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研究生:林思岑
研究生(外文):Sz-Tsen Lin
論文名稱:具重複使用性之磷酸銀/類沸石咪唑骨架羧甲基化纖維素薄膜於可見光源下光催化降解染料之研究
論文名稱(外文):Preparation of Ag3PO4/ZIF-8 composite of recyclable carboxymethylated cellulose membrane for photodegradation of dye solution under visible light source
指導教授:吳昌謀
指導教授(外文):Chang-Mou Wu
口試委員:黃旭曄陳俊傑陳榮宏安大中
口試委員(外文):Xu-Ye HuangJun-Jie ChenRong-Hong ChenDa-Zhong An
口試日期:2022-09-07
學位類別:碩士
校院名稱:國立臺灣科技大學
系所名稱:材料科學與工程系
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2022
畢業學年度:110
語文別:中文
論文頁數:112
中文關鍵詞:Ag3PO4@ZIF-8複合材料Ag3PO4@ZIF-8羧甲基化纖維膜可見光光催化染料降解
外文關鍵詞:Ag3PO4@ZIF-8 compositeAg3PO4@ZIF-8 carboxymethylated cellulose membranevisible lightphotocatalysisdye degradation
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源自於經濟成長和環境汙染等因素,全世界對能源的需求不斷增長進而助長了可再生能源的發展,因此利用再生能源處理汙染物的課題變得相當重要。然而太陽能清潔、豐富且容易獲得,且太陽為地球表面提供了巨大而持續的光能,使其成為最有前途的環境修復的再生能源之一。
Metal organic frameworks (MOFs) 是一種新穎的有機—無機混成材料由於金屬離子和有機配體間特殊的協調作用使MOF具有3D結構和多種功能的應用。然而MOFs的性質會受到金屬離子的種類和有機配體鍵結的方式所影響,本實驗使用的ZIF-8在水中具有良好的穩定性且具有較大的表面積能吸附水中的汙染物,但是ZIF-8的能階過大無法受可見光激發產生催化作用,因此引進Ag3PO4與ZIF-8複合後所形成的材料Ag3PO4@ZIF-8使其在可見光具有光催化能力得以降解水中的汙染物。
研究結果表示Ag3PO4@ZIF-8具有較低的電子-電洞結合率並且有較佳的光子利用率,且電子和電洞轉移速率更快。光降解研究結果顯示,Ag3PO4@ZIF-8粉體在可見光下經過120分鐘後分別可以降解99%的兩性離子型Rodamine B染料、95%的陰離子型Congo Red染料和90%的陽離子型Crystal Violet染料。降解效果和效率都比純Ag3PO4粉體和純ZIF-8粉體來的更佳。
最後本實驗將纖維素薄膜經過羧甲基化後與ZIF-8和Ag3PO4形成複合材料薄膜Ag3PO4@ZIF-8/FP進行光降解實驗,在可見光照射下經過120分鐘可以分別降解98.4%的RhB、93.6%的CR和89.8%的CV,且薄膜具有重複使用性,經過五次循環實驗對RhB仍保有95%的降解效果。
此研究顯示,本研究開發之Ag3PO4@ZIF-8複合材料在光催化應用上對三種離子型染料都具有良好的效能,與羧甲基化纖維素薄膜復合後的Ag3PO4@ZIF-8/FP同樣兼具優良的光催化效能和重複使用性。
Due to the economic growth and environmental pollution, using renewable energy to treat pollutants has become very important. Therefore, solar energy is clean, abundant, and available, and it is one of the most potential renewable energy sources for environmental remediation.
Metal organic frameworks (MOFs) are novel organic-inorganic hybrid materials. Because of the special coordination between metal ions and organic ligands, they have many applications and multiple functions. In this study we use ZIF-8 which has good stability in water and large surface area to adsorb pollutants. However, the energy band gap of ZIF-8 is too large to be excited by visible light, so we combine Ag3PO4 together to form Ag3PO4@ZIF-8 composite which has photocatalytic property under visible light source.
