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研究生： 王鵬華
Peng-Hua Wang
論文名稱： 提升SiO2@ZnIn2S4奈米核殼結構光觸媒光催化產氫研究
Improving Photocatalytic Hydrogen Productions based on SiO2@ZnIn2S4 Core-shell Particles
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： 2020
畢業學年度： 108
語文別： 中文
論文頁數： 166
中文關鍵詞： ZnIn2S4 、光觸媒產氫 、殼層結構
外文關鍵詞： ZnIn2S4, Photocatalytic hydrogen production, Core-shell
相關次數： 點閱：8  下載：0 
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    • 能源危機深深影響著我們的社會和環境。尋找乾淨的替代能源成為當今重要且迫切的議題。與化石燃料相比，可再生能源有著對於環境友好且可永續發展的優勢。在可再生能源之中，氫能被視為最具潛力能源，因為氫氣燃燒過後只會產生水及能量。因此，發展可見光驅動的光觸媒水分解產氫至關重要。
    過去的研究顯示將ZnIn2S4 (ZIS)可見光光觸媒包覆在具有二氧化矽外殼的金銀奈米粒子(Gold Silver-Nano Shell@ SiO2, GS-NS@SiO2) ，能夠藉由表面電漿共振效應有效提升產氫效率。由於GS-NS@SiO2不易合成，實驗以SiO2@ZIS作為主要研究重點，其原因是兩者的表面功能相同。我們若能從中理解ZIS反應機制，就能了解結構相關特性，從而優化產氫。
    藉由改變硫代乙醯胺 (Thioacetamide, TAA)濃度及金屬前驅物的陰離子，發現可以調整其能隙值並且提升產氫。此外，研究顯示微調ZIS暴露面比例可以有效提升產氫，並提出合理的合成機制對其進行解釋。我們選擇了最佳產氫樣品，改變溫度及pH值兩大重要參數來探討其對產氫的影響。研究發現，在140 oC和pH = 3.45的條件下可以提高產氫效率。最後，本研究的目的是使SiO2 @ ZIS核層結構光觸媒將太陽能有效地轉化為氫能。

    Energy crisis impacts our society and environment. It is urgent to find clean and renewable energies. Compared with fossil fuel, renewable energies are more environmentally friendly toward sustainable development. Among renewable sources, hydrogen has the biggest decarbonization potential , because it only produces water and energy after combustion. Therefore, the advances of visible-light-driven photocatalysts for water splitting is critical.
    ZnIn2S4 (ZIS) is a visible-light-driven photocatalyst, being used in this research. Our previous studies revealed that the gold-silver nanoshells (GS-NS) with SiO2 buffer layer (GS-NS@SiO2) embedded in ZIS matrix exhibited a unique plasmonic-enhanced photocatalytic hydrogen production. Due to the difficulty of synthesizing GS-NS@SiO2, our research focused on the preparation of SiO2@ZIS, since the surface functionalities on SiO2 for both systems are the same. If we can understand the deposition mechanism of ZIS on SiO2, the structure-property relation can be realized. Thus, the hydrogen productions can be optimized.
    By changing thioacetamide (TAA) concentration and the anions of metal salts in the precursor, it was found that energy band gap can be adjusted and hydrogen production efficiency can be improved. Furthermore, our research shows that delicate tuning the percentage of exposed facet can improve hydrogen production. A synthesis mechanism was proposed. Two important parameters, temperature and pH, were then varied to optimize hydrogen evolution rates. It shows that at 140 oC and pH=3.45 can improve hydrogen production. Finally, the purpose of this study is to effectively convert solar energy into hydrogen energy using SiO2@ZIS core-shell photocatalysts.

    摘要 i Abstract ii 誌謝 iii 目錄 v 圖目錄 ix 表目錄 xvi 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 光觸媒材料 7 2-2 光觸媒分解水產氫 11 2-3 影響光觸媒產氫重要因素 15 2-4 ZnIn2S4 光觸媒 23 2-5 二氧化矽(SiO2)奈米粒子合成與改質 27 2-6 Core-shell光觸媒結構研究 30 第三章 實驗方法及步驟 34 3-1 實驗藥品 34 3-2分析與實驗儀器 38 3-3實驗步驟 41 3-3-1 溶膠-凝膠法製備二氧化矽膠體及MPS表面改質 41 3-3-2 微波反應器合成ZnIn2S4 42 3-3-3 微波反應器合成SiO2@ ZnIn2S4 42 3-3-4 光觸媒粉體溶液產氫量測 45 3-3-5 產氫值表示方式 48 第四章 實驗結果與討論 49 4-1 前導 49 4-2 MPS改質二氧化矽 50 4-2-1 改質後粒徑分析 50 4-2-2 改質前後性質分析 54 4-3不同硫代乙醯胺量(TAA)合成SiO2@ZIS效應 59 4-3-1 TAA合成硫化光觸媒機制 59 4-3-2 SiO2@ZIS-2 TAA 成分分析 60 4-3-3 SiO2@ZIS- TAA效應結晶性分析 61 4-3-4 SiO2@ZIS- TAA效應之形貌和組成分析 63 4-3-5 SiO2@ZIS- TAA效應之光學性質分析 66 4-3-6 SiO2@ZIS- TAA效應之比表面積探討 68 4-3-7 SiO2@ZIS- TAA 產氫效率及相關性質探討 70 4-4不同金屬前驅物(陰離子效應)合成Bare ZIS / SiO2@ZIS 76 4-4-1陰離子效應之結晶性分析 76 4-4-2陰離子效應之形貌和組成分析 79 4-4-3陰離子效應之光學性質分析 82 4-4-4陰離子效應產氫效率及相關性質探討 84 4-4-5產氫量子效率探討 91 4-5最佳化產氫樣品Mix2之溫度效應 93 4-5-1 溫度效應結晶性分析 93 4-5-2 溫度效應光學性質分析 94 4-5-3 溫度效應形貌分析 95 4-5-4 溫度效應組成分析 97 4-5-5 溫度效應產氫效率及相關性質探討 98 4-6最佳化產氫樣品Mix2 pH效應 102 4-6-1 pH效應結晶性分析 103 4-6-2 pH效應光學性質分析 104 4-6-3 pH效應形貌和組成分析 106 4-6-4 pH效應產氫效率及相關性質探討 110 4-7最佳化產氫樣品Mix2 不同TAA濃度之產氫表現 116 第五章 結論與未來展望 118 附錄 120 A.低壓產氫循環系統 120 1. 產氫系統介紹 120 2. 氣相層析儀參數設定和分析 122 3. 氫氣定量分析量測和反應系統產氫計算 125 4. 產氫再現性 128 B.金銀奈米粒子表面電漿共振研究 129 1. 表面電漿共振 129 2. 應用於光觸媒產氫 131 3. GSNS@SiO2@ZnIn2S4 光觸媒 132 參考資料 136

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