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研究生： 蕭淂雍
Hsiao, Te-Yung
論文名稱： 綜合研究硫化動力學和過渡金屬離子吸附以增強 CdSe(en)0.5奈米片的 HER 性能：深入分析中孔結構變化和自由基形成
Comprehensive study on sulfurization kinetics and adsorption of transition metal ions to enhance the HER performance of CdSe(en)0.5 nanosheets: in-depth analysis of mesoporous structural changes and radical formation.
指導教授： 劉沂欣
Liu, Yi-Hsin
口試委員： 劉沂欣
Liu, Yi-Hsin
謝明惠
Shieh, Ming-huey
高琨哲
Kao, Kun-Che
口試日期： 2024/07/03
學位類別： 碩士
Master
系所名稱： 化學系
Department of Chemistry
論文出版年： 2024
畢業學年度： 112
語文別： 中文
論文頁數： 70
中文關鍵詞： 硒化鎘 、硫化鎘 、光催化水分解產氫 、各向異性蝕刻 、硫化
英文關鍵詞： Cadmium Selenide, Cadmium Sulfide, Sulfurization, Photocatalytic Water Splitting, Anisotropic Etching
研究方法: 實驗設計法
DOI URL： http://doi.org/10.6345/NTNU202401703
論文種類： 學術論文
相關次數： 點閱：117  下載：0 
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    • 在我們的研究中，我們全面研究了 CdSe(en)0.5 奈米片在不同條件下的硫化動力學，強調了不同硫前驅物(硫化鈉/亞硫酸鈉；硫粉) 和氣氛 (氮氣；大氣) 的影響。我們透過柯肯德爾效應的角度，使用高解析度透射電子顯微鏡(HR-TEM)和能量色散 X 射線光譜（EDS）映射等先進技術，仔細分析材料的微觀結構，以了解形態變化和元素分佈。X 射線繞射（XRD）、EA-ICP 和元素分析證實了晶體結構和化學成分 (N:Se:S) 的變化，並利用氣相層析阻擋放電離子偵測器（GC-BID）發現不同硫化條件下的材料其光催化水分解析氫的顯著變化。電子順磁共振（EPR）分析進一步強調了氮氫自由基在催化過程中的關鍵作用，以及硫化後材料對環境敏感度變化，為了解硫化對自由基形成的影響提供了見解。此外，我們關於形成各向異性介孔結構的發現為利用過渡金屬離子的化學吸附提高催化效率開闢了新途徑，並有望在二維半導體光催化方面取得進展。

    In our study, we comprehensively investigated the sulfidation kinetics of CdSe(en)0.5 nanosheets under different conditions, emphasizing the effects of different sulfur precursors (Na2S/Na2SO3; sulfur powder) and atmospheres (nitrogen; ambient). Through the perspective of the Kirkendall effect, we meticulously analyzed the microstructure of the materials using advanced techniques such as high-resolution transmission electron microscopy (HR-TEM) and energy-dispersive X-ray spectroscopy (EDS) mapping to understand morphological changes and elemental distribution. X-ray diffraction (XRD), EA-ICP, and elemental analysis confirmed the changes in crystal structure and chemical composition (N:Se:S), and gas chromatography-barrier ionization discharge (GC-BID) revealed significant changes in the photocatalytic hydrogen evolution from water splitting under different sulfidation conditions. Electron paramagnetic resonance (EPR) analysis further emphasized the critical role of nitrogen-hydrogen radicals in the catalytic process and the changes in environmental sensitivity of the material after sulfidation, providing insights into the effect of sulfidation on radical formation. Additionally, our findings on the formation of anisotropic mesoporous structures open up new avenues for enhancing catalytic efficiency through the chemical adsorption of transition metal ions, promising advancements in two-dimensional semiconductor photocatalysis.

    Abstract ii 圖次 v 第一章 緒論 1 1.1 二維結構及硫化半導體 1 1.2 硫化材料形貌差異及柯肯德爾效應(2D) 3 1.3 異質結構設計對催化之影響 5 1.4 研究動機 7 第二章 實驗方法 8 2.1 化學藥品 8 2.2 合成二維硒化鎘奈米片 9 2.2.1 硒前驅物製備 9 2.2.2 鎘前驅物製備 10 2.2.3 二維硒化鎘奈米片合成及純化 10 2.3 硫離子(sulfide ion)硫化奈米片製備實驗 11 2.4 硫粉(sulfur element)硫化奈米片製備實驗 12 2.5 光催化水分解實驗 12 2.6 儀器鑑定 14 2.6.1 穿透式電子顯微鏡 14 2.6.2 高解析掃描穿透式電子顯微鏡 14 2.6.3 高解析度X光粉末繞射儀 15 2.6.4 漫反射吸收光譜儀 15 2.6.5 螢光光譜儀 16 2.6.6 BET比表面積量測儀 16 2.6.7 元素分析儀 17 2.6.8 電子順磁共振光譜 17 2.6.9 氣相層析儀-阻擋放電離子化檢測器 17 2.6.10 四極探針台電性測量儀 18 2.6.11 X光吸收光譜-X光吸收延伸區精細結構 (Extend X-ray Absorption Fine Structure, EXAFS) 18 2.6.12 衰減式全反射傅立葉紅外光譜儀 19 2.6.13 感應耦合電漿質譜分析儀 19 2.6.14 恆電位電化學儀 20 第三章 結果與討論 21 3.1 二維單層硒化鎘奈米片CdSe(en)0.5的硫化 21 3.2 外緣中孔洞奈米片(Peripheral Porous Nanosheets) 22 3.3 空腔巨孔奈米片 (Cavity Macroporous Nanosheets) 27 3.4 分層薄膜奈米片 (Layered Thin Film Nanosheets) 31 3.5 均勻取代奈米片 (Uniformly Substituted Nanosheets) 36 3.6 硫化對內部鍵結與表面官能基影響 40 3.7 材料純化對晶體影響 44 3.8 光催化水分解析氫反應 48 3.9 電子結構 52 3.10 鎳離子吸附硫化樣品之光催化析氫實驗 61 第四章 結論與未來展望 63 文獻 65

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