透明PMOs凝膠獨石的控制制備及其光學性能
發(fā)布時間：2018-07-31 13:11
【摘要】：周期性介孔有機二氧化硅（PMOs）是采用橋聯(lián)倍半硅氧烷作前驅體，在表面活性劑模板作用下合成的一類新型有機-無機雜化介孔材料。由于其合成思想至少允許將兩種不同的功能化單元同步放置在介孔結構中兩個空間上相分離的區(qū)域—孔壁骨架和介孔孔道，使它在各種新型復合功能材料的研究領域顯示出更為廣泛的應用前景。顯然，若能控制合成具有宏觀形貌及尺寸可調的透明PMOs凝膠獨石，將較常規(guī)的粉體材料具有更好的可操作性，在新型光、電、磁性器件及固體染料激光器、傳感器等的研究領域具有重要意義，而目前PMOs材料的合成及應用研究仍局限于粉體或薄膜形貌。 基于上述思想，本工作采用商品化的亞乙基橋聯(lián)倍半硅氧烷作前驅體，在酸性條件下以不同非離子嵌段共聚物類表面活性劑作模板劑，系統(tǒng)開展了亞乙基橋聯(lián)的透明PMOs凝膠獨石的無裂紋化控制制備技術和規(guī)律研究，并將具有不同結構和物性的有機染料如羅丹明6G（Rh6G）、7-羥基-4-甲基香豆素（7H4MC）和亞甲基藍（MB）等采用直接合成的方式引入透明PMOs凝膠孔道，初步研究了染料摻雜后凝膠的光學性能。主要研究結果如下： 1、首先以F127作模板劑，通過對合成參數(shù)和制備條件的全面篩選和評價，在40℃恒溫敞口干燥的條件下首次控制合成了宏觀尺寸可隨容器形狀加以調節(jié)的透明PMOs凝膠獨石。通過對不同脫模板方法如乙醇萃取，水萃取，焙燒及高氯酸銨氧化等處理后樣品的N2吸附和TG分析，發(fā)現(xiàn)高氯酸銨氧化法是一種更為有效的脫模板方法，且在脫模板后仍能保持凝膠整體形貌的完整。其N2吸附等溫線呈含H2型滯后環(huán)的IV型曲線，暗示凝膠可能含有與SBA-16相似的類籠形介孔結構。對Rh6G摻雜后凝膠的UV-vis及熒光光譜研究發(fā)現(xiàn)，Rh6G在PMOs凝膠中的二聚傾向明顯減弱，發(fā)射光譜藍移。說明PMOs凝膠獨石中模板劑的存在有利于染料分子的更好分散和穩(wěn)定，進而改善材料的發(fā)光性能。 2、采用P123作模板劑，以甲醇作助溶劑，在14.5-35.5wt%的模板劑濃度范圍內(nèi)控制合成了具有類SBA-15結構的二維六方相亞乙基橋聯(lián)的透明PMOs透明凝膠獨石。將7H4MC香豆素染料引入透明PMOs凝膠獨石后的光學性能研究顯示，7H4MC/SiO-42比在10-2-10間調節(jié)時，隨染料濃度的增加，，發(fā)射光譜僅輕微紅移但其發(fā)光強度卻顯著增加。在固定7H4MC/SiO2比為10-3時，發(fā)現(xiàn)過高的模板劑濃度反而會因凝膠中染料占比的降低而使發(fā)光強度減弱，說明模板劑的存在不僅有利于更高濃度染料分子的分散，而且染料摻雜的濃度與所使用模板劑的濃度間在保證PMOs凝膠獨石整體完整的前提存在一定的最佳匹配關系。 3、采用Brij56作模板劑，乙醇作助溶劑，在模板劑濃度為5.2-35.5wt%的范圍內(nèi)控制合成了亞乙基改性的PMOs透明凝膠獨石材料。研究發(fā)現(xiàn)引入長鏈醇，如丁、戊、己醇或調節(jié)其濃度，均可在保證凝膠整體透明完整的前提下，使凝膠的孔徑有所增加。MB摻雜PMO凝膠后的紫外-可見及熒光光譜研究結果顯示，模板劑的存在同樣有助于MB染料分子的高濃度分散，進而使染料分子間二聚的趨勢減弱，發(fā)射光譜明顯藍移，有助于材料光學性能的改善
[Abstract]:Periodic mesoporous organic silica (PMOs) is a new type of organic-inorganic hybrid mesoporous material which is synthesized under the action of surfactant template with bridged sesquioxane as a precursor and at least two different functional units are allowed to be placed in two space separated areas in the mesoporous structure. The pore wall skeleton and mesoporous channel make it more widely applied in the research field of various new composite functional materials. Obviously, if the transparent PMOs gel with macro morphologies and adjustable sizes can be controlled, it will have better operability than the conventional powder materials in the new light, electricity, magnetic devices and solids. The research fields of dye lasers and sensors are of great significance, but the synthesis and application of PMOs are still limited to the morphology of powders or thin films.
