摘要
多级孔二氧化硅材料由于其具有不同等级尺度的孔道结构、高的比表面积和孔体积等优点，在催化、吸附、分离、生物医药等领域具有潜在的应用价值，一直以来成为多孔材料领域的的热点课题。近年来，多种模板合成路线相继被开发出来用以合成多级孔二氧化硅材料。虽然多级孔二氧化硅材料在合成方面已经取得了一定的进展，但是仍然存在一些未解决的问题，如形貌和尺寸难以控制、模板成本较高、操作程序复杂、不同模板剂之间的竞争作用难以控制等。本论文旨在开发出简单高效的多级孔二氧化硅材料合成路线以达到对多级孔二氧化硅材料形貌和尺寸的精确控制，通过对合成的多级孔二氧化硅材料进行改性，赋予多级孔二氧化硅材料更多优异的性能。在以合成方法为研究重点的基础上，考察了所合成的多级孔二氧化硅材料在生物材料固载、多相催化等领域的应用。论文主要内容包括以下三个方面：
1.多级孔结构介孔二氧化硅和有序介孔有机硅的合成及其生物固载性能研究
自然界中的生物矿物，如海藻和放射虫等，往往具有一致的粒子尺寸、精巧的形貌和从纳米到微米级的多级结构，而控制生物矿物沉积的过程往往是动态变化的有机质（种类和数量随矿化过程不断变化）调控无机物矿化的过程。受自然界这种奇妙的“制造材料”的启发，我们拟将动态模板机理引入到介孔二氧化硅的制备过程中，从而开发出简单高效的多级孔材料合成路线。本章中，以阴离子聚电解质聚丙烯酸（PAA）和阳离子表面活性剂氯代十六烷基吡啶(CPC)形成的有序介观结构复合物介晶为“动态模板”，在碱性条件下制备了具有多级孔结构的SBA-1单晶颗粒。通过扫描电镜（SEM），X射线衍射（XRD），X-射线小角散射（SAXS），透射电镜（TEM），氮气吸附等手段对合成的多级孔结构介孔二氧化硅的形貌和结构进行了表征。结果表明采用动态模板法合成的SBA-1单晶颗粒包含有序立方Pm3n结构的笼状介孔和较大孔径的二次纳米孔，且二次纳米孔穿插在有序介孔之间，并未破坏介孔的有序周期排列。SBA-1单晶颗粒的尺寸和形貌可以在一定PAA用量范围内进行调控。通过改变合成中加入的PAA量，可以制备出由亚微米球形向微米级多面体演变的多级孔二氧化硅。将合成的多级孔结构的介孔SBA-1单晶颗粒应用于固定化木瓜蛋白酶的研究中，并对固定化酶降解牛血清白蛋白的性能进行了评价。结果表明，与MCM-41相比，SBA-1具有较高的酶固载量和较好的降解蛋白质的能力；另外，通过在合成过程中加入扩孔剂1，3，5-三甲苯来合成改性SBA-1单晶颗粒，发现扩孔剂的加入并没有明显改变SBA-1单晶颗粒的形貌，而通过调节扩孔剂的加入量能够将SBA-1单晶颗粒中的有序介孔孔径在一定范围内进行调变（3.1~5.0nm）。采用CPC/聚马来酸复合物介晶为动态模板，也可以制备出多级孔结构的介孔二氧化硅单晶颗粒。此外，在SBA-1单晶颗粒的合成基础上，以有机硅1，2-双（三乙氧基硅）乙烷为硅源，成功地制备出具有多级孔结构的有序介孔有机硅（PMO）材料。以MCM-41和SBA-15为参比材料，研究了多级孔材料SBA-1和有序介孔有机硅材料在溶菌酶和牛血清白蛋白固定化中的应用。固载实验表明，多级孔结构的PMO材料表现出较高的固载量和较快的固载速率，这主要是由于其具有多级孔结构和疏水的有机官能团。最后，研究了多级孔材料SBA-1和PMO对溶菌酶和过氧化氢酶的共固载性能，结果表明，与单一孔径二氧化硅材料相比，多级孔SBA-1材料其多级孔的性质使得它在两种不同尺寸酶的共固载研究中体现出较优异的性能。
2.多级孔结构杂原子分子筛的合成及其性能研究
具有规整形貌的多级孔分子筛由于其多级孔结构、高的比表面积和孔体积及良好的热稳定性而在催化领域引起人们的广泛关注。但是多级孔分子筛在作为催化剂时，由于其较弱的酸性活性中心，大大限制了其在实际生产中的应用。本章在SBA-1单晶颗粒的合成基础上，以异丙醇铝为铝源，合成温度为120oC，通过一步法制备了多级孔结构介孔硅铝分子筛Al-SBA-1单晶颗粒。所合成的Al-SBA-1仍为亚微米尺度的球形颗粒，且球体内部可以清晰地观察到有序排列的介孔和二次纳米孔，说明在SBA-1骨架中引入铝并未对样品的形貌和内部结构产生很大的影响。通过控制合成过程中加入异丙醇铝的量，可以有效地控制制备的Al-SBA-1的硅铝比，且最高掺入量可达大约20%（Si/Al=5）。采用核磁共振（NMR）和氨程序升温脱附(NH_3-TPD)等测试对Al-SBA-1样品的酸性进行了表征。结果表明，Al-SBA-1中铝原子主要以四配位形式存在，且样品的酸性位点浓度随着合成过程中掺铝量的增加而增加。水热稳定性实验表明，Al-SBA-1单晶颗粒在100oC水热处理10天后表现出较好的水热稳定性，且颗粒形貌和多级孔结构得到了很好的保持。
以制备的Al-SBA-1单晶颗粒为催化剂，选择甲苯苯甲醇烷基化反应为模型反应考察了Al-SBA-1催化剂的催化活性和循环使用性。Al-SBA-1催化剂在反应中表现出较高的催化活性，这是因为Al-SBA-1的多级孔结构有利于反应过程中物料的传输，使得反应物分子更容易达到活性位点。同时，我们发现催化剂Al-SBA-1酸性位点的浓度对反应活性有很大的影响，酸性位点浓度越高，反应速率越快。另外，Al-SBA-1催化剂表现出较好的循环使用性能，在甲苯苯甲醇烷基化反应中循环使用4次后，催化活性没有明显的下降。
3.多级孔结构介孔二氧化硅纳米颗粒和介孔硅氢化合物纳米颗粒的制备及其性能研究