According to the results, Ag3PO4@ZIF-8 has a lower electron-hole recombination rate and better photon utilization, and its electron and hole transfer rate is faster which also enhanced the conductivity. Moreover, the results of photodegradation studies show that Ag3PO4@ZIF-8 can degrade 99% of the zwitterionic dye Rodamine B, 95% of the anionic dye Congo Red and 90% of the cationic dye Crystal Violet after 120 minutes under visible light. The degradation activities and efficiencies are better than those of pure ZIF-8 and pure Ag3PO4.
Finally, we use carboxymethylated cellulose membrane and combined with ZIF-8 and Ag3PO4 to make Ag3PO4@ZIF-8/FP composite membrane for photodegradation. After 120 minutes under visible light irradiation, Ag3PO4@ZIF-8/FP can degraded 98.4% of RhB, 93.6% CR and 89.8% CV. Moreover, after 5 cycles of experiments, the membrane still retains 95% degradation of RhB, which has reusable and stable behavior.
In summary, Ag3PO4@ZIF-8 composite shows a great photocatalytic performance for three different ionic dyes under visible light. After developing the Ag3PO4@ZIF-8/FP composite membrane, it has both excellent photocatalytic efficiency and reusability.
摘要
Abstract
目錄
圖目錄
表目錄
第1章 前言
1.1. 研究背景
第2章 文獻回顧與原理
2.1. 光催化材料簡介
2.1.1. 光催化反應
2.2. 修飾光催化劑的性質
2.2.1. 貴金屬沉積
2.2.2. 半導體複合物
2.2.3. 金屬或非金屬顆粒摻雜
2.2.4. 表面染料光敏化
2.3. 磷酸銀簡介
2.3.1. Ag3PO4與金屬氧化物複合
2.3.2. Ag3PO4與銀基材料複合
2.3.3. Ag3PO4與碳材料複合
2.4. 金屬有機骨架材料
2.4.1. MOF在光催化的研究
2.4.2. MOF光催化材料的優勢
2.5. MOF光催化劑的分類
2.5.1. ZIF-MOFs型
2.5.2. UiO-MOFs型
2.5.3. MIL-MOFs型
2.6. ZIF-8 材料簡介
2.6.1. ZIF-8的合成方法
2.6.2. ZIF-8的特性和應用
2.7. 可回收性光催化劑薄膜
2.8. 研究動機與目的
第3章 實驗
3.1. 實驗藥品
3.2. 實驗設備及儀器
3.3. 實驗流程圖
3.4. 樣品製備
3.4.1. 合成Ag3PO4粉體
3.4.2. 合成ZIF-8粉體
3.4.3. 合成Ag3PO4@ZIF-8粉體
3.4.4. 羧甲基化纖維素薄膜 (FP)
3.4.5. 製備ZIF-8/FP薄膜
3.4.6. 製備Ag3PO4@ZIF-8/FP薄膜
3.5. 分析方法
3.5.1. 場發射掃描式電子顯微鏡 (FE-SEM)
3.5.2. X射線繞射儀 (XRD)
3.5.3. 比表面積及孔徑分析儀 (BET)
3.5.4. X射線光電子能譜儀 (XPS)
3.5.5. 紫外光-可見光分析儀 (UV-Vis/NIR)
3.5.6. 螢光光譜儀 (PL)
3.5.7. 雷射奈米粒徑電位分析儀(Zetasizer)
3.5.8. 電化學工作站 (EIS)
第4章 結果與討論
4.1. Ag3PO4@ZIF-8複合材料的物性分析
4.1.1. 微結構分析 (FE-SEM)
4.1.2. 結晶度分析 (XRD)
4.1.3. 元素鍵結分析 (XPS)
4.1.4. 比表面積及表面電位分析 (BET、Zeta )
4.1.5. 光學特性分析 (UV-vis、PL)
4.1.6. 電化學阻抗分析 (EIS)
4.1.7. Mott-Schottky 分析
4.2. 光催化效能分析
4.2.1. 材料對三種染料的降解效果比較
4.2.2. 總有機碳量(TOC)分析
4.2.3. pH值對吸附和降解效果影響
4.2.4. 粉體重複降解效率
4.2.5. 複合材料的光催化機制
4.3. 複合材料纖維素薄膜特性分析
4.3.1. 微結構分析 (FE-SEM)
4.3.2. 薄膜光降解效能分析
第5章 結論
第6章 參考文獻
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