【作者】 于辉；

【导师】 翟庆洲； 邹明强；

【作者基本信息】 长春理工大学 ， 光学， 2009， 博士

【摘要】 采用微波辅助水热合成（MAHS）方法和水热法成功地合成出了SBA-15介孔分子筛。这两种方法都是采用聚乙二醇-嵌段-聚丙二醇-嵌段-聚乙二醇(EG₂₀PG₄₀EG₂₀)作为模板剂,采用正硅酸四乙酯作为硅源。采用本研究的微波水热辅助合成方法合成介孔SBA-15分子筛仅需要125min,而采用常规的水热合成方法则需要花费72h,采用本实验方法较常规水热合成法快34倍。本研究采用粉末X-射线衍射分析（Powder X-rayDiffraction,XRD）、傅立叶转换红外光谱（Fourier Transform Infrared Spectroscopy,FT-IR）、氮气吸附-解吸附技术、透射电镜（Transmission Electron Microscopy,TEM）、扫描电镜（Scanning Electron Microscopy,SEM）等表征手段对所制备的SBA-15分子筛材料的各种性质进行了深入的研究。粉末X-射线衍射分析的结果表明,采用微波辅助水热方法合成的SBA-15分子筛的衍射峰峰位和采用常规水热合成方法合成的SBA-15分子筛的衍射峰峰位是一致的,这说明采用该方法已经成功的合成了SBA-15分子筛。氮气吸附-解吸附实验的结果显示,采用微波辐照5 min方法合成的SBA-15分子筛（FS）的孔道直径是6.49nm,而采用微波辐照30min方法所合成的SBA-15分子筛（TS）的孔道直径是7.40nm。扫描电镜结果表明,所采用微波水热合成法所合成的SBA-15分子筛呈现针状晶体结构,对于FS样品来说晶粒的长度大约是100μm,对于TS样品来说晶粒的长度大约是64μm。对于FS样品来说晶粒直径是4.5μm,而对于TS样品来说晶粒直径大约是3.6μm。实验结果证明,采用微波水热辅助合成方法可以使体系受热均匀,加热速度快,从而使合成SBA-15分子筛的速度快,提高了生产效率,降低了能源的消耗,也降低了生产成本。在本研究中,La₂O₃成功地组装到了SBA-15介孔孔道中。本研究采用了三种方法将客体材料La₂O₃组装到主体SBA-15介孔分子筛材料中,第一种方法是液相移植法;第二种方法是直接固体热扩散法;第三种方法是微波辅助合成法。然后,采用化学分析、粉末X-射线衍射分析（XRD）、傅立叶变换红外光谱分析（FT-IR）、氮气吸附-解吸附分析、透射电镜分析（TEM）、扫描电镜分析（SEM）、紫外-可见固体扩散漫反射吸收光谱分析,发光性质研究等和激光激发光致发光光谱（PL）等手段对所制得的主-客体纳米复合材料的各种性质和性能进行了分析。La₂O₃组装到主体材料的孔道后,分子筛骨架保持完整,仍然具有较高的有序性。La₂O₃主要分布在分子筛的纳米孔道中,所制得的主-客体纳米复合材料具有发光特性。通过所制备的主-客体纳米复合材料样品的紫外-可见固体扩散漫反射吸收光谱的吸收峰发生了蓝移现象,可以认定La₂O₃已经组装到SBA-15分子筛孔道中,并且材料表现出了量子尺寸效应和量子限域效应,说明La₂O₃已经组装到了SBA-15分子筛的孔道中。从发光光谱可知,SBA-15分子筛本身是不发光的,组装了客体La₂O₃之后的复合材料却出现了发光现象,这说明:La₂O₃已经组装到了SBA-15分子筛中,而且制得的主-客体纳米复合材料显示出发光性质,并且发光强度较纯的La₂O₃材料高出1倍,该材料具有用作发光材料的潜力。从材料的激光激发荧光光谱可以看到,固相法合成的（SBA-15）-La₂O₃样品（SS）,以La₂O₃为镧源微波法合成的（SBA-15）-La₂O₃样品（MWSS）,以La（NO₃）₃为镧源微波法合成的（SBA-15）-La₂O₃样品（MWNS）以及液相法合成的（SBA-15）-La₂O₃样品（LS）的发光强度要较La₂O₃及La₂O₃（wt 5%）的机械混合物强得多。对于在532nm附近的发光峰来说,SS样品的峰强度是La₂O₃的8倍,是La₂O₃（wt 5%）的机械混合物的11倍,MWSS样品的峰强度是La₂O₃的6倍,是La₂O₃（wt 5%）的机械混合物的8倍,MWNS样品的峰强度是La₂O₃的3倍,是La₂O₃（wt 5%）的机械混合物的4倍,LS样品的峰强度是La₂O₃的5倍,是La₂O₃（wt 5%）的机械混合物的7倍。在本研究中,制备了介孔SBA-15分子筛,然后将其用作尼莫地平药物的载药系统,来运载尼莫地平,并且采用各种表征手段对制备材料的性质进行了表征,对该体系对尼莫地平药物的缓释作用进行了评价。尼莫地平向介孔SBA-15分子筛孔道中的组装过程是将尼莫地平先溶解在一种适当的溶剂中制得相应的尼莫地平溶液,然后将该溶液和SBA-15分子筛粉末混合搅拌一定时间得到目的产物。本研究对尼莫地平药物从SBA-15分子筛孔道中向模拟体液（SBF）中的释放过程进行了模拟监控,研究了载药体系的缓释作用。实验结果显示,尼莫地平药物的释放速率为12h～13h释放.50%,各个样品都是在24h～25h全部释放。而且,从释放曲线可以看到药品的释放过程非常平缓。此外,本研究在将尼莫地平药物向SBA-15分子筛中组装之前,先对SBA-15分子筛外表面进行了硅烷化处理,该过程采用的硅烷试剂有苯基三甲氧基硅烷和三甲基氯硅烷等。进行硅烷化处理的目的是为了消除分子筛外表面上的硅羟基,从而减小尼莫地平嫁接到分子筛外表面的可能性,为此,本研究在SBA-15分子筛脱模板前进行了硅烷化处理,然后再去除模板。采用化学分析、粉末X-射线衍射分析（XRD）、傅立叶变换红外光谱分析（FT-IR）、氮气吸附-解吸附技术、透射电子显微镜（TEM）和扫描电子显微镜（SEM）等表征方法,对制备材料的性质进行了研究。结果表明,本研究所描述的方法适合于尼莫地平药物的运载,为尼莫地平药物的负载找到了一个新的载体,同时也提高了尼莫地平药物药效。更多还原

