單層數的二硫化鉬是一個具有潛力的析氫材料，它具有兩種晶相：穩定態的半導體相(2H)和亞穩態的金屬相(1T)。單層數的2H-MoS2具有直接能隙1.9 eV，但是緩慢的載子偏移率會影響到產氫效率。1T-MoS2則具有較好的導電率。
在本論文中我們研究1T-MoS2的析氫反應，以及透過摻雜過渡金屬的方式(TM-MoS2)進一步研究其析氫反應。利用高溫使鋰離子嵌入塊材二硫化鉬的方式，可以大幅縮短離子插層法製備所需的時間且能製備出大量的1T-MoS2。我們使用紫外光-可見光光譜(UV-visible)、拉曼光譜(Raman spectroscopy)和X光繞射(XRD)鑑定為1T-MoS2。透過高解析度穿透式電子顯微鏡(HRTEM)的影像看到未摻雜以及有摻雜的二硫化鉬為層狀結構，並且利用HRTEM的附加功能能量散射光譜(EDS)得到摻雜過渡金屬的元素比例。為了得知的摻雜原子在TM-MoS2中的結構，我們使用X光吸收精密結構(XAFS)分析，確定摻雜原子並非氧化物。摻雜原子的周圍環境有鍵結在二硫化鉬邊緣的硫原子上或放在鉬原子上方與硫原子鍵結兩種情況。其中錳、鈷和鎳會鍵結在硫缺陷較多的位置，鉻、鐵和銅則鍵結在硫缺陷較少的位置。在電化學析氫(HER)的部分，無論1T-MoS2或TM-MoS2與原始電解水相比皆能大幅降低起始過電位(onset overpotential)。其中Mn-MoS2、Co-MoS2和Ni-MoS2有較優秀的起始過電位，尤其Co-MoS2具有最小的起始過電位為-227mV。二硫化鉬經摻雜過後其塔菲爾斜率及電化學阻抗皆有下降，故摻雜錳、鈷和鎳後的1T-MoS2為良好的析氫材料。

Single-layered molybdenum disulfide (MoS2) is considered as a promising catalyst for hydrogen evolution reaction (HER). There are two phases of MoS2 commonly used for HER applications, namely the semiconductor phase (2H) and the metallic phase (1T). The direct bandgap of the single layer 2H-MoS2 is 1.9 eV. But its low electron mobility has negative effects on the efficiency of hydrogen evolution reaction. On the other hand, the 1T-MoS2 has high electrical conductivity. Therefore, we have focused our research on the preparation of transition-metal-doped 1T-MoS2 (TM-MoS2) and their catalytic applications for hydrogen evolution reaction.
High quality 1T-MoS2 was prepared using ion intercalation method at high temperatures. By using our improved home-made autoclave, the reactive time can be largely reduced. UV-visible spectroscopy, Raman spectroscopy and X-ray diffraction (XRD) measurement were used to confirm the 1T phase of our sample. High resolution transmission electron microscope (HRTEM) also revealed the layered structures of the 1T-MoS2 and TM-MoS2 samples. Energy dispersive spectrometer (EDS) analysis was used to estimate the dopant concentration in TM-MoS2. The X-ray absorption near edge structure (XANES) analyses were used to exclude the possible existence of transition metal oxide. The extended X-ray absorption fine structure (EXAFS) analyses provide information of local structures surrounding the dopant atoms. The catalytic activity for HER is estimated by Linear sweep voltammetry (LSV) measurements using an electrochemical analyzer. We have found that Mn-doped MoS2、Co-doped MoS2 and Ni-doped MoS2 have better onset overpotential. The Co-MoS2 sample has the smallest onset overpotential of -277mV. As for Tafel slope and EIS, TM-MoS2 is better than 1T-MoS2. The Mn-doped MoS2、Co-doped MoS2 and Ni-doped MoS2 have better catalytic activity in HER than samples doped with other transition metals.

摘要 ……………………………………………………………………………….I
Abstract …………………………………………………………………………...II
誌謝 …………………………………………………………………………......IV
章節目錄 ……………………………………………………………………...…V
圖表目錄 ………………………………………………………………………..VI
第一章 序論
1-1 研究動機 ………………………………………………………...01
1-2 論文簡介 ………………………………………………………...02
第二章 文獻回顧
2-1 二硫化鉬(MoS2)材料之介紹 …………………………………..03
2-2 金屬相之二硫化鉬(1T-MoS2) ………………………………….05
2-3 二硫化鉬之析氫催化反應 ……………………………………..06
2-4 二硫化鉬製備方法 ……………………………………………..07
第三章 實驗方法與原理
3-1 紫外光-可見光光譜 …………………………………………….09
3-2 拉曼光譜 ………………………………………………………..10
3-3 高解析度穿透式電子顯微鏡 …………………………………..12
3-4 X光繞射 ………………………………………………………..14
3-5 X光吸收精密結構 ……………………………………………..15
3-6 電化學析氫反應 ………………………………………………..22
第四章 樣品製備與流程
4-1 樣品製備 ………………………………………………………..29
4-2 實驗藥劑與器材 ………………………………………………..30
4-3 製備流程 ………………………………………………………..31
4-4 製備步驟 ………………………………………………………..32
4-5 樣品名稱代號 …………………………………………………..35
第五章 數據分析與討論
5-1 紫外光-可見光光譜分析 ……………………….………………36
5-2 拉曼光譜分析 …………………………………………………..39
5-3 X光繞射分析 …………………………………………………..41
5-4 高解析度穿透式電子顯微鏡分析 ……………………………..42
5-5 X光吸收精密結構分析 ………………………………………..50
5-6 電化學析氫反應分析 …………………………………………..66
第六章 結果與討論
6-1 結論 ……………………………………………………………..74
6-2 未來發展 ………………………………………………………..75
附錄 參考資料 ………………………………………………………………..76

第二章
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第三章
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第五章
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