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研究生: 姚雅雪
Yao, Ya-Syue
論文名稱: 銀/鉑奈米島狀薄膜於電漿子增強的光催化產氫應用
Application of Ag/Pt Nanoisland Films in Plasmon-Enhanced Photocatalytic Hydrogen Evolution Reaction
指導教授: 陳家俊
Chen, Chia-Chun
口試委員: 陳家俊
Chen, Chia-Chun
陳俊維
Chen, Chun-Wei
郭聰榮
Kau, Tsung-Rong
王迪彥
Wang, Di-Yan
口試日期: 2021/07/29
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2021
畢業學年度: 109
語文別: 中文
論文頁數: 75
中文關鍵詞: 表面電漿共振銀/鉑奈米島狀薄膜賈凡尼置換反應產氫反應
英文關鍵詞: Surface plasmon resonance, Ag/Pt nanoisland films, Galvanic replacement reaction, Hydrogen evolution reaction
DOI URL: http://doi.org/10.6345/NTNU202101137
論文種類: 學術論文
相關次數: 點閱:111下載:0
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  • 近年來全球對於環保課題逐漸重視,積極發展對於環境友善的綠色能源,使得氫能受到廣泛注意。由於產氫反應(Hydrogen evolution reaction, HER)的動力學相當緩慢,需要開發具有良好效率的催化劑,以促進反應發生。貴金屬鉑(Pt)被證實是最佳的產氫催化材料,但其價格高昂並且地球含量稀少限制其發展應用,因此需開發出鉑負載量低且高活性的催化劑。本實驗利用金種誘導生長法,結合金種和多侖試劑(Tollens’ ragent),在ITO導電玻璃上製作銀奈米島狀薄膜(Ag nanoisland film, Ag-NIF)。通過調控Ag前驅物(AgNO3)、Ag+穩定劑(NH4OH)和還原劑(glucose)的濃度與生長時間等參數來調整島與島間隙(Gap)。接著在溴化十六烷基三甲銨 (CTAB)、抗壞血酸 (AA)、60℃環境下,以銀島狀結構做為模板,利用賈凡尼置換反應(Galvanic replacement),將鉑還原至銀表面形成銀/鉑奈米島狀薄膜(Ag/Pt-NIF),利用SEM圖研究奈米結構表面的變化,並利用感應偶合電漿質譜儀(ICP-MS)進行元素定量分析,最後將此材料應用在光催化產氫反應。結果顯示,催化效果最好的樣品Ag/Pt-NIFs (500 μM)置換比例為10:1(Ag: Pt),鉑含量僅有0.01396 mg/cm2;此外,當Ag/Pt-NIFs置換比例為70:1時,Gap distance約為15.2 nm其光催化產氫增強效果最好,僅需0.00264 mg/cm2鉑負載量,在電流密度為-10 mA/cm2時,與沒照光相比,照光後過電位降低約96 mV。由於銀奈米島狀結構具有強烈的表面電漿共振(Longitudinal surface plasmon resonance, LSPR)效應,其吸收光譜可以從可見光到近紅外光的範圍,實驗結果證明我們的銀/鉑奈米島狀薄膜在光催化可提升產氫的表現。

    In recent years, global environmental protection has received great attention, which has promoted the development of green energy, including the hydrogen evolution reaction (HER). Since the kinetics of HER is relatively slow, it is necessary to develop a catalyst with good efficiency to promote the reaction. Platinum (Pt) has been demonstrated to be the best catalytic material for HER. However, the high price and scarcity limit its development and application. A good HER catalyst should have low platinum loading and high activity. In this study, the seed-mediated growth method was used to prepare the Ag-NIFs by combining gold seeds and Tollens’ reagent. The gap distances of the Ag-NIFs can be controlled by adjusting the amount of silver precursor (AgNO3), silver stabilizer (NH4OH) and reducing agent (glucose). For the preparation of Ag/Pt-NIFs, the as-prepared Ag-NIFs were used as the templates to carry out the galvanic replacement reaction in a solution containing CTAB and AA at 60℃. SEM images were used to provide the information of surface changes on the nanostructures, and ICP-MS was used for quantitative analysis of elements. Then, the Ag-NIFs and Ag/Pt-NIFs were used for photocatalytic HER. According to the results, photocatalytic HER of the Ag/Pt-NIFs showed the best plasmon-enhancement, when the gap distance was 15.2 nm. In addition, the platinum loading was 0.00264 mg/cm2. Comparing the results of AM 1.5G irradiation and non-irradiation, at the current density of -10 mA/cm2, the applied overpotential decreased about 96 mV. Based on the LSPR of silver nanostructures, the absorption spectrum can range from visible light to near-infrared light. Our results demonstrated that our Ag/Pt-NIFs reveal the capability of plasmon-enhanced photocatalytic HER.