【Abstract】 SBA-15 molecular sieve has been successfully synthesized by a microwave-assisted hydrothermal synthesis（MAHS） method and hydrothermal synthesis method,using poly （ethylene glycol）-block-poly（propyl glycol）-block-poly（ethylene glycol）（EG20PG40EG20） as a template.The synthesis of SBA-15 molecular sieve by MAHS method only needs 125 min and synthesis is more than 34 times faster than that by the conventional hydrothermal synthesis method.Powder X-ray diffraction（XRD）,Fourier transform infrared spectroscopy （FT-IR）,nitrogen adsorption-desorption technique,transmission electron microscopy（TEM） and scanning electron microscopy（SEM） were used to characterize the materials.The powder X-ray diffraction results showed that the structures of the SBA-15 molecular sieves correspond to that by the hydrothermal method.The nitrogen adsorption-desorption results showed that the average pore diameter of the SBA-15 molecular sieve synthesized by MAHS method was 6.49 for microwave-assisted synthesis of SBA-15 molecular sieve in 5 min（FS） sample and 7.40 nm for microwave-assisted synthesis of SBA-15 molecular sieve in 30 min（TS） sample.The scanning electron microscopy results showed that the primary particles of the samples presented acicular crystals,crystals longness was 100μm for FS sample and 64μm for TS sample,crystals diameter was 4.5μm for FS sample and 3.6μm for TS sample,respectively.The use of microwave radiation can transfer energy uniformly and quickly,and complete the syntheses of SBA-15 molecular sieve within a short time.Lanthanum oxide was incorporated into SBA-15 mesoporous molecular sieve via liquid-phase grafting,thermal diffusion,and microwave-assisted synthesis methods.A series of characterizations including powder X-ray diffraction（XRD）,chemical analysis,Fourier transform infrared spectroscopy（FT-IR）,nitrogen adsorption-desorption technique, transmission electron microscopy（TEM）,scanning electron microscopy（SEM）,solid state diffuse reflection absorption spectra,fluorescence spectra and photoluminescence（PL） spectra were used to characterize the prepared materials.The results showed that in the prepared host-guest（SBA-15）-La₂O₃ materials the frameworks of the host molecular sieve kept intact and its structures were kept highly ordered.The incorporated lanthanum oxide located inside the pores of the SBA-15.The prepared host-guest composite materials showed the properties of luminescence.From the solid state diffuse reflection absorption spectra of the host-guest（SBA-15）-La2O₃ materials,the blue-shift phenomenon of the spectra can