聚溴化3-噻吩甲基-N,N-二甲基-N-烷基銨的合成及其在LGB光催化降解的應(yīng)用
發(fā)布時(shí)間：2019-06-28 20:38
【摘要】：共軛聚合物是具有離域大π鍵的有機(jī)半導(dǎo)體材料。由于它們具有獨(dú)特的物理化學(xué)性質(zhì),得到了研究者廣泛的關(guān)注。常見的共軛聚合物有聚苯胺、聚吡咯、聚乙炔和聚噻吩。這些材料可以通過(guò)引入側(cè)鏈的方式,改變聚合物的性質(zhì),從而改善材料的性能,還擴(kuò)大了共軛聚合物材料的門類。因?yàn)楣曹棪墟I的存在使得聚合物的能隙很低,容易吸收紫外可見光,同時(shí)低能隙可以讓共軛聚合物擁有較高的電荷分離能力和低的電子空穴復(fù)合率。當(dāng)該類聚合物與無(wú)機(jī)半導(dǎo)體光催化材料雜化,可以降低無(wú)機(jī)材料的帶隙,提高電荷分離能力和降低電子空穴對(duì)的復(fù)合率,以達(dá)到提高光催化材料的光催化性能。因此,探究新的共軛聚合物的合成以及在光催化方面的應(yīng)用有很重要的意義。本文合成了溴化3-噻吩甲基-N,N-二甲基-N-烷基銨(目標(biāo)產(chǎn)物標(biāo)記為s-n,n=10、12、14、16),通過(guò)化學(xué)氧化聚合方法合成了相應(yīng)的聚合物(標(biāo)記為Ps-n,n=10、12、14、16)。制備了Ps-12/ZnO光催化材料,并探討了該復(fù)合材料在紫外光下降解酸性綠50的光催化活性。具體內(nèi)容如下:通過(guò)簡(jiǎn)單的季銨化反應(yīng),以3-溴甲基噻吩為原料合成了s-n,并通過(guò)核磁共振譜圖和紅外光譜對(duì)s-n的結(jié)構(gòu)進(jìn)行了表征,并用MS測(cè)得其分子量。從量子化學(xué)計(jì)算結(jié)果可知,隨著烷基鏈的增加,目標(biāo)產(chǎn)物的反應(yīng)活性增加,動(dòng)力學(xué)穩(wěn)定性降低。但是,烷基鏈的改變對(duì)這種影響很小。從Fukui函數(shù)可知,目標(biāo)產(chǎn)物的反應(yīng)活性位點(diǎn)主要分布在噻吩環(huán)上的碳原子和硫原子上,這與化合物的結(jié)構(gòu)特征一致。通過(guò)FeCl3氧化催化法合成了聚合物Ps-n。通過(guò)UV-vis光譜測(cè)試,相比于s-n,發(fā)現(xiàn)聚合物的紫外吸收范圍增大,說(shuō)明聚合物分子中形成了更大的共軛體系,從側(cè)面證實(shí)了s-n發(fā)生了聚合。紅外光譜表明,相對(duì)于單體,聚合物中3080 cm-1左右處未出現(xiàn)噻吩環(huán)上的α位C-H的伸縮振動(dòng)吸收峰,這表明了s-n發(fā)生了聚合反應(yīng)生成了Ps-n。XRD分析結(jié)果表明制備的四種聚合物均為非晶型結(jié)構(gòu)。從量子化學(xué)計(jì)算結(jié)果可知,隨著目標(biāo)產(chǎn)物的烷基鏈增長(zhǎng),目標(biāo)產(chǎn)物的反應(yīng)活性增加,動(dòng)力學(xué)穩(wěn)定性降低。從Fukui函數(shù)可知,Ps-n的反應(yīng)活性位點(diǎn)主要分布在噻吩環(huán)上的碳原子和硫原子上。這與聚合物的結(jié)構(gòu)特征一致。通過(guò)比較了s-10和Ps-10的理論計(jì)算數(shù)據(jù),我們發(fā)現(xiàn)Ps-10噻吩環(huán)上的自然原子電荷低于s-10,這說(shuō)明聚合物的共軛體系使電子云密度平均化,提高了分子的穩(wěn)定性。從量子化學(xué)參數(shù)可知,s-10的化學(xué)活性高于Ps-10,Ps-10比s-10更穩(wěn)定。通過(guò)化學(xué)吸附法,制備了Ps-12-雜化ZnO材料,通過(guò)XRD、SEM、DRS、FT-IR和PL等方法對(duì)其晶體結(jié)構(gòu)、形貌特征、光學(xué)特性等進(jìn)行了表征分析。雜化后,Ps-12-雜化ZnO材料中氧化鋅的晶體結(jié)構(gòu)沒有發(fā)生改變。雜化材料子紫外光下對(duì)酸性綠50的降解率達(dá)96.6%。降解過(guò)程中的主要活性物種為超氧負(fù)離子自由基。在降解酸性綠50的過(guò)程中Ps-12-雜化ZnO材料表現(xiàn)出良好的穩(wěn)定性,重復(fù)使用5次,催化性能保持87%。在光催化機(jī)理中,Ps-12可能作為光敏劑來(lái)降低光生-電子空穴對(duì)的復(fù)合和提高光生-電子空穴對(duì)的分離來(lái)提高光催化活性。
[Abstract]:The co-conductive polymer is an organic semiconductor material having a defield large-scale bond. Because of their unique physical and chemical properties, the researchers have received extensive attention. Common copolymeric polymers are polyanilines, polypropylenes, polyacetylene, and polyacetylene. These materials can modify the properties of the polymer by introducing side chains in order to improve the properties of the material and also to expand the range of co-polymer materials. Because of the existence of the co-polar bond, the energy gap of the polymer is low, the ultraviolet visible light can be easily absorbed, and meanwhile, the low-energy gap can make the co-polar polymer have higher charge separation capacity and low electron-hole recombination rate. When the polymer is hybridized with the inorganic semiconductor photocatalytic material, the band gap of the inorganic material can be reduced, the charge separation capacity can be improved, and the recombination rate of the electron hole pair can be reduced, so that the photocatalytic performance of the photocatalytic material can be improved. Therefore, it is of great significance to explore the synthesis of new co-polymer and its application in photocatalysis. Brominated 3-methyl-N, N-dimethyl-N-alkyl (labeled as s-n, n = 10,12,14,16) were