    謝誌 I 摘要 II Abstract III 目錄 IV 圖目錄 VII 表目錄 XI 第一章 緒論 1 1-1 替代能源 1 1-2 產氫方法簡介 3 1-2-1 目前主流的產氫方法 3 1-2-2 電解水產氫法 4 1-2-3 光催化與光電化學產氫法 5 1-3 觸媒材料對於產氫反應的應用 7 1-3-1 過渡金屬複合材料 7 1-3-2 半導體材料 8 1-3-3 貴金屬奈米複合材料 9 1-4 Plasmon enhancement對催化反應影響 12 第二章 文獻回顧與研究動機 14 2-1 研究動機 14 2-2 產氫反應 (Hydrogen Evolution Reaction, HER) 15 2-3 銀奈米島狀薄膜 (Ag Nanoisland Film, Ag-NIF) 18 2-4 SPR與LSPR特性 20 2-4-1 表面電漿共振 (Surface Plasmon Resonance, SPR) 20 2-4-2 局部表面電漿共振 (Localized Surface Plasmon Resonance, LSPR) 20 2-5 賈凡尼置換反應 (Galvanic Replacement Reaction) 21 第三章 實驗藥品及儀器設備 22 3-1 實驗藥品 22 3-2 實驗儀器介紹及基本原理 24 3-2-1 氧電漿機 24 3-2-2 旋轉塗佈機 25 3-2-3 往返式恆溫水槽 25 3-2-4 恆溫循環水槽 26 3-2-5 溫控型電磁加熱攪拌器 27 3-3 分析儀器介紹及基本原理 28 3-3-1 紫外光-可見光-近紅外光吸收光譜儀 (UV/Visible/NIR Spectrophotometer) 28 3-3-2 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM) 29 3-3-3 感應耦合電漿質譜儀 (Inductively Coupled Plasma Mass Spectrometry, ICP-MS) 30 3-3-4 恆定電位儀 (Autolab) 30 第四章 實驗步驟 31 4-1 ITO基板清洗及表面改性 32 4-2 修飾ITO表面為NH2 32 4-3 銀奈米島狀薄膜的製備 32 4-4 利用置換反應合成銀/鉑奈米島狀薄膜 33 4-5 光電化學產氫性能量測 34 4-6 ICP-MS樣品前處理 34 第五章 結果與討論 35 5-1 ITO基板表面修飾分析(ITO-NH2) 35 5-2 銀奈米島狀薄膜表面形貌與光學性質分析 37 5-2-1 反應時間對銀奈米島狀薄膜之影響 39 5-2-1 前驅物硝酸銀濃度對銀奈米島狀薄膜之影響 43 5-3 不同置換比例對銀/鉑奈米島狀薄膜表面形貌與光學性質分析 47 5-3-1 硝酸銀濃度為250 μM之不同銀/鉑比例置換 47 5-3-2 硝酸銀濃度為500 μM之不同銀/鉑比例置換 50 5-3-3 硝酸銀濃度為750 μM之不同銀/鉑比例置換 53 5-4 光電化學產氫性能測試 56 5-4-1 銀奈米島狀薄膜產氫性能測試 56 5-4-2 銀/鉑奈米島狀薄膜產氫性能測試 58 5-5 元素分析及定量分析 67 第六章 結論與未來展望 69 參考文獻 70

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