近年來研究指出摻雜過度金屬元素的二氧化鈦以及少層數的二硫化鉬在催化產氫方面具有發展的潛力，本論文主要以二硫化鉬和二氧化鈦兩種材料的堆疊，對提升產氫效率做研究。
本論文使用離子插層法製備出少層數二硫化鉬；並利用水熱法製備出Fe摻雜濃度為0 at. %、0.25 at. %、1 at. %、3 at. %、5 at. %、7 at. % 的二氧化鈦薄膜。透過拉曼光譜峰值位置確認二硫化鉬層數為2層；二氧化鈦為銳鈦礦相(anatase)。由紫外-可見光光譜發現摻雜濃度的提升，能隙有遞減的趨勢；並透過光致發光光譜分析，螢光強度隨著摻雜濃度的增加而有猝滅(quenching)的現象。經由高解析穿透式電子顯微鏡以微觀尺度分析二氧化鈦樣品，得出奈米顆粒為圓形且粒徑為8-10nm。 接著利用延伸X光吸收精密結構數據擬合確認鐵成功摻雜，並取代晶格中鈦的位置，亦發現在低濃度摻雜時樣品為鐵二價與三價混合態，高濃度摻雜時價態轉變為三價，且摻雜過程中皆無氧化鐵的雜質。 最後我們利用滴定法將二硫化鉬沉積於二氧化鈦薄膜上，並使用三極式電化學分析，透過LSV圖觀察其起始電位，未摻雜的二氧化鈦樣品起始電位為 -2.10 V，經過摻雜0.25 at. % Fe後起始電位上升至- 1.75 V，再覆蓋1T-MoS2後更加上升至 -1.58 V，證明摻雜鐵元素和覆蓋1T-MoS2於二氧化鈦，皆有助於提升產氫催化效率。

Recently, hydrogen has been demonstrated to be a very promising renewable energy carrier for the future due to its high energy density and low impact of combustion on the environments. Numerous research works in the field have indicated that transition-metal-doped titanium dioxide and few-layer molybdenum disulfide have great potential for catalytic applications in the hydrogen evolution reaction. In this research, we investigated the hydrogen evolution reaction using molybdenum disulfide and titanium dioxide as catalysts.
Few-layer molybdenum disulfide was prepared by the ion intercalation method. Fe-doped titanium dioxide thin film samples were prepared using hydrothermal method with Fe concentrations of 0, 0.25, 1, 3 ,5 and 7 at.%. The thickness of molybdenum disulfide was found to be 2 layers by using Raman spectroscopy. The Raman data also demonstrate that all Fe-doped titanium dioxide thin-film samples are in anatase phase. A decreasing trend of energy gap values with increasing Fe doping concentrations was observed by using ultraviolet-visible spectroscopy. Photoluminescence spectroscopy shows that the fluorescence intensity is quenched as the Fe doping concentration increases. Titanium dioxide samples were also analyzed by a high-resolution transmission electron microscope. The TEM micrographs show that the nanoparticles were circular with diameters about 8-10 nm. The extended X-ray absorption fine structure analysis confirms that the iron impurity atoms occupy substitutional titanium sites in the host matrix. At low concentration, the iron impurity atoms are in a mixture of bivalent and trivalent states while the valence state of iron becomes purely trivalent at high dopant concentration. No iron oxide phases were detected. Finally, we used titration method to deposit molybdenum disulfide on the titanium dioxide thin films. Then, tripolar electrochemical analysis was used to determine the onset potential through the LSV diagram. For the undoped titanium dioxide sample, the onset potential is -2.10 V. With 0.25 at. % Fe doping, the onset potential is increased to -1.75 V, and can be further increased to -1.58 V with 1T-MoS2 covering. Therefore, we have proved that both the doping of iron and the covering of 1T-MoS2 in titanium dioxide can lead to higher hydrogen production catalytic activity.

摘要 I
Abstract II
致謝 IV
章節目錄 V
圖表目錄 VI
第一章 序論 1
1-1 研究動機 1
1-2 論文簡介 2
第二章 文獻回顧 3
2-1 二氧化鈦材料介紹 3
2-2 二氧化鈦結構 4
2-3 二硫化鉬材料介紹 4
第三章 實驗方法與原理 6
3-1拉曼光譜(Raman Spectroscopy) 6
3-2紫外-可見光光譜(Ultraviolet–visible spectroscopy; UV-Vis) 8
3-3 X光吸收精密結構(X-ray absorption fine structure; XAFS) 9
3-4光致發光光譜(Photoluminescence Spectrum ) 11
3-5高解析穿透式電子顯微鏡(HRTEM) 12
第四章 樣品製備與實驗流程 14
4-1-1 水熱合成法(hydrothermal synthesis method) 14
4-1-2 離子插層法 15
4-2 實驗藥劑 15
4-3 製備流程 17
4-4 製備步驟 18
4-4-1 FTO基板清洗 18
4-4-2 MoS2製備步驟 18
4-4-3 TiO2製備步驟 19
第五章 數據分析與討論 21
5-1拉曼光譜分析(Raman spectroscopy) 21
5-1-1拉曼光譜分析-二氧化鈦 21
5-1-2拉曼光譜分析-二硫化鉬 23
5-2紫外-可見光光譜(Ultraviolet-visible spectroscopy) 26
5-3光致發光光譜(Photoluminescence Spectrum) 30
5-4高解析穿透式電子顯微鏡(HRTEM) 33
5-5 X光吸收精密結構(X-ray absorption fine structure; XAFS) 36
5-5-1 X光吸收近邊緣結構(X-ray Absorption Near-Edge Structure; XANES) 36
5-5-2延伸X光吸收精密結構(Extended X-ray Absorption Fine Structure; EXAFS) 38
5-6電化學分析(Electrochemical analysis) 43
第六章 結果與討論 48
6-1結論 48
6-2未來展望 48
參考文獻 49

