發(fā)光高分子復合薄膜的制備及其傳感性能研究
發(fā)布時間：2019-02-23 14:34
【摘要】：隨著工業(yè)化進程的加劇,人們向環(huán)境中排放的有毒、有害物質(zhì)逐年增多,隨之而來的大氣、水體和土壤污染等問題也日益嚴重。這些問題不但會對生態(tài)環(huán)境造成不利影響,而且威脅著人類的生存。因此,針對有毒有害物質(zhì)研究的傳感材料就顯得尤為重要。光致發(fā)光復合薄膜材料,由于其在薄膜材料的內(nèi)部或表面引入了發(fā)光物種(無機熒光材料或有機熒光材料),故具有一定的光學性能,且薄膜易加工、透明度高、發(fā)光穩(wěn)定性好、發(fā)光效率高,目前該類新的復合薄膜材料已成為一類很有發(fā)展前景的功能材料。論文分別以鋁酸鍶、7-硝基苯并呋喃修飾的膽固醇(NBD-chol)為發(fā)光物質(zhì),易成膜高分子為基質(zhì),設(shè)計并制備一系列發(fā)光高分子復合薄膜材料,并系統(tǒng)研究了這些薄膜對氣相和液相中有害物質(zhì)的傳感性能。1.采用本體聚合法合成的聚甲基丙烯酸甲酯(PMMA)為成膜高分子基質(zhì),引入發(fā)光材料鋁酸鍶(SrAl2O4),制備得到SrAl2O4/PMMA復合薄膜材料。采用SEM、熒光顯微鏡等手段對薄膜進行表征;利用靜態(tài)熒光光譜、熒光壽命、熒光猝滅等光物理手段對其傳感性能進行研究;并分析了薄膜干燥方式、鑄膜液制備方法對薄膜傳感性能的影響。發(fā)現(xiàn)該薄膜對氣相中醇類化合物表現(xiàn)出靈敏的選擇性傳感,且傳感可逆性良好;熒光壽命測試結(jié)果表明,猝滅過程為靜態(tài)猝滅。2.為了檢測水溶液中的有害物質(zhì),考慮到其在復合薄膜中快速的擴散,采用親水性更強的聚甲基丙烯酸羥乙酯(PHEMA)為成膜基質(zhì),以具有自組裝能力的熒光物質(zhì)NBD-chol為發(fā)光物種,制備得到一系列熒光復合傳感薄膜。采用SEM、熒光顯微鏡等手段對薄膜進行表征;傳感性能實驗表明,液相中的胺類化合物對該薄膜的熒光發(fā)射具有明顯的猝滅作用,可以實現(xiàn)高靈敏度的檢測,而且傳感過程可逆;通過熒光壽命的變化情況,證實了薄膜對胺類化合物的猝滅過程為靜態(tài)猝滅,并對猝滅機理進行了研究。3.結(jié)合上述的研究結(jié)果,首先制備得到NBD-chol/PMMA發(fā)光薄膜,考慮到用于液相中有害物質(zhì)的檢測,將NBD-chol/PMMA薄膜經(jīng)濃硫酸水解處理,制備得到NBD-chol/PMAA復合薄膜。采用紅外光譜對薄膜組分進行表征;薄膜傳感特性的研究結(jié)果表明,液相中乙醚對該薄膜的熒光發(fā)射具有較為明顯的猝滅作用,且傳感可逆性良好。熒光壽命測試結(jié)果顯示,猝滅過程為靜態(tài)猝滅。
[Abstract]:With the aggravation of industrialization, the poisonous and harmful substances discharged into the environment are increasing year by year, and the following problems such as air, water and soil pollution are becoming more and more serious. These problems will not only adversely affect the ecological environment, but also threaten the survival of mankind. Therefore, the sensing materials for the study of toxic and harmful substances are particularly important. Photoluminescence composite thin film materials, because of the introduction of luminescent species (inorganic fluorescent materials or organic fluorescent materials) into the inner or surface of thin film materials, have certain optical properties, and the films are easy to process and transparent. With good luminescence stability and high luminescence efficiency, this kind of new composite thin films has become a kind of functional materials with good development prospects. In this paper, a series of luminescent polymer composite film materials were designed and prepared by using strontium aluminate, cholesterol modified by 7-nitrobenzofuran (NBD-chol) as luminescent material and easy film forming polymer as substrate. The sensing properties of these films to harmful substances in gas phase and liquid phase were studied systematically. 1. SrAl2O4/PMMA composite films were prepared by bulk polymerization of poly (methyl methacrylate) (PMMA) as film forming polymer matrix and luminescent material strontium aluminate (SrAl2O4). The thin films were characterized by SEM, fluorescence microscope, and their sensing properties were studied by means of static fluorescence spectrum, fluorescence lifetime, fluorescence quenching and other photophysical methods. The effects of the drying method and the preparation method of casting solution on the sensing properties of the film were analyzed. It is found that the film is sensitive to the selective sensing of alcohols in the gas phase, and the sensing reversibility is good, and the fluorescence lifetime measurement shows that the quenching process is static quenching. 2. In order to detect the harmful substances in aqueous solution and to consider the rapid diffusion in the composite film, the hydrophilic polyhydroxyethyl methacrylate (PHEMA) was used as the film substrate. A series of fluorescent composite sensing films were prepared by using NBD-chol, a fluorescent substance with self-assembly ability, as a luminescent species. The films were characterized by SEM, fluorescence microscope. The sensing performance experiments show that the amine compounds in the liquid phase have obvious quenching effect on the fluorescence emission of the film, which can achieve high sensitivity detection, and the sensing process is reversible. The quenching process of amine compounds was confirmed by the change of fluorescence lifetime, and the quenching mechanism was studied. Based on the above results, the NBD-chol/PMMA thin films were prepared. Considering the detection of harmful substances in liquid phase, the NBD-chol/PMMA films were hydrolyzed with concentrated sulfuric acid to prepare NBD-chol/PMAA composite films. The infrared spectra were used to characterize the composition of the thin films, and the results showed that the fluorescence emission of the films was quenched by ether in liquid phase, and the sensing reversibility was good. The fluorescence lifetime test shows that the quenching process is static quenching.