Based on the above thought, a commercialized ethylenediethylsilsesquioxane is used as a precursor, and under acidic conditions, different nonionic block copolymer surfactants are used as templates. The preparation technology and law study of the transparent PMOs gel single stone without crack control are systematically carried out, and the different structures will have different structures. The organic dyes, such as Luo Danming 6G (Rh6G), 7- hydroxyl -4- methyl coumarin (7H4MC) and Ya Jiaji blue (MB), are introduced into the transparent PMOs gel channel by direct synthesis, and the optical properties of the gels after the dye doping are preliminarily studied. The main results are as follows:
1, first, by using F127 as a template, through the comprehensive screening and evaluation of the synthetic parameters and preparation conditions, the transparent PMOs gel monolith, which can be adjusted with the shape of the container, is synthesized for the first time under the condition of constant temperature and drying at 40 C. Through the different deformable methods such as ethanol extraction, water extraction, calcination and ammonium perchlorate oxidation The N2 adsorption and TG analysis of the samples after treatment showed that the ammonium perchlorate oxidation method was a more effective deformable method, and the whole morphology of the gel could remain intact after the deformability. The N2 adsorption isotherm showed a IV type curve containing the H2 type hysteresis loop, suggesting that the gel may contain a cage like mesoporous structure similar to that of SBA-16. The doping of the gel to Rh6G is possible. The UV-vis and fluorescence spectra of the post gel show that the two polymerization tendency of Rh6G in PMOs gel weakens obviously and the emission spectrum is blue shift. It shows that the presence of template in PMOs gel is beneficial to the better dispersion and stability of dye molecules, and thus improve the luminescence properties of the materials.
2, using P123 as a template, using methanol as a cosolvent, the transparent PMOs transparent gel single stone with a two dimensional six square phase ethyl bridge with SBA-15 like structure is controlled within the concentration range of the template of 14.5-35.5wt%. The optical properties of 7H4MC coumarin dye introduced into the transparent PMOs gel show that 7H4MC/SiO-42 is compared to 10-2-10 When the dye concentration increases, the emission spectrum is only slightly red shift but its luminous intensity increases significantly. When the fixed 7H4MC/SiO2 ratio is 10-3, it is found that the high concentration of the template will weaken the luminescence intensity because of the decrease of the dye occupation ratio in the gel, indicating that the presence of the template is not only beneficial to the higher concentration of dye molecules. Moreover, there is a certain optimum matching relationship between the concentration of dye doping and the concentration of template used to ensure the integrity of PMOs gel monolith.
3, Brij56 is used as a template and ethanol as a cosolvent to control the synthesis of ethyl modified PMOs transparent gel monolith in the range of template concentration of 5.2-35.5wt%. It is found that the introduction of long chain alcohols, such as butyl, amyl, hexanol, or its concentration, can increase the pore size of the gel under the premise of transparent and complete gel whole body. The results of UV visible and fluorescence spectra of MB doped PMO gel show that the existence of template is also helpful to the high dispersion of MB dye molecules, and the trend of the two polymerization of dye molecules is weakened and the emission spectrum is obviously blue shift, which helps to improve the optical properties of the materials.