介孔二氧化硅纳米颗粒由于具有多孔性、高度生物相容性和化学稳定性以及光学稳定性等优点，因而在催化、吸附、分离等特别是生物医药领域作为药物载体引起了广泛的关注。目前，文献报道的多级孔结构介孔二氧化硅材料通常都具有相对较大的颗粒尺寸（亚微米或微米级）。纳米级多级孔结构介孔二氧化硅材料将赋予多级孔结构介孔二氧化硅材料更加优异的性能。本章以阴离子聚电解质PAA和阳离子表面活性剂形成的有序介观结构复合物介晶为“动态模板”，正硅酸乙酯为硅源，采用“稀溶液法”制备具有多级孔结构的SBA-1纳米颗粒。考察了不同阳离子表面活性剂对多级孔结构的SBA-1纳米颗粒形貌的影响。结果表明，以CPC或十六烷基三甲基溴化铵（CTAB）为阳离子表面活性剂，均可以在该体系中成功地合成出多级孔结构的SBA-1纳米颗粒。纳米颗粒的尺寸在50-300nm之间，颗粒内部可以观察到二次纳米孔以及有序介孔的存在。另外，考察了不同硅源对该体系的影响。当以正硅酸丙酯为硅源时，仅得到具有单一介孔孔道的SBA-1纳米颗粒，颗粒尺寸为75nm左右。这可能是因为相对于正硅酸乙酯而言，正硅酸丙酯水解速度较慢，聚合物PAA有充分的时间被排挤出去，因此在该体系中PAA未起到二次孔模板的作用。最后，我们考察了多级孔结构SBA-1纳米颗粒对溶菌酶的固载能力，结果表明，与具有单一孔结构的SBA-1纳米颗粒相比，多级孔结构的纳米颗粒对溶菌酶有较快的固载速率和较高的固载量。
含有大量硅氢键的硅氢化合物在高温下能转为光致发光材料，在太阳能材料领域具有潜在的应用价值。最近，文献首次报道了以双亲三嵌段共聚物P123为介孔模板剂，三乙氧基硅烷为硅源，在酸性条件下可以制备出粒径为100~400nm的介孔硅氢化合物。在本论文中，我们通过在该体系中加入季铵盐型阳离子氟碳表面活性剂（FC-04）为抑制剂，研究了抑制剂的加入对介孔硅氢化合物颗粒的形貌、尺寸以及介观结构的影响。结果表明调节合成体系的FC-04用量，可以制备出由实心向空心演变的纳米硅氢颗粒，且颗粒的尺寸由几百纳米减小至50nm左右。以空心的介孔硅氢化合物纳米颗粒为催化剂载体和还原剂，一步法制备了介孔硅氢化合物负载的贵金属纳米颗粒催化剂。将介孔硅氢化合物负载贵金属纳米颗粒催化剂应用于催化还原对硝基苯酚反应中，该催化剂表现出较好的催化活性。
Hierarchically porous silica materials with well-defined morphologies havebeen of growing interest, because of their potential applications in catalysis,adsorption, separation, and biomedical systems. In the past decades, a variety oftemplating approaches have been proposed to synthesize hierarchically porous silicamaterials, and colloidal particles, polymers, emulsion droplets, and surfactants havebeen employed to create porous structures with different sizes. Bimodal or trimodalporous materials, including micro-meso, meso-meso, meso-macro, and evenmicro-meso-macro, have been reported. However, in most cases, the control ofwell-ordered mesostructure and well-defined morphology was difficult, because ofthe mixing of different types of templates in the syntheses. In this thesis, we aim todesign facile and effective preparation methods for synthesis of the hierarchicallyporous silica materials with well-defined morphologies, size and functionality andevaluate the application of the synthesized hierarchically porous silica materials inbioimmobilization and catalysis. The main contents are as follows:
1. Synthesis of hierarchically mesoporous silica and periodic mesoporousorganosilica (PMO) and their bioimmobilized properties
In nature, some biominerals (for instance, sea urchin spines) possess complexand spongelike morphology but still remain single crystalline. The formationmechanism of the “porous” single crystals of biominerals can be ascribed to atime-dependent cooperative organization with complex organic matrix as dynamictemplates. Inspired by this, we try to explore facile and effective preparation methodsfor the synthesis of hierarchically porous silica materials with well-definedmorphologies via a “dynamic template mechanism”. In this