【學位授予單位】：長安大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TB383.2
本文編號：2428922
[Abstract]:With the aggravation of industrialization, the poisonous and harmful substances discharged into the environment are increasing year by year, and the following problems such as air, water and soil pollution are becoming more and more serious. These problems will not only adversely affect the ecological environment, but also threaten the survival of mankind. Therefore, the sensing materials for the study of toxic and harmful substances are particularly important. Photoluminescence composite thin film materials, because of the introduction of luminescent species (inorganic fluorescent materials or organic fluorescent materials) into the inner or surface of thin film materials, have certain optical properties, and the films are easy to process and transparent. With good luminescence stability and high luminescence efficiency, this kind of new composite thin films has become a kind of functional materials with good development prospects. In this paper, a series of luminescent polymer composite film materials were designed and prepared by using strontium aluminate, cholesterol modified by 7-nitrobenzofuran (NBD-chol) as luminescent material and easy film forming polymer as substrate. The sensing properties of these films to harmful substances in gas phase and liquid phase were studied systematically. 1. SrAl2O4/PMMA composite films were prepared by bulk polymerization of poly (methyl methacrylate) (PMMA) as film forming polymer matrix and luminescent material strontium aluminate (SrAl2O4). The thin films were characterized by SEM, fluorescence microscope, and their sensing properties were studied by means of static fluorescence spectrum, fluorescence lifetime, fluorescence quenching and other photophysical methods. The effects of the drying method and the preparation method of casting solution on the sensing properties of the film were analyzed. It is found that the film is sensitive to the selective sensing of alcohols in the gas phase, and the sensing reversibility is good, and the fluorescence lifetime measurement shows that the quenching process is static quenching. 2. In order to detect the harmful substances in aqueous solution and to consider the rapid diffusion in the composite film, the hydrophilic polyhydroxyethyl methacrylate (PHEMA) was used as the film substrate. A series of fluorescent composite sensing films were prepared by using NBD-chol, a fluorescent substance with self-assembly ability, as a luminescent species. The films were characterized by SEM, fluorescence microscope. The sensing performance experiments show that the amine compounds in the liquid phase have obvious quenching effect on the fluorescence emission of the film, which can achieve high sensitivity detection, and the sensing process is reversible. The quenching process of amine compounds was confirmed by the change of fluorescence lifetime, and the quenching mechanism was studied. Based on the above results, the NBD-chol/PMMA thin films were prepared. Considering the detection of harmful substances in liquid phase, the NBD-chol/PMMA films were hydrolyzed with concentrated sulfuric acid to prepare NBD-chol/PMAA composite films. The infrared spectra were used to characterize the composition of the thin films, and the results showed that the fluorescence emission of the films was quenched by ether in liquid phase, and the sensing reversibility was good. The fluorescence lifetime test shows that the quenching process is static quenching.
【學位授予單位】：長安大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TB383.2
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