臺灣博碩士論文加值系統

本研究將產氫觸媒與產氧觸媒結合使用NaI水溶液當作I-/IO3-氧化還原媒介進行兩步驟光催化水分解反應系統(Z-scheme)之探討。產氫觸媒以固態反應法(Solid-state reaction)製備六鈮酸鉀K4Nb6O17，並探討添加不同比例Rh共觸媒對其產氫活性影響，可發現有添加Rh金屬共觸媒在甲醇當作犧牲試劑下擁有不錯的紫外光水分解活性以添加量於1.5wt%時擁有最高活性(24mmoleg-1h-1)較單一相K4Nb6O17(337 μmoleg-1h-1) 高出數倍，之後再使用剝落法(Exfoliation)將其剝落成奈米片狀結構進而增進其紫外光水分解活性(1392μmoleg-1h-1)，並也進行添加不同比例Rh共觸媒對其產氫活性影響，結果也是以添加量1.5wt%擁有最高活性(71 mmoleg-1h-1)。
產氧觸媒使用WO3負載0.5wt%Pt，我們將產氫觸媒與產氧觸媒同時置入Z-scheme系統中。SS-K4Nb6O17光觸媒我們分別進行的不同pH值的調控與NaI濃度的調控作為我們的變因，經過測試發現在pH為11時NaI濃度為4mM，擁有最高的產氣活性(H2:263μmoleg-1h-1，O2:126μmoleg-1h-1)，此為我們在SS- K4Nb6O17觸媒上找到最適合的Z-scheme系統的條件，添加1.5wt%Rh共觸媒得到更高的水分解活性(H2:533μmoleg-1h-1，O2:259μmoleg-1h-1)，並以添加1.5wt%Rh金屬奈米片光觸媒NS-K4Nb6O17得到本實驗最高的光催化水分解產氣活性(H2:1329μmoleg-1h-1，O2:341μmoleg-1h-1)。

In this study, we combine H2 evolution photocatalyst with O2 evolution photocatalyst, and use an aqueous NaI solution as I-/IO3- shuttle redox mediator in Z-scheme photocatalysis system for water splitting. We use solid state reaction to prepare H2 evolution photocatalyst, K4Nb6O17, and loading Rh as cocatalyst to improve hydrogen production. When the amount of loading Rh up to 1.5wt%, we get H2 evolution rate about 24mmol h-1 g-1 was higher than K4Nb6O17(337μmoleg-1h-1) as prepared. Then, we use exfoliation method to prepare our nanosheets photocatalyst, NS-K4Nb6O17, and loading Rh as cocatalyst, and exhibited a highest H2 evolution rate about 71 mmoleg-1h-1 when 1.5wt%Rh was loading.
O2 evolution photocatalyst use WO3 loading 0.5wt%Pt as cocatalyst. The rate of H2 evolution and O2 evolution under UV irradiation significantly changed with the concentration of NaI, and the pH value of the reactant solution. The H2 and O2 production rate of K4Nb6O17/WO3-0.5wt%Pt Z-scheme photocatalysis system was 263μmol h-1 g-1 and 126μmol h-1 g-1, respectively. The optimal NaI concentration of the reactant solution 4mM at pH = 11. The H2 evolution and O2 evolution rate of K4Nb6O17/WO3-0.5wt%Pt Z-scheme photocatalysis system were enhanced by loading Rh nanoparticles as cocatalyst(H2:533μmoleg-1h-1，O2:259μmoleg-1h-1). The Z-scheme photocatalysis system with NS-K4Nb6O17 -1.5 wt%Rh/WO3-0.5wt%Pt photocatalysts exhibited a highest photoactivity with a H2 evolution rate of 1329μmol h-1 g-1 and a O2 evolution rate of 341μmol h-1 g-1.

致謝 I
摘要 II
Abstract III
目錄 IV
圖目錄 VII
表目錄 XII
第一章 研究背景與文獻回顧 1
1.1 前言 1
1.2 研究目的 2
1.3 文獻回顧 2
1.3.1 光催化水分解反應 2
1.3.2 反應溶液影響 6
1.3.3 共觸媒影響 7
1.3.4 K4Nb6O17光觸媒 10
1.3.5 剝落法/再離子交換製備奈米片光觸媒 11
1.3.6 Z-scheme系統 13
第二章 實驗方法與步驟 23
2.1 實驗藥品與耗材 23
2.2 實驗設備與儀器 24
2.3 光觸媒製備 24
2.3.1 製備K4Nb6O17光觸媒 24
2.3.2 製備金屬Rh添加於K4Nb6O17光觸媒 25
2.3.3 製備H3.1K0.9Nb6O17光觸媒 26
2.3.4 製備NS-K4Nb6O17光觸媒 26
2.3.5 製備金屬Rh添加於NS-K4Nb6O17光觸媒 27
2.3.6 製備金屬Pt添加於WO3光觸媒 28
2.4 光觸媒性質分析 29
2.4.1 X-Ray繞射儀(XRD) 29
2.4.2 紫外-可見光(UV-visible) 30
2.4.3 氣相層析儀(Gas Chromatography) 30
2.4.4 場發射掃描式電子顯微鏡(FE-SEM) 31
2.4.5 X光光電子能譜(XPS) 32
2.4.6 解析型穿透式電子顯微鏡(TEM) 33
2.5 GC檢量線製作 33
2.5.1 氫氣檢量線 33
2.5.2 氧氣檢量線 34
2.6 光催化水分解產氣實驗 35
2.6.1 光觸媒於甲醇水溶液下產氫實驗 35
2.6.2 光觸媒於純水中產氣實驗 37
2.6.3 產氫觸媒於碘化鈉水溶液下產氫實驗 37
2.6.4 產氧觸媒於硝酸銀水溶液下產氧實驗 37
2.6.5 產氧觸媒於碘酸鈉水溶液下產氧實驗 37
2.6.6 光觸媒於Z-scheme系統中產氣實驗 38
第三章 實驗結果與討論 39
3.1 SS-K4Nb6O17&NS-K4Nb6O17 39
3.2 SS-K4Nb6O17添加金屬Rh共觸媒 45
3.3 NS-K4Nb6O17添加金屬Rh共觸媒 58
3.4 WO3添加金屬Pt共觸媒 68
3.5 SS-K4Nb6O17/WO3運用於Z-scheme系統中 73
3.6 NS-K4Nb6O17/WO3運用於Z-scheme系統中 86
第四章 結論 93
參考文獻 95

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