光電化學分解水產氫的發展已經有數十年歷史，已開發的電極材料不勝其數，其中二氧化鈦為最早使用的光觸媒，其合適的價帶和導帶位置，使其能與水進行氧化和還原反應產生氧氣和氫氣。但受限於材料本身能隙過寬的因素，二氧化鈦必須在紫外光驅動下，才能進行光催化反應。本研究針對此問題，透過異質結構搭配的策略，期望改善二氧化鈦的光電化學效能。
本實驗所設計的三明治奈米結構—氫化碳摻雜銳鈦礦二氧化鈦奈米晶/氮摻雜碳/金紅石二氧化鈦奈米柱能有效提升金紅石二氧化鈦奈米柱之光電化學性能表現。其中，透過水熱法合成出的一維結構二氧化鈦奈米柱具有載子傳遞直接且快速的優點;而氮摻雜碳則是以多巴胺作為碳氮來源，利用簡易的一鍋合成法，在多巴胺自聚合機制下修飾於二氧化鈦奈米柱表面，並經過高溫碳化後，形成嵌有碳點的碳層結構。其中的碳點能扮演光敏劑的角色有效吸收可見光，提升太陽光的利用率，而碳層則能幫助內外層所產生的光生電子電洞傳遞至導電基材FTO。氫化碳摻雜銳鈦礦奈米粒則在水熱法與低濃度氫氣氫化的搭配下成功合成，其能吸收可見光，進一步提升光電流。
於光電化學測試上，本研究合成出的三明治結構電極，以1M氫氧化鉀作為電解質，在太陽模擬光(AM1.5G)照射下，其光電流大小於理論水分解電位1.23 V驅動下為0.8 mA/cm2 ，相對於單純金紅石二氧化鈦奈米柱提升約86 %;而在400 nm波長以上的可見光照射下，同樣於偏壓1.23 V，光電流表現為82 μA/cm2 ，相對於單純二氧化鈦奈米柱提升達228 %，顯示碳點/層與氫化碳摻雜銳鈦礦奈米粒對可見光波段的太陽光具有良好的吸收效果，且材料搭配上能有效進行載子傳遞，分離電子電洞。在長效性方面，本研究以5小時作為穩定性測量的標準，其施加的偏壓為最高光轉換效率所對應的電位，結果為本研究所合成出的三明治結構能維持84 %初始光電流，相對於單純二氧化鈦奈米柱的60 %有顯著提升。

Photoelectrochemical water splitting is a long investigated research topic, and a great deal of electrode materials have been developed. Among them, TiO2 is the first photocatalyst studied. Because of the appropriate positions of valence and conduction bands, TiO2 can produce oxygen and hydrogen from the corresponding redox reactions with water. Nevertheless, because of the large band gap, TiO2 can only function under illumination of UV light. The goal of this research is to improve the photocatalytic efficiency of TiO2 through design of heterostructure and matching materials.
A sandwiched nanostructure of hydrogenated carbon doped anatase TiO2 nanoparticle/ nitrogen doped carbon dots@layer/ rutile TiO2 nanorod was developed for the above purpose. In this design, we used a hydrothermal method to synthesize rutile TiO2 nanorod array that has the beneficial characteristic of direct and fast charge transfer. For the coating of the nitrogen doped carbon layer on the rutile TiO2 nanorods, dopamine was chosen as the carbon and nitrogen sources and the coating was carried out with a one pot synthesis involving the self-polymerization of dopamine. After high temperature carbonization a carbon dot embedded carbon layer was formed on the surface of the rutile TiO2 nanorods. The carbon dots function as a photosensitizer to absorb visible light, thus significantly increasing the utilization of sun light. The carbon layer, located in the middle of the sandwiched nanostructure, served as a mediator and conduction layers, which facilitate the transport of photo-induced charges from the innermost and outermost layers. As for the outermost layer, the hydrogenated carbon doped anatase TiO2 nanoparticles were first prepared with hydrothermal method followed by hydrogenation in an atmosphere of low concentration hydrogen. The hydrogenated carbon doped anatase TiO2 nanoparticles can absorb visible light for generation of photo-induced charges and serve to further boost the photocurrent density of the composite electrode.
The photocurrent density achieved by sandwiched nanostructure electrode was 0.8 mA/cm2 at 1.23V(vs. RHE) under irradiation of simulated sun light at 100 mW/cm2 (AM1.5G), a 86% improvement over the plain rutile TiO2 nanorod array electrode. If illuminated under the light of λ > 400 nm, the sandwiched nanostructure electrode offered a photocurrent density of 82 μA/cm2 at 1.23V(vs. RHE), a 228% improvement over the plain rutile TiO2 nanorod array electrode. These improvements may be attributed to the much improved light harvesting and the implement of a central charge transport highway layer, enhancing also the charge separation. For the operation stability, the sandwiched nanostructure maintained 84% of the starting current density after 5 h operation at an applied potential set at the corresponding maximum photoconversion, significantly outperforming 60% of the plain rutile TiO2 nanorod array electrode.

