[[alternative]]Silver chloride films for photocatalytic degradation of orange II dye

碩士[[abstract]]本研究已提出一種新穎氯化銀薄膜製備方法，將硝酸銀水溶液相 變化成固態後，滴入氯化鈉水溶液，藉由析出反應製得氯化銀薄膜。 該薄膜下表面形態具有高吸附面積之大量小晶粒堆積成棒狀結構。將 此薄膜之下表面晶態分別以UV 光與可見光催化降解Orange II 偶氮 染料，並比較8.4M、6.3M、4.2M 及2.1M 硝酸銀水溶液濃度所製得 之氯化銀薄膜與相同表面積之奈米二氧化鈦粉末對Orange II 偶氮染 料之光催化降解效果。UV 光催化降解實驗中，氯化銀薄膜可有效降 解Orange II 偶氮染料，其色度可於兩個小時內去除98%；在可見光 催化下，表面含有銀原子簇的氯化銀薄膜對Orange II 染料亦有降解 效果，但與UV 光催化比較之下，效果較差，色度在兩個小時內僅能 去除31%。其中以硝酸銀水溶液濃度4.2M 所製得之氯化銀薄膜因具 有較高之吸附面積，故光催化降解效果最佳。在相同吸附面積比較之 下，氯化銀薄膜之染料光催化降解效果大於奈米二氧化鈦粉末。[[abstract]]This study has proposed a novel method to fabricate silver chloride film. The silver chloride film was obtained by precipitating reaction that infusing sodium chloride aqueous solution on the silver nitrate aqueous solution which was phase changed into solid-state. The morphology of under-surface of the silver chloride film has many stick structures with high absorption area which heaps by a lot of small particles. The under-surface of the film was used to do photocatalytic degradation of orange II azo dye under ultraviolet light and visible light separately, and the degradation effect of the silver chloride film was compared with the film which was obtained with 8.4M, 6.3M, 4.2M, and 2.1M silver nitrate aqueous solution and the nano titanium dioxide powder which have same specific surface area. In ultraviolet light photocatalysis, the Orange II azo dye could be degraded by the silver chloride film effectively. Its color could be removed 98% during 2 hours. And in visible light photocatalysis, the silver chloride film with silver clusters degrades orange II azo dye effectively but not significantly when compared to ultraviolet photocatalytic. And the color could be removed 31% during 2 hours. Among them, the silver chloride obtained from 4.2M silver chloride aqueous solution due to the higher absorption area, so the photocatalytic degradation is better than other concentration. Under the same absorption area, the photocatalytic degradation effect of the silver chloride film was larger than that of nano titanium dioxide powder.[[tableofcontents]]總目錄 中文摘要............................................................................................................I 英文摘要.......................................................................................................... II 總目錄.............................................................................................................IV 圖目錄........................................................................................................... VII 表目錄.............................................................................................................IX 壹、導論........................................................................................................... 1 1.1 前言......................................................................................................... 1 1.2 文獻回顧................................................................................................. 2 1.2.1 染料.................................................................................................. 2 1.2.2 光化學反應...................................................................................... 4 1.2.3 氯化銀簡介...................................................................................... 6 1.2.4 氯化銀光催化.................................................................................. 7 1.2.5 氯化銀光催化染料降解.................................................................. 9 1.2.6 氯化銀薄膜製備方法.................................................................... 11 1.2.6.1 真空蒸鍍法(vacuum evaporation) ........................................ 11 1.2.6.2 濺鍍法(sputtering)................................................................. 11 1.2.6.3 溶膠-凝膠法(sol-gel)............................................................. 12 1.2.6.4 化學浴沉積法(chemical bath deposition)............................. 13 1.3 研究範疇............................................................................................... 14 貳、實驗步驟................................................................................................. 25 2.1 實驗材料與設備................................................................................... 25 2.1.1 實驗材料......................................................................................... 25 2.1.2 實驗設備........................................................................................ 25 2.2 氯化銀薄膜之製備............................................................................... 26 2.3 氯化銀薄膜之性質分析....................................................................... 28 2.3.1 顯微結構觀察(SEM) ..................................................................... 28 2.3.2 X-光繞射分析(XRD)...................................................................... 