SBA-15孔内共轭有机分子的组装及微孔构建

发布时间：2018-03-07 14:12

  本文选题：无机—有机杂化材料　切入点：共轭　出处：《北京化工大学》2016年硕士论文　论文类型：学位论文

【摘要】：本论文第一体系以Y-氨丙基三乙氧基硅烷(APTES)烷基化修饰的SBA-15为主体,将一种含p二酮硼二氟取代基团的共轭有机分子4,40-(9-(正十六烷基)咔唑-3,6-取代基)二(6-(4-二苯胺苯基)-2,2-二氟-1,3,2(2H)-二氧杂环己烷-硼)(以下简称BDOBC16)组装到APTES-SBA-15主体孔内。利用400 MHz的29Si核磁技术手段检测发现烷基化后分子筛孔内壁的羟基数量大幅减少；分析BET孔径分布数据发现SBA-15孔径随着硅烷化修饰和BDOBC16的组装从最初的7.9 nm减小到6.5 nm、最后降至4.9nm;FT-IR图上的N-H的伸缩振动吸收由APTES-SBA-15在3507 cm-1处蓝移至组装体在3515cm-1、B-F的吸收峰1161 cm-1却在组装后红移至1135 cm-1处,所有这些都告诉我们硅烷化修饰和组装均已成功；TG-DTA数据显示组装到APTES-SBA-15孑L内的BDOBC16的质量约占整个组装体的15.5%,客体分子BDOBC16的分解温度得到了提高。荧光性质研究结果显示组装到硅烷化的SBA-15内的BDOBC16发射绿光而纯净的客体分子本身发红光,BDOB C16分子组装前后发射光能量变化很明显且发光强度增强了75倍。我们分析认为主客体分子之间存在较强的氢键作用是客体分子在组装后发光性质发生巨大改变的主要原因。分子聚集对发光有极大的危害,而将共轭有机分子BDOBC16组装到硅烷化的分子筛孔中可以使其高度分散,因而提高其发光强度。第二体系在原有的S BA-15的基础上通过化学修饰法于孔内构建微孔,合成了一种微介孔混合型的多级孔杂化材料HSSBA-15。该材料并未破坏SBA-15原有的骨架,仅是在介孔内构建了微孔,但又由于新构建的微孔结晶度很低,所以其晶面结构在XRD图上无法显示出峰。SBA-15原有的介孔直径在8nm左右,而新出现的微孔每个直径在1.9nm左右,同时原来的母孔孔径变为6.5 nm,孔体积减小了0.0214 cm3/g,比表面积却由原来的395.9 m2/g变为微孔构建后的667.4 m2/g。从HR-TEM图像上可以看到原介孔孔道壁上出现了大量的微孔结构,且原来的母孔轮廓变得模糊了。该杂化材料结合了微孔与介孔两种组分的性质,其优越的的吸附性能被充分显示出来。本论文应用微介孔杂化材料HSSBA-15对海水中的Na+和Cl-离子进行了吸附研究,研究结果表明该复合杂化材料能够达到纯化海水的目的。我们在论文中系统地研究了多级孔材料HSSBA-15对Na+和Cl-离子的吸附动力学和热力学,考察了不同初始浓度、不同吸附温度以及不同吸附时间对吸附效果的影响,三方结合得到最佳吸附效果的条件。结果显示：在一定浓度范围内对比低浓度的NaCl,HSSBA-15对高浓度的NaCl有更强的吸附能力。分子筛孔壁上富电子的O-H与带正电荷的Na+之间能够形成较强的静电作用,而被吸附的Na+又可以吸附带负电荷的Cl-,如此正负交替,使得Na+和Cl-同时被该主体材料吸附。吸附曲线告诉我们,吸附量qe在最初的一段时间里急剧增加,而10小时以后基本趋于稳定,48小时后达吸附平衡；在一定浓度范围内,NaCl的初始浓度越高吸附量就越大,高于此范围,吸附量将不再随着NaCl初始浓度的增加而增加；20 ℃左右时吸附量最大,低于或高于此稳定吸附量都将降低,尤以高温降低最为显著,这是由于高温加剧了分子的热运动,分子热运动的能量高于静电结合能,因此Na+和Cl-更加容易挣脱静电力束缚返回到溶液中去。综合结果显示20℃、吸附质的初始浓度为5g/L时,吸附剂HSSBA-15的吸附效果最佳,其最大吸附量qe达到517.5 mg/g,而原分子筛SBA-15在相同条件下的吸附量只有133.4 mg/L,仅为HSSBA-15的25.8%。
[Abstract]:The first system of this thesis Y- aminopropyltriethoxysilane (APTES) alkylation modified SBA-15 as the main body, a P containing two boron fluorine substituent ketone two conjugated organic molecules 4,40- (9- (sixteen alkyl) carbazole substituted -3,6- (6-) two (4- two -2,2- two fluoro aniline phenyl) -1,3,2 (2H) - two - 4 dioxane boron) (hereinafter referred to as BDOBC16) assembled to the APTES-SBA-15 body hole. By means of 29Si NMR detection of 400 MHz was found to significantly reduce the number after alkylation of molecular sieve on the inner wall of the hydroxyl group; pore size distribution analysis of BET data showed that SBA-15 hole diameter with the assembly of silylation and BDOBC16 decreased from 7.9 nm to 6.5 nm, and finally to 4.9nm; stretching vibration on the FT-IR N-H absorption at APTES-SBA-15 from the blue shift at 3507 cm-1 in the 3515cm-1 assembly, B-F absorption peak at 1161 cm-1 was assembled after the red shifted to 1135 cm-1, all of which are Tell us the silylation modification and assembly have been successfully assembled to the quality of TG-DTA data; APTES-SBA-15 alone L BDOBC16 in accounting for the assembly of 15.5%, the decomposition temperature of the guest molecule BDOBC16 has been improved. Research results show that the fluorescence properties of assembled silylated SBA-15 in BDOBC16 emits green light and pure object molecule itself red, before and after BDOB C16 molecular assembly emits light energy changes obviously and the intensity was increased by 75 times. We analyzed that there are strong hydrogen bonds between the molecules of subject and object is the main reason of guest molecules in the assembly after the luminescence matter of great change. The molecular aggregation has great harm on the luminescence, and conjugated organic molecules BDOBC16 molecular