摘要 I
Abstract III
誌謝 V
總目錄 VI
圖目錄 IX
表目錄 XIII
第一章 緒論 1
1-1 前言 1
1-2 本多-藤島效應 (Honda-Fujishima effect) 2
1-3 光觸媒原理 3
1-3.1光觸媒催化原理 3
1-3.2光分解水原理 5
1-4 半導體光觸媒 7
1-4.1 半導體材料 7
1-4.2 光電極種類 8
1-4.3半導體費米能階 (Fermi Level) 8
1-5 光催化水分解裝置 9
1-5.1 光電化學反應裝置 10
1-5.2 對電極 10
1-5.3 參考電極 11
1-6 研究動機 13
第二章 文獻回顧 14
2-1 二氧化鈦的基本性質 14
2-2 一維二氧化鈦奈米柱合成法 16
2-2.1 水熱合成法(Hydrothermal Methods) 16
2-2.2 微波輔助法(Microwave Assisted Methods) 17
2-2.3 化學/物理氣相沉積法(Chemical/Physical Vapor Deposition) 17
2-3 碳量子點(Carbon Quantum Dots, CQDs) 性質與合成 18
2-3.1 碳量子點的合成 20
2-3.2氮摻雜碳量子點合成 22
2-3.3 碳量子點與氮摻雜碳量子點在光催化領域上的應用 23
2-4 碳化聚多巴胺合成與應用 27
2-5 黑色二氧化鈦 32
2-6 三明治結構 35
第三章 實驗內容 41
3-1 實驗藥品 41
3-2 實驗器材 42
3-3 分析儀器 43
3-4 光電極製備 47
3-4.1 FTO導電玻璃前處理 47
3-4.2 一維二氧化鈦奈米柱製備方法(第一層結構) 47
3-4.3 氮摻雜碳點/層修飾於二氧化鈦奈米柱(第二層結構) 48
3-4.4 氫化後碳摻雜二氧化鈦奈米粒修飾於碳點/層(第三層結構) 48
3-4.5 三明治結構整體製備流程圖 49
3-4.6 光電極封膠製備 50
3-5電化學量測 50
3-5.1 光電流密度量測 51
3-5.2 光轉換效率(photoconversion efficiency) 52
3-5.3 莫特-肖特基方程(Mott-Schottky equation, M-S ) 53
第四章 結果與討論 54
4-1 金紅石二氧化鈦奈米柱鑑定 54
4-2 氮摻雜碳點/層包覆二氧化鈦奈米柱鑑定 58
4-3 二氧化鈦奈米粒修飾後的三明治結構鑑定 62
4-3.1 氫化碳摻雜銳鈦礦二氧化鈦奈米粒鑑定 62
4-3.2二氧化鈦奈米粒修飾於碳包覆二氧化鈦奈米柱鑑定 66
4-4 光學分析 71
4-5 光電化學分析 79
4-5.1 第二、三層最適化條件選擇 79
4-5.2 三者各層材料搭配後的光電化學表現比較 82
第五章 結論 86
第六章 參考文獻 87

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