synthesized and the corresponding polymers (labeled Ps-n, n = 10,12,14,16) were synthesized by chemical oxidative polymerization. The photocatalytic material of Ps-12/ ZnO was prepared, and the photocatalytic activity of the composite was discussed. In this paper, the structure of s-n is synthesized by a simple and seasonal reaction, and the structure of s-n is characterized by the nuclear magnetic resonance spectrum and the infrared spectrum, and the molecular weight of the s-n is measured by the MS. The result of the quantum chemical calculation shows that with the increase of the alkyl chain, the reaction activity of the target product is increased, and the kinetic stability is reduced. However, the change in the alkyl chain is very small for this effect. It can be seen from the Fukui function that the reactive sites of the target product are mainly distributed on the carbon and sulfur atoms on the alicyclic ring, which is consistent with the structural characteristics of the compound. The polymer Ps-n were synthesized by the FeCl3 oxidation catalytic process. By UV-vis spectroscopy, it was found that the ultraviolet absorption range of the polymer increased as compared with s-n, indicating that the polymer molecule formed a larger co-polymerization system, and it was confirmed that s-n had been polymerized from the side. The infrared spectra show that the expansion vibration absorption peak of C-H is not present at 3080 cm-1 in the polymer, which shows that the generation of Ps-n by the polymerization of s-n. The results of the XRD analysis show that the prepared four polymers are amorphous. The result of the quantum chemical calculation shows that with the increase of the alkyl chain of the target product, the reaction activity of the target product is increased, and the kinetic stability is reduced. As can be seen from the Fukui function, the reactive sites of Ps-n are mainly distributed on the carbon and sulfur atoms on the alicyclic ring. This is consistent with the structural features of the polymer. By comparing the theoretical calculation data of s-10 and Ps-10, we find that the natural atom charges on the Ps-10 and Ps-10 are lower than s-10, which means that the common system of the polymer can average the density of the electron cloud and improve the stability of the molecules. From the quantum chemical parameters, the chemical activity of s-10 is higher than that of Ps-10 and Ps-10 is more stable than that of s-10. The crystal structure, morphology and optical properties of the Ps-12-hybrid ZnO material were characterized by means of chemical adsorption, XRD, SEM, DRS, FT-IR and PL. The crystal structure of the zinc oxide in the Ps-12-hybrid ZnO material has not changed after the hybridization. The degradation rate of the acid green 50 was 96.6% under the sub-ultraviolet light of the hybrid material. The main active species in the degradation process are superoxide anion free radicals. In the process of degradation of the acid green 50, the Ps-12-hybrid ZnO material exhibits good stability, can be used for 5 times, and the catalytic performance is maintained for 87%. In the light catalytic mechanism, Ps-12 may be used as photosensitizers to reduce the recombination of photo-generated-electron-hole pairs and to improve the separation of photo-generated-electron-hole pairs to improve the photocatalytic activity.