section,single-crystal-like, hierarchically mesoporous silica SBA-1was synthesized withanionic polymer PAA and cationic surfactant hexadecylpyridinium chloride (CPC) mesomorphous complexes as dynamic template under alkaline condition. Scanningelectron microscopy （SEM）, power X-ray diffraction (XRD), small angle X-rayscattering (SAXS), transmission electron microscopy (TEM), nitrogen adsorptionanalyzer were employed to characterize the morphology and mesostrucuture of thesynthesized hierarchically mesoporous silica. The results indicated that the obtainedmaterials possess global mesopore size of SBA-1and secondary interstitialnanoporous pores. The presence of a large amount of foamlike secondary nanoporesdid not disturb the single-crystal characteristic of the SBA-1particles. By adjustingthe amount of PAA in the synthesis, the silica particles involved fromsubmicrometer-sized spherical particles to micrometer-sized drum-like polyhedronparticles. The synthesized hierarchically mesoporous silica (SBA-1-4) was chosen asa typical support for the bioimmobilization of the papain and the digestibility of bullserum albumin (BSA) by the papain immobilized hierarchically mesoporous silicawas also evaluated. The results demonstrated that the papain immobilizedhierarchically mesoporous silica reveals a high enzyme immobilized amount andgood digestibility compare to that of the MCM-41. By means of pore-expanding with1,3,5-trimethylbenzene, the mesopore size of the SBA-1could be easily tuned from3.1nm to5.0nm, while the morphology of the particles was not changed. Moreover,hierarchically mesoporous PMO were also prepared by employing bridgedsilsesquioxane species (RO)3Si-CH2-CH2-Si(RO)3as a silica precursor. In order tostudy the bioimmobilization ability of the hierarchically nanoporous SBA-1andH-PMO, SBA-1-7.5and H-PMO-3.6were used as typical examples in theimmobilization of lysozyme and BSA. Due to the fact that PMO has not only ahierarchically nanoporous structure but also uniformly distributed bridged-ethylenegroups that provide a hydrophobic surface, the H-PMO showed a good adsorptioncapacity and rapid adsorption dynamics. To further explore the bioimmobilizationability of the hierarchically nanoporous SBA-1-7.5and H-PMO-3.6, theco-immobilization ability of SBA-1-7.5and H-PMO-3.6for two kinds of enzymewith different size were studied. Compare to that of the silica materials with singlepore structure, the hierarchical pore structure of the SBA-1-7.5makes it reveal preferable co-immobilization ability.
