利用微波水熱法提升SiO2@ZnIn2S4奈米光觸媒表面均質與結晶性及其光催化產氫研究

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研究生：	黃彥禎 Yen-Chen Huang
論文名稱：	利用微波水熱法提升SiO2@ZnIn2S4奈米光觸媒表面均質與結晶性及其光催化產氫研究 Improving Coverage and Crystallinity of SiO2@ZnIn2S4 Nanoparticles Using Microwave-assisted Hydrothermal Method for Photocatalytic Hydrogen Evolution
指導教授：	李岱洲 Tai-Chou Lee
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程與材料工程學系 Department of Chemical & Materials Engineering
論文出版年：	2018
畢業學年度：	106
語文別：	中文
論文頁數：	133
中文關鍵詞：	奈米光觸媒、產氫、殼層結構、ZnIn2S4包覆二氧化矽
外文關鍵詞：	Nanoparticles photocatalyst, Hydrogen evolution, Core-shell structure, SiO2@ZnIn2S4
相關次數：	點閱：18 下載：0
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現代社會面臨能源以及環境危機，尋找乾淨的替代能源已為趨勢，太陽能因為取之無盡的太陽光照而具有最大的發展潛力，不過因為太陽能難以儲存，所以需要另尋方法儲存能量，其中一個儲存方式是將太陽能轉換成化學能，因此我們使用光觸媒接收太陽光能量後分解水產生氫氣的方式儲存太陽能。氫氣經過燃燒後只會產生能量以及水，是個乾淨無汙染的能源。
　　ZnIn2S4 (ZIS)是能隙值為2.4 eV的半導體可見光光觸媒，在太陽光的照射下會分解水產生氫氣。我們使用微波水熱法的方式合成ZIS光觸媒，之前的研究顯示如果將ZIS包覆在具有二氧化矽介電層外殼的金銀奈米粒子(GSNS@SiO2@ZIS)能夠藉由表面電漿效應有效地提升產氫效率，不過ZIS並不能均勻地包覆在GSNS@SiO2上，若能提升包覆的表面均質性與結晶性並且控制ZIS厚度，或許能夠更加理解影響產氫效率的因素。因為GSNS@SiO2合成不易，於是使用SiO2作為ZIS包覆的研究對象。
　　我們發現在純水溶液合成的SiO2@ZIS具有良好的結晶性，純乙醇合成的則是有較好的表面均質性，加入鹽酸控制在低pH值的情況下合成在兩種溶液中皆會提升結晶性，SiO2@ZIS的產氫效率隨著結晶性的增加而提升。乙醇與水的混和溶液結合了兩種溶液的優點，不過合成的SiO2@ZIS其性質卻難以詳細分析，雖然在不同比例混和溶液下合成不同層的ZIS能夠增加ZIS包覆SiO2的厚度，不能確實控制厚度以及只有外層ZIS參與分解水反應限制了重複包覆的實用性。最後我們在純乙醇溶液加入鹽酸合成SiO2@ZIS的方式達到提升表面均質以及結晶性的目的，並且能夠藉由改變ZIS前驅物的濃度控制ZIS的厚度。然而因為GSNS@SiO2與SiO2之間性質的差異，需要更長時間的研究才能將SiO2@ZIS相關的製程套用在GSNS@SiO2@ZIS上，不過也因如此我們對於使用複雜殼層結構光觸媒(GSNS@dielectirc@photocatalyst)優化太陽能產氫減少碳排放的目標又有了更進一步的發展。

Our society is facing growing challenges of energy and environment. In order to find clean and renewable energy resources instead of fossil fuels, many researchers worked hard and tried to find a way to solve the problem. Among these renewable energy resources, the biggest potential to develop is solar energy due to the endless of sun irradiation. To store the solar energy is another problem. One of the solutions is converting solar energy to chemical energy. So we use water-splitting photocatlyst to produce hydrogen under sun irradiation for energy storage. Hydrogen is a clean energy resource because it only produces water and energy after combustion.
ZnIn2S4 (ZIS) is a visible-light-driven photocatalyst with the energy band gap of 2.4 eV. We developed a microwave-assisted hydrothermal method to generate ZIS particles. In particular, our studies showed that the gold-silver nanoshells with SiO2 shell(GSNS@SiO2) embedded in ZIS matrix exhibited a unique plasmonic-enhanced photocatalytic hydrogen production. However, the coverage and thickness of ZIS on top of GS-NS were not precisely controlled. If we improve the crystallinity and coverage of ZIS to control shell thickness of ZIS, we can find out the factor which could affect hydrogen production efficiency. Because GSNS@SiO2 is hard to synthesize, our research is focusing on SiO2 core instead of GSNS@SiO2.
We found that SiO2@ZIS synthesized in pure water solution has better crystallinity, though synthesized in pure ethanol solution has better coverage. Adding HCl into both water and ethanol solution to lower pH condition would increase crystallinity, better crystallinity related to better hydrogen production efficiency. SiO2@ZIS synthesized in ethanol-water mixed solution would combine the advantage of two solutions, but the properties of the samples were too complex to analyze. Though ZIS shell could get thicker by repeating coating ZIS synthesized in different ratio of ethanol-water solution, not precisely controlling ZIS shell and only outer ZIS shell participating water-splitting reaction limited the use of repeating coating method. Finally we could increase crystallinity and coverage of SiO2@ZIS by adding HCl into pure ethanol solution, ZIS shell thickness could also be controlled by different concentration of ZIS precursor. However, due to the different properties between SiO2 core and GSNS@SiO2, it takes time to study SiO2@ZIS synthesis process applied to GSNS@SiO2. Thus, our facile procedure paves the way to generate a more complex structure GS-NS@dielectric@ photocatalyst, for optimization of solar hydrogen production.

