length could be obtained by stirring and dialysis as post hydrothermal treatment.
    To study the photocatalytic activity performance of the short TNTs obtained with post-treatment for H2 production, the short TNTs were loaded with 1 wt% Pt by photodeposition, and the results were compared with that of the TNTs synthesized via conventional method (without post-treatment). We found that the photocatalytic activity performances were strongly affected by the presence of Na in TNTs, and TNTs prepared with different methods showed difference in the stability owing to the changes of Pt chemical states during catalysis according to XPS results.
    In addition to the post-treatment, we further developed a one-pot synthesis method for Pt incorporation into TNTs, and various Pt amount were tested to optimize photocatalytic activity for H2 production. Based on our results, TNTs with 1 wt% Pt obtained under pH=2 showed highest performance among all the samples.

    摘要………………………………………………………………………….I Abstract……………………………………………………………………...II 目錄………………………………………………………………………...IV 圖目錄………………………………………………………….….............VII 表目錄…………………………………………………………………..…XII 第一章 緒論 1 1.1 全球能源短缺與產氫技術 1 1.2 光催化產氫介紹 3 1.3 二氧化鈦光觸媒 8 1.3.1 二氧化鈦光觸媒簡介 8 1.3.2 二氧化鈦光催化產氫活性的改善 11 1.4 二氧化鈦奈米管簡介 16 1.4.1 二氧化鈦奈米管的合成方式 16 1.4.2 二氧化鈦奈米管特性與形成機制 18 1.4.3 二氧化鈦奈米管的修飾與改質 29 1.5 研究動機 32 第二章 實驗部分 34 2.1 實驗藥品 34 2.2 鈦酸鹽奈米管的合成 35 2.2.1 鈦酸鹽奈米管的合成 35 2.2.2 添加物對鈦酸鹽奈米管合成的影響 37 2.3 鉑修飾之二氧化鈦的製備 39 2.3.1 光沉積金屬鉑 39 2.3.2 一步驟合成法-水熱後加入鉑-乙二氨金屬溶液 41 2.4 光催化產氫反應研究 42 2.5 樣品命名 45 2.6 實驗鑑定與分析 46 2.6.1 X光粉末繞射儀 46 2.6.2 掃描式電子顯微鏡 47 2.6.3 能量散射光譜儀 49 2.6.4 穿透式電子顯微鏡 50 2.6.5 紫外/可見光吸收光譜儀 51 2.6.6 拉曼光譜儀 52 2.6.7 X光光電子能譜儀 53 2.6.8 光致發光光譜儀 54 2.6.9 X光螢光光譜儀 56 2.6.10 氮氣物理吸附儀 56 2.6.11 動態光散射 63 第三章 結果與討論 65 3.1 光觸媒合成與鑑定 65 3.1.1 鈦酸鹽奈米管的合成鑑定 65 3.1.2 添加物影響 71 3.1.3 鉑修飾之二氧化鈦材料鑑定 84 3.2 鉑修飾之二氧化鈦材料的光催化產氫結果 95 3.2.1 光沉積金屬鉑的產氫活性結果 95 3.2.2 一步驟合成法製備鉑修飾二氧化鈦材料的產氫活性結果 102 3.2.3 不同修飾鉑的方式產氫活性比較 104 第四章 結論 108 第五章 參考文獻 110 圖目錄 圖1- 1本多─藤島效應示意圖 3 圖1- 2兩種不同的光催化反應分類：上坡與下坡反應 4 圖1- 3綠色植物行光合作用與光催化水分解 4 圖1- 4光催化原理 5 圖1-5光觸媒水分解產氫的反應原理 6 圖1-6常見之半導體能階分佈圖 7 圖1- 7二氧化鈦晶體結構：(a)金紅石；(b)銳鈦礦；(c)板鈦礦 9 圖1- 8犧牲試劑反應機制 