sieve assembled to silanized can make highly dispersed, thus improving the luminescence intensity. Second system based on S BA-15 on the original. After chemical modification in the hole construction of microporous, mesoporous hybrid materials HSSBA-15. a multistage micro mesoporous hybrid materials which did not destroy the original SBA-15 framework was synthesized only in the mesoporous microporous construction, but because of the construction of new microporous crystalline degree is very low, so the crystal structure in XRD on the map to show a peak.SBA-15 of the original mesoporous diameter at about 8nm, and the emergence of new microporous each about 1.9nm in diameter, and the aperture of the original parent is 6.5 nm, pore volume decreased by 0.0214 cm3/g, the specific surface area is increased from 395.9 m2/g to 667.4 after the construction of micro hole m2/g. from the HR-TEM images can see the emergence of a large number of porous structures the original mesoporous pore wall, and the mother of the original hole profile has become blurred. The hybrid material combines the properties of microporous and mesoporous two components, its excellent adsorption performance was fully displayed. This The application of micro mesoporous hybrid materials of HSSBA-15 Na+ in seawater and Cl- ion adsorption studies were performed, the results show that the composite material can achieve the purpose of purifying water. We studied the hierarchical porous materials of Na+ HSSBA-15 and Cl- ion adsorption kinetics and thermodynamics of the system in the paper, the effect of different initial concentration. Effect of different adsorption temperature and adsorption time on the adsorption effect, combined with the three party to get the best effect of adsorption conditions. The results showed that in a certain concentration range compared to the low concentration of NaCl, HSSBA-15 on the NaCl concentration had a stronger adsorption capacity. Between the molecular sieve on the wall of the electron rich O-H and Na+ with the positive charge to form a strong electrostatic interaction, and the adsorbed Na+ and the adsorption of negatively charged Cl-, so alternate, which makes the Na+ and Cl- is also the main material adsorption adsorption curve. The line tells us that the adsorption capacity of QE increased sharply in the initial period of time, and 10 hours after basically stabilized, after 48 hours of adsorption equilibrium; in a certain range of concentration, the initial concentration of NaCl higher adsorption amount is higher, higher than this range, the adsorption amount will no longer with the increase of the initial concentration of NaCl increased; about 20 DEG C when the maximum adsorption capacity, lower or higher than the stable adsorption capacity will be reduced, especially in the high temperature decreased most significantly, this is due to the high temperature increased the thermal motion of molecules, molecular thermal motion energy is higher than the static binding energy, so Na+ and Cl- are more likely to get rid of the static power bound to return to the solution go. Comprehensive results show that 20 DEG C, the initial concentration of the adsorbate was 5g/L, the adsorption effect of adsorbent HSSBA-15 is best, the maximum adsorption capacity of QE reached 517.5 mg/g, while the original SBA-15 molecular sieve adsorption under the same conditions, the amount of only 133.4 mg/ L, 25.8%. only for HSSBA-15

【学位授予单位】：北京化工大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.1;O647.3
，

本文编号：1579626