目錄
摘要 ........................................................................................................................ I
Abstract .............................................................................................................. III
第一章、緒論 ....................................................................................................... 1
1-1 前言 ........................................................................................................ 1
1-2 光觸媒產氫 ............................................................................................ 3
1-3 研究動機 ................................................................................................ 5
第二章、文獻回顧 ............................................................................................... 7
2-1 光觸媒分解水產氫原理 ....................................................................... 7
2-2 光觸媒材料 .......................................................................................... 10
2-3 光觸媒材料的改進方式 ..................................................................... 14
2-3-1 能帶工程 .................................................................................. 14
2-3-2 產氫輔助觸媒 .......................................................................... 15
2-3-3 摻雜金屬 .................................................................................. 16
2-3-4 異質結構設計 .......................................................................... 17
2-3-5 表面電漿效應 .......................................................................... 18
2-4 ZnIn2S4光觸媒 ..................................................................................... 21
2-5微波水熱法製備光觸媒 ...................................................................... 25
2- 6 GSNS@SiO2@ZnIn2S4殼層結構光觸媒 ........................................... 27
2-7 二氧化矽奈米粒子的合成與改質 ..................................................... 31
第三章、實驗方法 ............................................................................................. 34
3-1 實驗藥品 ............................................................................................ 34
3-2 分析與實驗儀器 ................................................................................. 37
3-3 實驗步驟 .............................................................................................. 40
3-3-1 溶膠-凝膠法製備二氧化矽膠體以及MPS表面改質 .......... 40
3-3-2 微波水熱法合成ZnIn2S4 / SiO2@ZnIn2S4 .............................. 40
3-3-3 光觸媒粉體溶液產氫速率量測 .............................................. 41
3-3-4 奈米殼結構合成(GSNS@SiO2 / GSNS@SnO2) .................... 44
第四章、實驗結果與討論 ................................................................................. 48
4-1 前導 ...................................................................................................... 48
4-2 MPS改質二氧化矽性質 ..................................................................... 49
4-3 水溶液/乙醇溶液在pH控制下合成SiO2@ZIS ............................... 53
4-3-1 SiO2@ZIS成分分析 ................................................................. 53
4-3-2 水溶液/乙醇溶液在pH控制下合成SiO2@ZIS-表面均質性 ............................................................................................................. 54
4-3-3水溶液/乙醇溶液在pH控制下合成SiO2@ZIS-結晶性 ....... 57
4-3-4水溶液/乙醇溶液在pH控制下合成SiO2@ZIS-能隙值 ....... 60
4-3-5水溶液/乙醇溶液在pH控制下合成SiO2@ZIS-產氫效率 ... 61
4-4 乙醇與水混合溶液在pH控制下合成SiO2@ZIS ............................ 66
4-4-1乙醇與水混合溶液在pH控制下合成SiO2@ZIS-表面均質性與結晶性 ............................................................................................. 66
4-4-2乙醇與水混合溶液在pH控制下合成SiO2@ZIS-能隙值 .... 69
4-4-3乙醇與水混合溶液在pH控制下合成SiO2@ZIS-產氫效率 71
4-4-4 以不同乙醇與水混合溶液合成ZIS重複包覆SiO2 ............. 75
4-5 純乙醇加入鹽酸合成SiO2@ZIS結晶性與厚度控制 ...................... 79
4-5-1鹽酸加入量對純乙醇合成SiO2@ZIS厚度與結晶性影響 ... 80
4-5-3鹽酸加入量對純乙醇合成SiO2@ZIS能隙值影響 ................ 82
4-5-4鹽酸加入量對純乙醇合成SiO2@ZIS產氫效率影響 ............ 83
4-5-5 改變ZIS前驅物濃度控制純乙醇加鹽酸合成SiO2@ZIS厚度及其性質 ............................................................................................. 84
4-6 GSNS@SiO2@ZIS套用SiO2@ZIS合成法試合成 ........................... 90
第五章、結論與未來展望 ................................................................................. 96
附錄 ..................................................................................................................... 98
低壓產氫循環系統 ..................................................................................... 98
低壓產氫系統介紹 ............................................................................. 98
氫氣檢量線測定 ............................................................................... 100
產氫效率計算 ................................................................................... 102
產氫再現性 ....................................................................................... 104
奈米殼結構(GSNS@SiO2, GSNS@SnO2, GSNS@porousSiO2 @SnO2, GSNS=Ag@Au)的合成 ............................................................................ 105
Gold-silver nanoshells, GSNS金銀奈米粒子合成 ......................... 105
GSNS@SiO2二氧化矽外殼金銀奈米粒子合成 ............................ 107
GSNS@SnO2二氧化錫外殼金銀奈米粒子合成 ............................ 108
GSNS@porousSiO2@SnO2孔洞二氧化錫外殼金銀奈米粒子合成 ........................................................................................................... 109
參考文獻 ........................................................................................................... 111
                                

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