【學(xué)位授予單位】：西華師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36;O644.1
本文編號(hào)：2507597
[Abstract]:The co-conductive polymer is an organic semiconductor material having a defield large-scale bond. Because of their unique physical and chemical properties, the researchers have received extensive attention. Common copolymeric polymers are polyanilines, polypropylenes, polyacetylene, and polyacetylene. These materials can modify the properties of the polymer by introducing side chains in order to improve the properties of the material and also to expand the range of co-polymer materials. Because of the existence of the co-polar bond, the energy gap of the polymer is low, the ultraviolet visible light can be easily absorbed, and meanwhile, the low-energy gap can make the co-polar polymer have higher charge separation capacity and low electron-hole recombination rate. When the polymer is hybridized with the inorganic semiconductor photocatalytic material, the band gap of the inorganic material can be reduced, the charge separation capacity can be improved, and the recombination rate of the electron hole pair can be reduced, so that the photocatalytic performance of the photocatalytic material can be improved. Therefore, it is of great significance to explore the synthesis of new co-polymer and its application in photocatalysis. Brominated 3-methyl-N, N-dimethyl-N-alkyl (labeled as s-n, n = 10,12,14,16) were synthesized and the corresponding polymers (labeled Ps-n, n = 10,12,14,16) were synthesized by chemical oxidative polymerization. The photocatalytic material of Ps-12/ ZnO was prepared, and the photocatalytic activity of the composite was discussed. In this paper, the structure of s-n is synthesized by a simple and seasonal reaction, and the structure of s-n is characterized by the nuclear magnetic resonance spectrum and the infrared spectrum, and the molecular weight of the s-n is measured by the MS. The result of the quantum chemical calculation shows that with the increase of the alkyl chain, the reaction activity of the target product is increased, and the kinetic stability is reduced. However, the change in the alkyl chain is very small for this effect. It can be seen from the Fukui function that the reactive sites of the target product are mainly distributed on the carbon and sulfur atoms on the alicyclic ring, which is consistent with the structural characteristics of the compound. The polymer Ps-n were synthesized by the FeCl3 oxidation catalytic process. By UV-vis spectroscopy, it was found that the ultraviolet absorption range of the polymer increased as compared with s-n, indicating that the polymer molecule formed a larger co-polymerization system, and it was confirmed that s-n had been polymerized from the side. The infrared spectra show that the expansion vibration absorption peak of C-H is not present at 3080 cm-1 in the polymer, which shows that the generation of Ps-n by the polymerization of s-n. The results of the XRD analysis show that the prepared four polymers are amorphous. The result of the quantum chemical calculation shows that with the increase of the alkyl chain of the target product, the reaction activity of the target product is increased, and the kinetic stability is reduced. As can be seen from the Fukui function, the reactive sites of Ps-n are mainly distributed on the carbon and sulfur atoms on the alicyclic ring. This is consistent with the structural features of the polymer. By comparing the theoretical calculation data of s-10 and Ps-10, we find that the natural atom charges on the Ps-10 and Ps-10 are lower than s-10, which means that the common system of the polymer can average the density of the electron cloud and improve the stability of the molecules. From the quantum chemical parameters, the chemical activity of s-10 is higher than that of Ps-10 and Ps-10 is more stable than that of s-10. The crystal structure, morphology and optical properties of the Ps-12-hybrid ZnO material were characterized by means of chemical adsorption, XRD, SEM, DRS, FT-IR and PL. The crystal structure of the zinc oxide in the Ps-12-hybrid ZnO material has not changed after the hybridization. The degradation rate of the acid green 50 was 96.6% under the sub-ultraviolet light of the hybrid material. The main active species in the degradation process are superoxide anion free radicals. In the process of degradation of the acid green 50, the Ps-12-hybrid ZnO material exhibits good stability, can be used for 5 times, and the catalytic performance is maintained for 87%. In the light catalytic mechanism, Ps-12 may be used as photosensitizers to reduce the recombination of photo-generated-electron-hole pairs and to improve the separation of photo-generated-electron-hole pairs to improve the photocatalytic activity.
【學(xué)位授予單位】：西華師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36;O644.1
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