臺灣博碩士論文加值系統

雙氯芬酸（DFC）是一種非類固醇抗發炎藥物，廣泛用於治療炎症和疼痛性疾病。近年來，由於這些藥物在水生環境中對於水生生物和人類的健康構成威脅而越來越受到關注，有鑒於此，必須透過提升降解效率的方法來減少其在環境中的存在。從環境可持續性和綠色化學方法來看，高級氧化處理程序（AOPs）是處理含水介質中的DFC 和其他抗生素等有害且不可生物降解污染物之理想選擇。至此，硼與磷共摻雜於氮化碳（BPCN）的一維材料已透過簡易的水熱輔助熱聚合方法成功合成並作為光催化降解 DFC 的有效光催化劑。隨後，再利用 465 nm 可見光照射下對於 DFC 的降解來評估 BPCN 的光催化活性。當可見光照射 90 分鐘，BPCN 可於 10 mg L-1 的 DFC 初始濃度下達到 99 % 的降解效率。增強的光催化活性歸因於使用 460 – 470 nm 範圍內的可見光而促進 B，P 共摻雜的 C3N4 材料之光誘導電荷的分離。再者，透過測量 DFC 分解的速率常數來分析環境參數的影響，包括初始 DFC 濃度、pH 值及各種陰離子的存在。當 pH 5.0 和初始 DFC 濃度高達 30 mg L-1 條件下使用 BPCN 可達到的優異的光催化活性。這很明顯地說明當硼與磷摻雜率分別為 7.9 % 和4.9 % 之 BPCN-3 光催化劑對於 DFC 的分解可有效提升的光催化活性（0.047 min-1）且相較於未摻雜的 C3N4（0.01 min-1）相差約為 4.7 倍。本研究所開發出的一維 BPCN 的降解能力可有效提升，其歸因於增加表面積、可見光感應及光致電荷分離而進而克服了原 g-C3N4 的缺點。這些結果清楚地表明，不含金屬的硼和磷共摻雜的 C3N4 是一種可靠的綠色技術方法，用於製備可見光感應光催化劑，可應用於抗生素和其他新出現的水處理污染物的分解並具有很大的潛力。

Diclofenac (DFC) is a non-steroidal anti-inflammatory drug, widely used in treatment of inflammation and painful diseases. In recent years, presence of these pharmaceuticals in the aquatic environment has been of growing interest as it poses a dangerous threat to aquatic organisms and human health. The need for enhanced methods to reduce its presence in the environment has become evident. From the environmental sustainability and green chemistry approaches, advanced oxidation processes (AOPs) represent a good choice for the treatment of hazardous non-biodegradable pollutants like DFC and other antibiotics from the aqueous medium. Herein, boron and phosphorus co-doped one dimensional C3N4 (BPCN) has been successfully synthesized by a facile hydrothermal–assisted thermal polymerization approach as effective photocatalyst for photocatalytic degradation of DFC. Subsequently, the photocatalytic activity of BPCN was evaluated through the degradation of DFC under visible light irradiation of 465 nm. BPCN could achieve 99% degradation of DFC at 10 mg L-1 initial concentration within 90 min of irradiation. The enhanced photocatalytic activity is attributed to the promoted photoinduced charge seperation of B, P co-doped C3N4 using visible light in the range of 460 to 470 nm. The effect of environmental parameters including initial DFC concentration, pH and the presence of various anions were studied by the measurement of the rate constant for DFC decomposition. Superior performance photocatalytic activity using BPCN is achieved in the pH 5.0 and initial DFC concentration up to 30 mg L-1. It is clear that the BPCN-3 photocatalyst exhibits enhanced phototocatalytic activity for DFC decomposition (0.047 min-1), which is about 4.7 times higher in comparision with undoped C3N4 (0.01 min-1) with an optimized boron and phosphorus doping of 9.7% and 2.1 %, respectively. The enhanced degradation abilities of newly developed one dimensional BPCN, can be attributed to the increased surface area, visible-light response and photoinduced charge separation, overcoming the shortcomings of bare g- C3N4. These results clearly demonstrate that the metal free boron and phosphorus co-doped C3N4 is a reliable green technology approach to prepare visible-light-responsive photocatalyst with great potential for application in the decomposition of antibiotics and other emerging pollutants for water treatment.

Contents
摘要 i
Abstract vi
Index of Figure viii
Index of Table x
Abbreviation xi
Chapter 1. Introduction 1
1.1. Motivation 1
1.2 Objectives 2
Chapter 2. Literature review 4
2.1. Diclofenac and the removal of diclofenac in the environment 4
2.2. Metal-free g- C3N4 photocatalyst 8
2.2. Applications of g-C3N4 11
2.3. Modification of g-C3N4 based photocatalyst 13
2.3.1. Doping g-C3N4 13
2.3.2. Dimensional tuning 19
Chapter 3. Materials and method 21
3.1. Chemicals 21
3.2. Experimental section 21
3.2.1. Synthesis one-dimensional (1-D) Boron, Phosphorous co-doped C3N4 (BPCN) 22
3.2.2. Photocatalytic activities of B,P co-doped 1-D C3N4 toward Diclofenac degradation 23
3.2.3. Reaction kinetics 24
3.3. Analytical methods 25
3.3.1. X-ray Diffraction (XRD) 25
3.3.2. Brunauer-Emmett-Teller (BET) 25
3.3.3. Scanning electron microscope (SEM) 26
3.3.4. Transmission Electron Microscopy (TEM) 27
3.3.5. Fourier transform infrared spectroscopy (FTIR) 27
3.3.6. X-ray photoelectron spectroscopy analysis (XPS) 27
3.3.7. Thermogravimetric analysis (TGA) 28
3.3.8. UV-visible spectroscopy (UV-Vis) and band gap 28
3.3.9. Zeta potential measurement (ξ) 29
Chapter 4. Results and discussion 30
4.1. Optimization of hydrothermal condition 30
4.2. Surface characterizations 35
4.2.1. XRD properties 35
4.2.2. Morphological properties of B, P co-doped 1-D C3N4 and the possible mechanism for the formation of tubular structure 36
4.2.3. Textural properties of B, P co-doped 1-D C3N4 41
4.2.4. XPS analysis of B, P co-doped 1-D C3N4 44
4.2.5. FTIR spectra of B, P co-doped 1-D C3N4 47
4.2.6. Thermal stability of B, P co-doped 1-D C3N4 48
4.2.7. Optical properties of B, P co-doped 1-D C3N4 49
4.2.8. Fluorescence analysis of B, P co-doped 1-D C3N4 52
4.3. Application of P- C3N4 for photocatalytic degradation of Diclofenac (DFC) 54
4.3.1. Photocatalytic activity of B, P co-doped 1-D C3N4 under visible light irradiation 54
4.3.2. Effect of initial DFC concentration on photocatalytic performance of B, P co-doped 1-D C3N4 57
4.3.3. Effect of pH value on photocatalytic performance of B, P co-doped 1-D C3N4 59
4.3.4. Effect of radical scavengers on photocatalytic performance of B, P co-doped 1-D C3N4 61
Chapter 5. Conclusion 63

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