- 學位論文
磷摻雜石墨型氮化碳應用於薄膜觸媒反應器之設計及應用
Design and Application of Photocatalytic-Membrane Reactor using Phosphorus-Doped Graphitic Carbon Nitride as Photocatalyst
摘要
如何有效的解決廢水問題是目前備受矚目的議題，其中光觸媒薄膜反應器(Photocatalytic-Membrane Reactor, PMR)是近年來嶄新處理廢水的系統。相較於傳統批次光催化反應，光觸媒薄膜反應器具有以下優點，限制光觸媒在反應環境內、控制分子在反應器內的滯留時間，並可在連續操作過程中將產物與光觸媒分離。因此本實驗將設計一個薄膜觸媒反應混和系統，利用光化學氧化法以及薄膜過濾處理有機廢水。 本實驗以三聚氯化磷腈(HCCP)與三聚氰胺(melamine)作為前驅物，經固相法高溫鍛燒後得到磷離子摻雜石墨型氮化碳(PCN)，並改變反應物之重量百分比來檢測對晶體結構與型態之影響。XRD結果顯示，透過重量百分比5、10、15的磷離子摻雜後，PCN仍保持著13.1與27.1度的石墨型氮化碳(100)與(002)結晶面繞射峰； PL中則可發現，經由磷摻雜後之PCN其放光特性皆比石墨型氮化碳小，表示磷摻雜有助於減少電子電洞對再結合。接著利用可見光照射進行光催化降解反應，其中以重量百分比10的磷離子摻雜石墨型氮化碳(10PCN)具有最佳的光催化反應，利用一階動力模型計算後可得速率常數k值為 0.019 min-1。 而本研究選擇無機陶瓷膜做為薄膜觸媒混和系統之薄膜，因其機械強度相對於高分子聚合物薄膜高，亦可長時間操作，中空纖維膜之膜孔直徑約為1.2 mm，膜厚約為200 μm。 並透過結合高催化活性的磷摻雜氮化碳(PCN)光觸媒與薄膜過濾設置一光觸媒薄膜反應器，於金屬鹵素燈照射下對於有機染劑甲基藍(Methyl Blue, MB)進行移除，其效率相對於批次光催化系統和薄膜系統分別提升了1.63和1.22倍，並且具有良好的穩定性；在移除甲基橙(Methyl Orange, MO)時，PMR系統能有效減緩薄膜結垢的問題；在移除苯酚(phenol)時，PMR系統能將有毒物質礦化成小分子化合物。並且經由模擬工廠廢水，PMR系統能有效降解3種不同有機廢水。經上述實驗測試，證明PMR系統能夠有效的處理不同種類的有機廢水。 KEYWORDS: 光觸媒薄膜反應器、磷摻雜、石墨型氮化碳、甲基藍、可見光
並列摘要
Photocatalytic-Membrane Reactor (PMR) has been widely used in wastewater removal in recent years. Compared to batch photodegradation system, not only photocatalyst can be separated from liquid phase in PMR, but also the removal efficiency can be increased significantly. In this study, we design a PMR system to remove wastewater containing methyl blue, methyl orange, phenol, and mixed organic dyes. In this study, phosphorus-doped graphite-type carbon nitride (PCN) was prepared in an attempt to coat on the substrate. XRD patterns show the diffraction peaks of PCN are located at 13.1° and 27.1°, which can be confirm as the (100) and (002) crystal plane of graphite-type carbon nitride(C3N4). In PL analysis, the emission peak of PCN is lower than C3N4, which can be contributed to the phosphorus doping. In photodegradation reactions, 10 wt% of phosphorus-doped C3N4 (10PCN) showed the highest degradation activity under visible light irradiation among the samples. In the hollow fiber membrane system, an inorganic hollow fiber membrane was prepared by spinning using an alumina solution. SEM images revealed the pore diameter of the membrane was approximately 1.2 mm and the membrane thickness was around 200 μm. To fabricate a PMR system, PCN was integrated with PMR system for wastewater treatment under irradiation of metal halide lamp. The removal efficiency of the PMR system is 1.63 and 1.22 times higher than the batch photodegradation system and the membrane system, respectively. The PMR system show high stability and can effectively removal different kinds of organic wastewater. KEYWORDS: Photocatalytic-Membrane Reactor, phosphorus doping, graphite carbon nitride, methyl blue, visible light
參考文獻
延伸閱讀
- 楊順文（2002）。電漿聚合碳氮層-TPX複合膜應用於氧氮分離之研究〔碩士論文，中原大學〕。華藝線上圖書館。https://doi.org/10.6840/cycu200200241
- 林頌哲（2016）。以旋轉塗布磷摻雜源製程應用於超高密度矽量子點薄膜之研究〔碩士論文，國立交通大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0030-2212201712174798
- 姜妍忻（2016）。以化學氣相沉積法成長硼摻雜型石墨烯和新穎氮化矽薄膜前驅物之合成〔碩士論文，國立清華大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0016-0901201710354709
- 劉守靜（2008）。Synthesis of nano-photocatalysts using hydrothermal method and its efficiencies, mechanisms of photocatalytic degradation with triphenylmethane dyes〔碩士論文，中山醫學大學〕。華藝線上圖書館。https://doi.org/10.6834/CSMU.2008.00001
- 林冠宇（2017）。Hydrophobic Nanocomposite Photocatalyst for Photocatalytic Carbon Dioxide Hydrogenation〔碩士論文，國立臺灣大學〕。華藝線上圖書館。https://doi.org/10.6342/NTU201701703