be ascribed to the stereoconfinement of the pores of the SBA-15 and quantum size effect is clearly associated with the nanosize of La₂O₃.The solid state diffuse reflectance absorption spectra prove that La₂O₃ has been successfully trapped in the channels of the SBA-15 molecular sieve.From the luminescence spectra of the materials,there are no phenomena of luminescence of the host SBA-15 molecular sieve.However,for the prepared （SBA-15）-La₂O₃ composite materials,the phenomena of luminescence appeared.The luminescent intensities of the（SBA-15）-La₂O₃ materials samples are about 2 times of bulk La₂O₃.They have the potentiality as luminescent materials.From the PL spectra of the samples,the luminescent intensities of SS（Solid thermal diffusion）,MWSS（Microwave La₂O₃ diffusion）,MWNS（Microwave La（NO₃）₃ diffusion） and LS（Liquid phase grafting） samples are much higher than those of bulk La₂O₃ and the mechanical mixture of SBA-15 and La₂O₃（5 wt%）.For the peaks which locate near 532 nm,the luminescent intensities of SS sample is about 8 times of bulk La₂O₃ and 11 times of the mechanical mixture of SBA-15 and La₂O₃（5 wt%）,the luminescent intensities of MWSS sample is about 6 times of bulk La₂O₃ and 8 times of the mechanical mixture of SBA-15 and La₂O₃（5 wt%）,the luminescent intensities of MWNS sample is about 3 times of bulk La₂O₃ and 4 times of the mechanical mixture of SBA-15 and La₂O₃（5 wt%）,the luminescent intensities of LS sample is about 5 times of bulk La₂O₃ and 7 times of the mechanical mixture of SBA-15 and La₂O₃ （5 wt%）,respectively.In this study,mesoporous SBA-15 molecular sieve was prepared to evaluate its application as nimodipine drug delivery system.The nimodipine was doped inside the pores of SBA-15 by contacting a solution of the nimodipine in an appropriate solvent with the porous solid,and the drug release process from the matrix into a simulated body fluid（SBF） solution has been studied.The results showed that the release effect of nimodipine was 50% in 12 h～13 h,100%in 24 h²5 h,and followed by a very slow release pattern.The surface of SBA-15 was functionalized with phenyltrimethoxysilane or trimethylchlorosilane before calcination.Chemical analysis,powder X-ray diffraction（XRD）,Fourier transform infrared spectroscopy（FT-IR）,nitrogen adsorption-desorption technique,transmission electron microscopy（TEM） and scanning electron microscopy（SEM） were used to characterize the materials.The approaches described in this thesis provide methods for carry of nimodipine and improve effect of nimodipine.更多还原