【學位授予單位】：太原理工大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TB383.4;TQ427.26
本文編號：2155678
[Abstract]:Periodic mesoporous organic silica (PMOs) is a new type of organic-inorganic hybrid mesoporous material which is synthesized under the action of surfactant template with bridged sesquioxane as a precursor and at least two different functional units are allowed to be placed in two space separated areas in the mesoporous structure. The pore wall skeleton and mesoporous channel make it more widely applied in the research field of various new composite functional materials. Obviously, if the transparent PMOs gel with macro morphologies and adjustable sizes can be controlled, it will have better operability than the conventional powder materials in the new light, electricity, magnetic devices and solids. The research fields of dye lasers and sensors are of great significance, but the synthesis and application of PMOs are still limited to the morphology of powders or thin films.
Based on the above thought, a commercialized ethylenediethylsilsesquioxane is used as a precursor, and under acidic conditions, different nonionic block copolymer surfactants are used as templates. The preparation technology and law study of the transparent PMOs gel single stone without crack control are systematically carried out, and the different structures will have different structures. The organic dyes, such as Luo Danming 6G (Rh6G), 7- hydroxyl -4- methyl coumarin (7H4MC) and Ya Jiaji blue (MB), are introduced into the transparent PMOs gel channel by direct synthesis, and the optical properties of the gels after the dye doping are preliminarily studied. The main results are as follows:
1, first, by using F127 as a template, through the comprehensive screening and evaluation of the synthetic parameters and preparation conditions, the transparent PMOs gel monolith, which can be adjusted with the shape of the container, is synthesized for the first time under the condition of constant temperature and drying at 40 C. Through the different deformable methods such as ethanol extraction, water extraction, calcination and ammonium perchlorate oxidation The N2 adsorption and TG analysis of the samples after treatment showed that the ammonium perchlorate oxidation method was a more effective deformable method, and the whole morphology of the gel could remain intact after the deformability. The N2 adsorption isotherm showed a IV type curve containing the H2 type hysteresis loop, suggesting that the gel may contain a cage like mesoporous structure similar to that of SBA-16. The doping of the gel to Rh6G is possible. The UV-vis and fluorescence spectra of the post gel show that the two polymerization tendency of Rh6G in PMOs gel weakens obviously and the emission spectrum is blue shift. It shows that the presence of template in PMOs gel is beneficial to the better dispersion and stability of dye molecules, and thus improve the luminescence properties of the materials.
2, using P123 as a template, using methanol as a cosolvent, the transparent PMOs transparent gel single stone with a two dimensional six square phase ethyl bridge with SBA-15 like structure is controlled within the concentration range of the template of 14.5-35.5wt%. The optical properties of 7H4MC coumarin dye introduced into the transparent PMOs gel show that 7H4MC/SiO-42 is compared to 10-2-10 When the dye concentration increases, the emission spectrum is only slightly red shift but its luminous intensity increases significantly. When the fixed 7H4MC/SiO2 ratio is 10-3, it is found that the high concentration of the template will weaken the luminescence intensity because of the decrease of the dye occupation ratio in the gel, indicating that the presence of the template is not only beneficial to the higher concentration of dye molecules. Moreover, there is a certain optimum matching relationship between the concentration of dye doping and the concentration of template used to ensure the integrity of PMOs gel monolith.
3, Brij56 is used as a template and ethanol as a cosolvent to control the synthesis of ethyl modified PMOs transparent gel monolith in the range of template concentration of 5.2-35.5wt%. It is found that the introduction of long chain alcohols, such as butyl, amyl, hexanol, or its concentration, can increase the pore size of the gel under the premise of transparent and complete gel whole body. The results of UV visible and fluorescence spectra of MB doped PMO gel show that the existence of template is also helpful to the high dispersion of MB dye molecules, and the trend of the two polymerization of dye molecules is weakened and the emission spectrum is obviously blue shift, which helps to improve the optical properties of the materials.
【學位授予單位】：太原理工大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TB383.4;TQ427.26
【參考文獻】
相關期刊論文 前2條
1 奚紅霞,黃仲濤;凝膠的干燥[J];膜科學與技術;1997年01期
2 朱桂茹;楊啟華;李燦;;乙烷橋鍵介孔材料的制備及其在反相液相色譜中的應用[J];色譜;2007年04期
本文編號：2155678
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