12 圖1- 9二氧化鈦負載金屬共催化劑 13 圖1- 10結晶性、晶粒大小與電子電洞對移動路徑 14 圖1- 11二氧化鈦掺雜陽離子與陰離子之光催化機制示意圖 15 圖1- 12模板法 18 圖1- 13陽極氧化法 18 圖1- 14合成態之鈦酸鹽奈米管之SEM與TEM影像 19 圖1- 15鈦酸鹽結構示意圖 21 圖1- 16各種不同結構鈦酸鹽奈米管的XRD繞射圖 22 圖1- 17奈米管隨溫度升高在形貌上的轉換 22 圖1- 18奈米管層間結構之示意圖 23 圖1- 19奈米管形成機制 25 圖1- 20奈米片形成奈米管的原因 28 圖1- 21修飾鈦酸鹽奈米管的方法 29 圖1- 22聚集如海膽狀之二氧化鈦奈米管 31 圖1- 23 (a)有序之TiO2微管作為前驅物；(b)水熱後產生之奈米管 31 圖1- 24經(a)PEG；(b)PEI修飾與(c)未修飾之奈米管 31 圖2- 1高壓釜構造圖 36 圖2- 2製備鈦酸鹽奈米管的實驗流程圖 36 圖2- 3添加en與對照組之實驗流程圖 38 圖2- 4 製備as-D-TNT-2的實驗流程圖 39 圖2- 5一步驟合成法製備鉑修飾之二氧化鈦材料流程圖 42 圖2- 6 LED燈與反應器 44 圖2- 7系統架設圖 44 圖2- 8布拉格繞射定律 46 圖2- 9 SEM構造示意圖 48 圖2- 10原子受電子束激發後產生歐傑電子之示意圖 49 圖2- 11 TEM構造示意圖 51 圖2- 12入射X光激發光電子示意圖 54 圖2- 13 PL裝置圖 55 圖2- 14光致發光原理 55 圖2- 15 PL光譜圖 55 圖2- 16氮氣吸附儀儀器架構 58 圖2- 17氣體等溫吸附曲線型態示意圖 58 圖2- 18遲滯曲線的型態示意圖 59 圖2- 19 t-plot法的示意圖 61 圖2- 20圓柱型孔洞示意圖 62 圖2- 21動態光散射的例子 ：上部顆粒較大、下部顆粒較小 64 圖3- 1不同pH值之鈦酸鹽奈米管XRD圖 66 圖3- 2不同pH值下的SEM影像 70 圖3- 3 as-TNT-7的TEM圖 70 圖3- 4 Si-TNT之SEM圖 73 圖3- 5 添加偏矽酸鈉的XRD結構鑑定 73 圖3- 6添加偏矽酸鈉後的FT-IR結構圖 73 圖3- 7 加入酯類後的SEM圖 75 圖3- 8 (a)~(c)水熱後產生的奈米片；(d)~(f)加入TEA後攪拌3小時；(g)、(h)水洗至pH=7的奈米管 78 圖3- 9 (a)~(c) en-1d；(d)~(f) en-3d；(g)、(f)Ti-3d的SEM圖 82 圖3- 10透析前(左)；透析後(右)的DLS光譜 83 圖3- 11 (a)、(b) en-3d透析後；(c)、(d)對照組透析後的SEM圖 83 圖3- 12 (a) as-TNT-7；(b) as-TNT-2；(a) as-D-TNT-7；(a) as-D-TNT-2 85 圖3- 13 鈦酸鹽奈米管經鍛燒後相轉換成銳鈦礦之XRD圖 87 圖3- 14材料經鍛燒後的Raman光譜 87 圖3- 15 光沉積金屬鉑於二氧化鈦材料之XRD圖 88 圖3- 16 (a) TNT-7-Pt；(b) TNT-2-Pt；(c) D-TNT-7-Pt；(d) D-TNT-2-Pt的SEM圖 89 圖3- 17 as-1Pt-TNT-7的SEM圖 92 圖3- 18 材料經空氣鍛燒(上)與經氫氣還原(下)之XRD圖 92 圖3- 19 (a) 1Pt-TNT-7-H2；(b)1Pt-TNT-2-H2的SEM圖 93 圖3- 20 1Pt-TNT-2-H2的TEM圖 94 圖3- 21光沉積1 wt%金屬鉑於不同二氧化鈦材料之產氫活性 95 圖3- 22不同材料的 PL光譜圖 97 圖3- 23 (a)、(b)TNT-2-Pt；(c)、(d)D-TNT-2-Pt的TEM圖 98 圖3- 24 各材料在Pt 4f 區域之XPS光譜分析 101 圖3- 25以一步驟合成法製備的金屬鉑二氧化鈦奈米管產氫活性 103 圖3- 26 一步驟合成1wt% Pt二氧化鈦奈米管的PL光譜圖 104 圖3-27 經鉑修飾之二氧化鈦材料產氫活性比較 106 圖3-28 經鉑修飾之二氧化鈦材料PL光譜圖 106 圖3-29 1Pt-TNT-2-H2反應前(a)；反應後(b)的XPS撮合圖 107 表目錄 表1- 1 anatase、rutile及brookite各項晶體結構的參數 10 表1- 2以結構分類之奈米管參考文獻 26 表3- 1一步驟合成法製備之材料命名 91 表3- 2 EDS元素分析 99 表3- 3 各材料利用XPS光譜分析之Pt0與PtOx的束縛能與比例 101 表3- 4 以一步驟合成法製備的金屬鉑二氧化鈦奈米管元素分析 103 表3- 5 材料利用XPS光譜分析之Pt0與PtOx的束縛能與比例 107

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