[1] G. Liu, H. G. Yang, J. Pan, Y. Q. Yang, G. Q. Lu and H.-M. Cheng, Chem. Rev. 114 9559–612 (2014).
[2] T. Sun, J. Fan, E. Liu, L. Liu, Y. Wang, H. Dai, Y. O. Yang, W. Hou, X. Hu and Z. Jiang, Powder Technol. 228 210–21 (2012).
[3] V. C. Papadimitriou, V. G. Stefanopoulos, M. N. Romanias, P. Papagiannakopoulos, K. Sambani, V. Tudose and G. Kiriakidis, Thin Solid Films. 520 1195–201 (2011).
[4] V. D. Binas, K. Sambani, T. Maggos, A. Katsanaki and G. Kiriakidis, Appl. Catal. B. 113–4 79–86 (2012).
[5] T. B. Nguyen, M. J. Hwang and K. S. Ryu, Appl. Surf. Sci. 258 7299–305 (2012).
[6] M. J. Powell, R. G. Palgrave, C. W. Dunnill, I. P. Parkin, Thin Solid Films. 562 223-228 (2014).
[7] S. B. Rawal, D. P. Ojha, S. D. Sung, W. I. Lee, Catal. Commun. 56 55-59 (2014).
[8] K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva, and A. A. Firsov, Science. 306, 666–669 (2004).
[9] Y. Yu, S.-Y. Huang, Y. Li, S. N. Steinmann, W. Yang and L. Cao, Nano Lett. 14, 553–558 (2014).
[10] Nord. G. L., Jr. (1992) Imaging transformation-induced microstructure. In: Mineral and reactions at the atomic scale: transmission electron microscopy, Rev Mineral, 27. 455–508 (P. R. Buseck. Ed.).
[11] K.-F. Mak, C. Lee, J. Hone, J. Shan, and T.-F. Heinz, Phys. Rev. Lett. 105, 136805, (2010).
[12] A. Splendiani, L. Sun, Y. Zhang, T. Li, J. Kim, C.-Y. Chim, G. Galli, and F. Wang, Nano Lett. 10, 1271-1275 (2010).
[13] Y. Yu, S.-Y Huang, Y. Li, S. N. Steinmann, W. Yang, L. Cao, Nano Lett. 14, 553–558 (2014).
[14] X. Liu, Y. Zhao, Y. Dong, Q. Fan, Q. Kuang, Z. Liang, X. Lin, W. Han, Q. Li, and M. Wen, Elec. trochim. Acta. 174, 315-326 (2015).
[15] K. Roy, M. Padmanabhan, S. Goswami, T. P. Sai, G. Ramalingam, S. Raghavan, and A. Ghosh, Nat. Nanotech. 8, 826-830 (2013).
[16] J. Shi, D. Ma, G.-F. Han, Y. Zhang, Q. Ji, T. Gao, J. Sun, X. Song, C. Li, Y. Zhang, X.-Y. Lang, Y. Zhang, Z. Liu, ACS Nano. 8, 10196-10204 (2014).
[17] Jiaguo Yu, Jianfeng Xiong, Bei Cheng, Chinese Journal of Catalysis. 26(9):745-749 (2005).
[18] X. Liu, Y. Zhao, Y. Dong, Q. Fan, Q. Kuang, Z. Liang, X. Lin, W. Han, Q. Li, and M. Wen, Elec. trochim. Acta. 174, 315-326 (2015).
[19] D. Y. Leung, X. Fu, C. Wang, M. Ni, M. K. Leung, X. Wang, X. Fu, ChemSusChem. 3, 681-694 (2010).
[20] L. Kernazhitsky, V. Shymanovska, T. Gavrilko, V. Naumov, L. Fedorenko, V. Kshnyakin, J. Baran, Ukr. J. Phys. 59 (3), 246-253 (2014).
[21] C. Lee, H. Yan, L.-E. Brus, T.-F. Heinz, J. Hone and S. Ryu, ACS Nano. 4, 2695-2700 (2010).
[22] H. Li, Q. Zhang, C.-C.-R. Yap, B.-K. Tay, T.-H.-T. Edwin, A. Olivier, and D. Baillargeat, Adv. Funct. Mater. 22, 1385-1390 (2012).
[23] P. B. Nair, V. B. Justinvictor, G. P. Daniel, K. Joy, V. Ramakrishnan, D. D. Kumar and P. V. Thomas, Thin Solid Films. 550, 121– 127 (2014).
[24] C. P. Saini, A. Barman, D. Banerjee, O. Grynko, S. Prucnal, M. Gupta, D. M. Phase, A. K. Sinha, D. Kanjilal and W. Skorupa, J. Phys. Chem. C. 121, 11448-11454 (2017).
[25] J. Zhu, W. Zheng, B. He, J. Zhang, M. Anpo, J. Mol. Catal. A. 216, 35–43 (2004).
[26] X. Pan, M.-Q. Yang, X. Fu, N. Zhang and Y.-J. Xu, Nanoscale. 5, 3601–3614 (2013).
[27] B. Bharti, S. Kumar, H‐N. Lee, R. Kumar, Sci. Rep. 6, 32355 (2016).
[28] Y. Pi, Z. Li, D. Xu, J. Liu, Y. Li, F. Zhang, G. Zhang, W. Peng and X. Fan, ACS Sustainable Chem. Eng. 5, 5175–5182 (2017).