28 2.3.3 比表面積測定(BET)...................................................................... 28 2-4 Orange II 染料光催化降解................................................................. 29 2-4.1 實驗流程及裝置............................................................................ 29 2-4.2 實驗方法........................................................................................ 30 2.4.2.1 預備實驗.................................................................................. 30 2.4.2.2 光催化降解實驗..................................................................... 31 2.4.3 分析方法........................................................................................ 33 2.4.3.1 真色色度分析( ADMI ) ........................................................ 33 參、結果與討論............................................................................................. 38 3.1 氯化銀薄膜之性質分析....................................................................... 38 3.1.1 顯微結構觀察(SEM) ..................................................................... 38 3.1.2 X-光繞射分析(XRD)...................................................................... 42 3.1.3 比表面積測定(BET)....................................................................... 43 3.2 預備實驗............................................................................................... 44 3.2.1 揮發實驗......................................................................................... 44 3.2.2 直接光解實驗................................................................................. 44 3.2.3 吸附實驗......................................................................................... 44 3.3 光催化降解實驗................................................................................... 45 3.3.1 UV 光催化降解實驗...................................................................... 45 3.3.2 可見光催化降解實驗.................................................................... 46 肆、結論......................................................................................................... 60 參考文獻......................................................................................................... 62 圖目錄 圖1.1 Orange II 之化學結構......................................................................... 16 圖1.2 太陽光的光譜..................................................................................... 17 圖1.3 氯化銀/銀簇能隙示意圖.................................................................... 18 圖1.4 在可見光照射下Ag/AgCl (■) 與N-Doped TiO2 (▲)針對甲基橙染 料降解效率的比較............................................................................. 19 圖1.5 AgCl/Ag-NP、AgCl 及N-Doped TIO2 之UV/Vis 擴散反射光譜... 20 圖1.6 不同光觸媒(N-Doped TiO2、AgCl、AgCl/Ag-Bulk、AgCl/Ag-NP50 及AgCl/Ag-NP20)在可見光照射下對甲基藍染料降解效率比較. 21 圖2.1 氯化銀薄膜製備裝置圖..................................................................... 34 圖2.2 實驗光源之光譜(a)UV 光；(b)可見光............................................. 35 圖2.3 染料光催化降解實驗流程圖............................................................. 36 圖2.4 染料光催化降解實驗裝置................................................................. 37 圖3.1 氯化銀薄膜上表面之顯微結構(a)10 分鐘；(b)12 小時；(c)24 小時 ............................................................................................................. 48 圖3.2 氯化銀薄膜下表面之顯微結構(a)10 分鐘；(b)12 小時；(c)24 小時 ............................................................................................................. 49 圖3.3 氯化銀薄膜剖斷面之顯微結構(a)10 分鐘；(b)12 小時；(c)24 小時 ............................................................................................................. 50 圖3.4 不同硝酸銀水溶液濃度之氯化銀薄膜之上表面顯微結構............ 51 (a)6.3 M；(b)4.2 M；(c)2.1M ........................................................... 51 圖3.5 不同硝酸銀水溶液濃度之氯化銀薄膜之下表面顯微結構............ 52 (a)6.3 M；(b)4.2 M；(c)2.1M ........................................................... 52 圖3.6 不同硝酸銀水溶液濃度之氯化銀薄膜之上表面顯微結構............ 53 (a)6.3 M；(b)4.2 M；(c)2.1M ........................................................... 53 圖3.7 氯化銀薄膜之X-光繞射圖(a)UV 光照射前；(b)UV 光照射後..... 54 圖3.8 揮發實驗之Orange II 染料殘餘分率............................................... 55 圖3.9 以UV 光與可見光直接光解之Orange II 染料殘餘分率............... 56 圖3.10 吸附實驗之Orange II 染料殘餘分率............................................. 57 圖3. 11 UV 光照射下不同硝酸銀濃度所製得氯化銀薄膜之Orange II 染料 殘餘分率........................................................................................... 58 圖3.12 可見光照射下不同硝酸銀濃度所製得氯化銀薄膜之Orange II 染 料殘餘分率....................................................................................... 59 表目錄 表1.1 染料之發色團..................................................................................... 22 表1.2 染料之助色團..................................................................................... 23 表1.3 各種氧化劑之標準氧化電位............................................................. 24[[note]]學號: 697370095, 學年度: 9