大氣電漿噴塗氮摻雜還原態二氧化鈦光觸媒塗層製程開發並應用於光催化降解抗生素

Abstract

本篇研究中，提出一個結合仿地質概念與大氣電漿噴塗，快速且一步驟完成多孔性氮摻雜還原態二氧化鈦光觸媒塗層的新穎製程。是第一篇利用大氣電漿技術實現氮摻雜材料修飾的研究。在噴塗過程中，透過自然啟發的蒸氣造孔技術，將儲存在基材孔洞中的含氮水溶液快速蒸發，使氮來源分解形成氨氣，與二氧化鈦粉體進行摻雜。研究中先後對於氮來源的濃度以及種類進行比較與分析，再針對四環素(TC)以及環丙沙星(CIP)進行可見光降解實驗，以此來評價光觸媒的光催化活性。並且透過液相層析質譜儀以及犧牲試劑測驗，了解其降解機制以及路徑。結果在較高的濃度下，化學表面吸附氮比例上升，這種形式的氮不會提升二氧化鈦在可見光下的光催化活性。在濃度較低的情況下，反而可以有效提升晶格氮/吸附氮的比例，可以增強光催化活性。以5 wt% (TN5)與15 wt% (TN15)的乙醯胺做為氮來源的結果中可以看到，TN5的降解率比TN15高56.47%。在不同種類的氮來源比較下選用的是結構中擁有一個氮原子的乙醯胺以及兩個氮原子的尿素。結構中擁有氮的數量會決定氮摻雜時環境中氮的濃度。從結果表明，以乙醯胺做為氮摻雜來源所製備出的樣品(T1N)比以尿素做為氮摻雜來源所製備出的樣品(T2N)，在TC以及CIP的降解中，分別高出32.91以及31.2%。本次研究最大的價值在首次利用大氣電漿技術實現氮摻雜材料修飾，並且在製備時間上具有非常大的優勢。這是一個適合放大規模的製程，省時且對自然環境無害。除了替材料合成開創新的可能性之外，在未來也是非常具有商業化以及工業化潛力的一項技術。

In this study, a novel process combining simulated geological concepts with atmospheric plasma spraying is proposed to achieve a rapid and one-step fabrication of porous nitrogen-doped reduced TiO2 photocatalytic coatings. This is the first study to utilize atmospheric plasma technology for nitrogen-doped material modification. During the spraying process, a naturally inspired vapor-induced pore formation technique is employed to rapidly evaporate the nitrogen-containing solution stored in the substrate pores, resulting in the decomposition of nitrogen sources to form ammonia gas, which is then doped into TiO2 powder. The study compares and analyzes the concentration and types of nitrogen sources, and subsequently conducts visible light degradation experiments on tetracycline (TC) and ciprofloxacin (CIP) to evaluate the photocatalytic activity of the catalyst. Additionally, liquid chromatography-mass spectrometry and sacrificial reagent tests are employed to understand the degradation mechanism and pathways. The results show that at higher concentrations, the proportion of chemisorbed nitrogen on the surface increases, but this form of nitrogen does not enhance the photocatalytic activity of titanium dioxide under visible light. At lower concentrations, however, the proportion of lattice nitrogen/adsorbed nitrogen is effectively increased, leading to enhanced photocatalytic activity. The results from using 5 wt% (TN5) and 15 wt% (TN15) acetamide as nitrogen sources indicate that the degradation rate of TN5 is 56.47% higher than TN15. Among different types of nitrogen sources, acetamide with one nitrogen atom in its structure and urea with two nitrogen atoms are selected for comparison. The quantity of nitrogen in the structure determines the nitrogen concentration during doping. The results suggest that samples prepared with acetamide as the nitrogen source (T1N) outperform those prepared with urea as the nitrogen source (T2N) in TC and CIP degradation, with improvements of 32.91% and 31.2%, respectively. The major significance of this study lies in the first-time utilization of atmospheric plasma technology for nitrogen-doped material modification, offering significant advantages in preparation time. This process is suitable for scaling up, saving time, and being environmentally friendly. In addition to opening new possibilities for material synthesis, this technology also holds strong potential for commercialization and industrialization in the future.