本文選題：無機(jī)—有機(jī)雜化材料　切入點(diǎn)：共軛　出處：《北京化工大學(xué)》2016年碩士論文　論文類型：學(xué)位論文

【摘要】：本論文第一體系以Y-氨丙基三乙氧基硅烷(APTES)烷基化修飾的SBA-15為主體,將一種含p二酮硼二氟取代基團(tuán)的共軛有機(jī)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)-二氧雜環(huán)己烷-硼)(以下簡稱BDOBC16)組裝到APTES-SBA-15主體孔內(nèi)。利用400 MHz的29Si核磁技術(shù)手段檢測發(fā)現(xiàn)烷基化后分子篩孔內(nèi)壁的羥基數(shù)量大幅減少；分析BET孔徑分布數(shù)據(jù)發(fā)現(xiàn)SBA-15孔徑隨著硅烷化修飾和BDOBC16的組裝從最初的7.9 nm減小到6.5 nm、最后降至4.9nm;FT-IR圖上的N-H的伸縮振動(dòng)吸收由APTES-SBA-15在3507 cm-1處藍(lán)移至組裝體在3515cm-1、B-F的吸收峰1161 cm-1卻在組裝后紅移至1135 cm-1處,所有這些都告訴我們硅烷化修飾和組裝均已成功；TG-DTA數(shù)據(jù)顯示組裝到APTES-SBA-15孑L內(nèi)的BDOBC16的質(zhì)量約占整個(gè)組裝體的15.5%,客體分子BDOBC16的分解溫度得到了提高。熒光性質(zhì)研究結(jié)果顯示組裝到硅烷化的SBA-15內(nèi)的BDOBC16發(fā)射綠光而純凈的客體分子本身發(fā)紅光,BDOB C16分子組裝前后發(fā)射光能量變化很明顯且發(fā)光強(qiáng)度增強(qiáng)了75倍。我們分析認(rèn)為主客體分子之間存在較強(qiáng)的氫鍵作用是客體分子在組裝后發(fā)光性質(zhì)發(fā)生巨大改變的主要原因。分子聚集對發(fā)光有極大的危害,而將共軛有機(jī)分子BDOBC16組裝到硅烷化的分子篩孔中可以使其高度分散,因而提高其發(fā)光強(qiáng)度。第二體系在原有的S BA-15的基礎(chǔ)上通過化學(xué)修飾法于孔內(nèi)構(gòu)建微孔,合成了一種微介孔混合型的多級孔雜化材料HSSBA-15。該材料并未破壞SBA-15原有的骨架,僅是在介孔內(nèi)構(gòu)建了微孔,但又由于新構(gòu)建的微孔結(jié)晶度很低,所以其晶面結(jié)構(gòu)在XRD圖上無法顯示出峰。SBA-15原有的介孔直徑在8nm左右,而新出現(xiàn)的微孔每個(gè)直徑在1.9nm左右,同時(shí)原來的母孔孔徑變?yōu)?.5 nm,孔體積減小了0.0214 cm3/g,比表面積卻由原來的395.9 m2/g變?yōu)槲⒖讟?gòu)建后的667.4 m2/g。從HR-TEM圖像上可以看到原介孔孔道壁上出現(xiàn)了大量的微孔結(jié)構(gòu),且原來的母孔輪廓變得模糊了。該雜化材料結(jié)合了微孔與介孔兩種組分的性質(zhì),其優(yōu)越的的吸附性能被充分顯示出來。本論文應(yīng)用微介孔雜化材料HSSBA-15對海水中的Na+和Cl-離子進(jìn)行了吸附研究,研究結(jié)果表明該復(fù)合雜化材料能夠達(dá)到純化海水的目的。我們在論文中系統(tǒng)地研究了多級孔材料HSSBA-15對Na+和Cl-離子的吸附動(dòng)力學(xué)和熱力學(xué),考察了不同初始濃度、不同吸附溫度以及不同吸附時(shí)間對吸附效果的影響,三方結(jié)合得到最佳吸附效果的條件。結(jié)果顯示：在一定濃度范圍內(nèi)對比低濃度的NaCl,HSSBA-15對高濃度的NaCl有更強(qiáng)的吸附能力。分子篩孔壁上富電子的O-H與帶正電荷的Na+之間能夠形成較強(qiáng)的靜電作用,而被吸附的Na+又可以吸附帶負(fù)電荷的Cl-,如此正負(fù)交替,使得Na+和Cl-同時(shí)被該主體材料吸附。吸附曲線告訴我們,吸附量qe在最初的一段時(shí)間里急劇增加,而10小時(shí)以后基本趨于穩(wěn)定,48小時(shí)后達(dá)吸附平衡；在一定濃度范圍內(nèi),NaCl的初始濃度越高吸附量就越大,高于此范圍,吸附量將不再隨著NaCl初始濃度的增加而增加；20 ℃左右時(shí)吸附量最大,低于或高于此穩(wěn)定吸附量都將降低,尤以高溫降低最為顯著,這是由于高溫加劇了分子的熱運(yùn)動(dòng),分子熱運(yùn)動(dòng)的能量高于靜電結(jié)合能,因此Na+和Cl-更加容易掙脫靜電力束縛返回到溶液中去。綜合結(jié)果顯示20℃、吸附質(zhì)的初始濃度為5g/L時(shí),吸附劑HSSBA-15的吸附效果最佳,其最大吸附量qe達(dá)到517.5 mg/g,而原分子篩SBA-15在相同條件下的吸附量只有133.4 mg/L,僅為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

【學(xué)位授予單位】：北京化工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O621.1;O647.3
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本文編號：1579626