臺灣博碩士論文加值系統

高級氧化(Advanced Oxidation Processes, AOPs)是一種可行的方式來處理染整廢水。高級氧化處理利用物化方式降解水中污染物，將污染物轉化為低毒性或易分解小物質。其中光催化反應，是經常被探討到的高級氧化程序之一，現今最具代表性的光觸媒材料為二氧化鈦，擁有來源豐富低成本、無毒性、穩定性高、強氧化還原能力，並且在反應過程中無有害物質產生避免二次污染等優點。

二氧化鈦亦存在些缺點，像能隙高、低孔洞性、吸附效果不佳等，透過文獻得知金屬有機骨架(Metal-organic frameworks, MOFs)擁有提升高表面積，框架及孔徑可調等特性，利用金屬有機骨架製備二氧化鈦，使在框架中的二氧化鈦在熱解後仍能承受一定程度的永久性孔隙度，可展現高接觸面積，吸附效能佳等優點。石墨烯(Graphene)為目前世界上電阻率最低之材料，且擁有良好之導電性以及透光性，以上特點可以使得石墨烯在光催化反應中扮演電子傳遞角色，促使光催化材料二氧化鈦電子電洞對恢復時間拉長，提供更好的氧化還原能力。故本研究透過複合式材料MOF-TiO2-RGO進行光催化降解偶氮染料Acid Red 27(AR-27)。實驗結果顯示在酸性條件下光降解效果最好，石墨烯添加參數比例以5 %、10 %、15 %、20 %進行實驗，隨著比例過高或過低並無明顯更好反而在10 %時效果最好。研究中也嘗試以無機鹽類作為競爭者，發現有一定程度之影響。

Advanced Oxidation Processes (AOPs) as a feasible way to deal with dye wastewater. AOPs use physical and chemical means to degrade pollutants in the water and convert the pollutants to low-toxic or easily decomposable substances. Among them, the photocatalytic reaction is one of the AOPs that is often explored. Titanium dioxide is one of the most representative photocatalyst materials available today. It has the advantages of rich source, low cost, non-toxicity, high stability, strong oxidation and reduction ability, and no harmful substances in the reaction process to avoid secondary pollution.

Titanium dioxide also has some shortcomings, such as high energy gap, low porosity and poor adsorption. According to the literature, Metal-organic frameworks (MOFs) possesses such features as high surface area, adjustable framework and adjustable aperture. The use of metal organic framework preparation of titanium dioxide, titanium dioxide in the frame after pyrolysis can still withstand a certain degree of permanent porosity, can demonstrate high contact area, adsorption efficiency and so on. Graphene is the lowest resistivity material in the world and possesses good electrical conductivity and light transmittance. These features make graphene play an electron transfer role in photocatalytic reaction. Promote photocatalytic titanium dioxide electron hole elongated recovery time, to provide better redox ability. In this study, the azo dye Acid Red 27(AR-27) was photocatalytically degraded by the composite MOF-TiO2/RGO. The experimental results show that photodegradation is best under acidic conditions. Addition of graphene at 5 %、10 %、15 %、20 % in the experiment. With the increase or decrease in the proportion did not increase but the best effect at 10%. The study also tried to use inorganic salts as a competitor and found that there is a certain degree of impact.

摘要 i
Abstract ii
目錄 iii
圖目錄 vii
表目錄 ix
第一章 緒論 1
1-1 研究緣起 1
1-2 研究目的 3
第二章 文獻回顧 4
2-1染料概述 4
2-1-1 染料 4
2-1-2 發色原理 4
2-1-3 染料分類 6
2-2 染整廢水概述 7
2-2-1 染整廢水特性 7
2-2-2 染整廢水處理概論 9
2-3偶氮染料 11
2-4染料AR-27概述 12
2-4-1 AR-27 基本性質 12
2-4-2 AR-27降解機制 13
2-5 光化學概述 15
2-5-1 光化學反應理論 15
2-5-2 光化學反應的分類 17
2-6半導體概述 18
2-7二氧化鈦概述 19
2-7-1 晶型構造 20
2-7-2二氧化鈦光催化反應原理 22
2-7-3 二氧化鈦製備方式 24
2-8金屬有機架構概述 27
2-8-1 金屬有機架構介紹 27
2-8-2金屬有機架構的應用 29
2-8-3 金屬有機架構金屬中心 29
2-9 石墨烯概述 30
2-9-1 石墨烯 30
2-9-2石墨烯製備方式 32
2-9-3 氧化石墨烯 34
2-9-4 還原石墨烯 35
2-10 金屬有機架構複合還原石墨烯 36
第三章實驗設備與方法 38
3-1實驗藥品 38
3-2實驗設備與分析儀器 39
3-3 實驗架構 41
3-4 光觸媒材料製備 43
3-4-1 金屬有機架構-二氧化鈦製備 43
3-4-2 石墨烯製備 46
3-4-3 複合式材料MOTR製備 48
3-5 實驗內容與方法 49
3-5-1背景實驗 49
3-5-2 光催化實驗 50
3-5-3 光催化實驗系統 50
3-5-4 檢量線之建立 51
3-5-5 樣品採樣處理與分析 52
3-5-5 參數控制 53
3-5-6 反應動力模式探討 54
3-6 分析項目及方法 55
3-6-1 材料及表面特性分析 55
3-6-2 水樣分析 56
第四章 結果與討論 59
4-1材料鑑定 59
4-1-1 穿透式電子顯微鏡分析 59
4-1-2 傅立葉紅外光譜儀分析 63
4-1-3 氧化石墨烯紫外光/可見光光譜分析 65
4-1-4 紫外光/可見光光譜分析 67
4-1-5 比表面積分析 68
4-2 背景實驗 70
4-2-1 AR-27染料水溶液的吸光特性 70
4-2-2 可見光直接光解實驗 71
4-2-3 太陽光直接光解實驗 72
4-3 複合式材料探討 74
4-4 暗吸附實驗 75
4-4-1 吸附平衡 75
4-4-2 溶液pH值效應 76
4-4-3 觸媒於不同pH值條件下之吸附效應 78
4-4-4 不同添加量之吸附 80
4-5 競爭吸附 81
4-5-1 競爭離子吸附影響 81
4-5-2 競爭離子吸附變化 83
4-5-3 不同濃度競爭離子 84
4-6 不同光觸媒材料之比較 85
4-7 系統PH值之變化 86
4-8 最佳參數試驗 87
4-8-1觸媒添加量 87
4-8-2 石墨烯複合比例 89
4-8-3不同初始濃度 91
4-8-4 不同濃度觸媒去除量 92
4-9 材料降解染料之色度與TOC殘餘率比較 93
4-10 含有無機鹽類離子之光降解 94
4-11 脫附實驗 95
4-12 完全礦化實驗 98
4-13真實太陽光照實驗 99
4-14 可見光實驗 101
4-15 動力學探討 103
4-15-1 動力學簡介 103
4-15-2 擬一階反應動力常數探討 105
4-15-3 不同參數之動力學探討 105
第五章 結論與建議 110
5-1 結論 110
5-2 建議 112
參考文獻 113
中文部分 113
西文部分 114
附錄 122

中文部分
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