2. Synthesis of hierarchically structured heteroatom molecular sieves andtheir properties
Hierarchically porous materials with well-defined morphologies have been ofgrowing interest in catalysis system, because of their hierarchical structure, highspecific surface area, high pore volume and superior thermal stability. Nevertheless,a main drawback of these materials with pure silica framework is that they oftendisplay relatively poor hydrothermal stability, which will restrain their extensiveindustrial application. In this section, mesoporous aluminosilicates Al-SBA-1withhierarchical pore structure have been successfully synthesized under alkalinecondition at120°C by employing organic mesomorphous complexes ofpolyelectrolyte (poly(acrylic acid)(PAA)) and cationic surfactant (hexadecylpyridinium chloride (CPC)) as template, aluminum isopropoxide as aluminumsource. The prepared Al-SBA-1exhibited submicrometer spherical morphology withthe presence of interstitial nanopores inside the submicrospheres as well as orderedalignment of mesopores through the whole particle, indicating that the incorporationof Al into the silica framework did not significantly disturb the interior texture andpore structure of the SBA-1. The molar ratio of the Si/Al could be effectivelycontrolled by adjusting the amount of the aluminum in the synthesis, and the Alcontaining could be as high as about20%(Si/Al=5). In order to investigate theacidic properties of the obtained Al-SBA-1materials,27Al MAS NMR andNH_3-TPD have been employed to characterize the synthesized Al-SBA-1materials.It is demonstrated that the incorporated Al atoms in the Al-SBA-1framework mainlyexist in the form of Al(IV) and the acid strength increase with the increasing of theAl content. Hydrothermal treatment showed that the Al-SBA-1materials exhibited ahigh hydrothermal stability and remained stable even after being treated in boilingwater for10days.
The catalytic activity of the Al-SBA-1materials was investigated by employingAl-SBA-1as catalyst, commercial HZSM-5as reference sample, Friedel–Crafts alkylation of toluene with benzyl alcohol as a model reaction. Compared withcommercial HZSM-5which possess a strong acidity but a micropore structure, theAl-SBA-1exhibited higher catalytic activity due to the hierarchically mesoporousstructure. Moreover, the results indicated that the more acidic sites could efficientlypromote the catalytic reaction rate. Recycling experiment shows that the catalyticactivity of the Al-SBA-1has not significantly reduced after reused four times in thealkylation toluene with benzyl alcohol.
3. Synthesis of hierarchically mesoporous silica nanoparticles andmesoporous hydridosilica nanoparticles and their properties
Mesoporous silica nanoparticles (MSNs) have received much attention inpractical fields, such as catalysis, adsorption, separation and biomedicineapplications due to their unique chemical, magnetic and optical properties, and highlevel of biocompatibility. It has been demonstrated that the control of structure,morphology, size, and surface properties of MSNs is important for their biomedicalapplications. However, the reported hierarchically mesoporous silica materials oftenhave relative large particle sizes (sub-micrometre or micrometer). In this section,hierarchically structured single-crystal mesoporous silica SBA-1nanoparticles(HMSNs) were synthesized by using a cationic surfactant and anionic polymerpoly(acrylic acid)(PAA) mesomorphous complexes as a template, tetraethoxysilaneas silica source via the dilute solution method. The effect of different cationicsurfactant to the morphology and the interior structure of the nanoparticles wereinvestigated. The results indicated that hierarchically structured mesoporous silicaSBA-1nanoparticles could be successfully prepared by using CPC or CTAB assurfactant. The size of the nanoparticles was in the range of50-300nm, thesecondary interstitial nanopore and ordered mesopore could be observed. Moreover,mesoporous silica SBA-1nanoparticles synthesized with different silica source wasalso explored. It is found that when tetrapropyl orthosilicate was chosen as silicasource, only the single pore nanoparticles could be obtained and the particle size wasabout75nm. This was mainly due to that hydrolysis rate of tetrapropyl orthosilicate which was slower than that of the tetraethoxysilane. During the hydrolysis process,the polymer of PAA was completely extruded, and the PAA could not play a role asthe secondary template. The bioimmobilization ability of the synthesized HMSNswas investigated by chosen the lysozyme as a typical enzyme. The results revealedthat the HMSNs exhibit a rapid immobilization rates and high immobilized amountsthan that of the MSNs synthesized with tetrapropylorthosilicate as the silica source.
The hydridosilica with Si-H groups could be transformed intophotoluminescent materials at high temperatures, and have potential applications insolar energy systems. It was reported that the mesoporous hydridosilica particleswith size of100-400nm could be prepared under acidic condition by using triblockcopolymer P123as surfactant, triethoxysilane as silica source. In this section, thefluorocarbon surfactant (FC-04) was used to control the growth of hydridosilicaparticles and the effect of FC-04to the morphology, particle size and meso-structureof the mesoporous hydrosilica was investigated. By adjusting the amount of FC-04,the morphology of the particles involved from solid to hollow, and the sizedecreased from few hundreds of nanometers to50nm. Moreover, by using thehollow mesoporous hydridosilica nanoparticle as support and reducing agent,mesoporous hydridosilica materials supported noble metal nanoparticles catalystswere prepared via one pot method. The performance of mesoporous hydridosilicamaterials supported noble metal nanoparticles catalysts were investigated usingcatalytic reduction of4-nitrophenol as a model reaction and they exhibited excellentcatalytic activity.
引文
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