硅溶胶改性及其应用研究进展

二氧化硅在自然界中通常为晶态,而以溶胶-凝胶、水热、模板剂等方法人工合成的二氧化硅纳米颗粒(SiO₂ NPs)通常为无定形态。无定形SiO₂ NPs广泛应用于航空航天、催化剂载体、靶向送药等众多高端领域。生产SiO₂ NPs的方法有很多,但制备结构、形貌简单的SiO₂ NPs的主要方式为离子交换法、硅醇盐水解法、单质硅粉水解法,这些方法可制备粒径在10～800 nm的单分散SiO₂ NPs,同时可根据生产条件控制粒子的单分散性与粒径大小。寻找一种成本低廉且成品单分散性好、粒径可控的生产方法成为目前研究的热点。本文简介了SiO₂ NPs的结构形貌、基础性质、生产方法和最佳合成条件,总结了各方法的优缺点与适用领域。随后介绍了近年来SiO₂ NPs的改性研究与应用,最后在此基础上展望了合成硅溶胶存在的挑战与未来需解决的问题。     

Effect of nano-sized SiO2 on the optical properties of YVO4:Eu3+ phosphors

In this paper, YVO₄: 1%Eu³⁺ phosphor was synthesized via solid state method at 1100 °C. Then TEOS was used as the source of silica, to coat the phosphors, using sol–gel approach. HRTEM analysis confirmed the formation of adhered and smooth coating layer with the thickness of 40–50 nm. From the experiments and characterizations, we found that although the amounts of added SiO₂ to the phosphors were not remarkable, but it resulted in enhancement of photoluminescence properties. Interestingly, under the excitation wavelength of 310 nm, the efficiency of the phosphors increased by about 20%. Also, a considerable effect of coating layer on decrease in surface oxygen vacancies was studied using ESR technique. Finally it was found that SiO₂ coating of YVO₄:Eu³⁺ phosphors, improves both chemical stability and thermal quenching, effectively.     

Synthesis and characterization of double –SO3H functionalized Brönsted acidic hydrogensulfate ionic liquid confined with silica through sol-gel method

Imidazolium-based metal and halogen-free Brönsted acidic ionic liquid (BAIL) (3,3′-(hexane-1,6-diyl)bis(2-methyl-1-(3-sulfopropyl)-1H-benzimidazolium) hydrogensulfate [HbMBIM-PS][HSO₄] was synthesized. The physicochemical properties of this BAIL were investigated using a variety of different analytical and spectroscopic techniques such as ¹H and¹³C-NMR, FT-IR, mass, UV–vis and TGA spectra. A porous silica matrix has been synthesized using BAIL and tetraethoxysilane (TEOS) as silica source by nonhydrolytic sol–gel method. The properties of IL confined silica gel matrix have been studied using FTIR, TGA, SEM, N₂-sorption measurement (BET characterization for determining pore parameters), and NH₃-TPD techniques. From the N₂-sorption measurement, it has been found that BET surface area decreased while pore volume, average pore size and porosity decreased. The thermal stability of the IL has been found to increase upon confinement in silica gel matrix. The results suggested that IL had been successfully confined on silica gel. This IL confined silica gel catalyst is environment friendly and useful for alkane isomerization and esterification reactions.     

Nanoscale Janus Particles with Dual Protein Functionalization

Biofunctionalized Janus particles with tailored surface chemistry are gathering interest for applications as catalysts, multifunctional cell surface targets, nanomotors, and drug delivery systems. The dual nature of the surface chemistry of Janus particles can be exploited to immobilize drugs, cell surface targets, and/or other functional molecules on both sides of the particle surface. In this study, a model system is established for the scalable preparation of nanoscale Janus particles with dual protein functionalization with the proteins ferritin and streptavidin. 80 nm silica nanoparticles (SiNPs) modified with azidosilane are used to prepare Pickering emulsions with molten wax as the droplet phase. The azide‐functionalized SiNPs on the Pickering emulsion droplets are further subjected to face‐selective silanization with biotin‐polyethylene glycol ethoxy silane. Afterward, ferritin is grafted on the azide‐functionalized side via a click‐reaction and the biotin groups are conjugated with streptavidin which is labeled with ultrasmall gold nanoparticles. In order to elucidate the advantages and limits of this approach, a detailed characterization is performed of the particles at every process step. The results show that this method represents a scalable platform for the versatile preparation of nanoscale Janus nanoparticles that can potentially be used with a wide variety of proteins.     

Oscillatory dynamics induced in polyelectrolyte gels by a non-oscillatory reaction: A model

We develop a general model and the associated numerical algorithm to compute the swelling dynamics of chemo-responsive polyelectrolyte gels immersed in a reactive ionic solution kept at a non-equilibrium stationary state by a permanent feed of fresh reactants. Using an autocatalytic bistable but nonoscillatory reaction, namely, the bromate-sulfite reaction, we predict that a piece of hydrogel that swells/shrinks as a function of p H can exhibit spontaneous mechanical and chemical oscillations. This constitutes the extension to realistic and experimentally feasible conditions of results previously obtained on a toy model with artificial swelling conditions.     

Preparation and characterization of Nd doped gadolinium gallium garnet nanopowders and crystals

The structural and optical features of gallium gadolinium garnet (GGG) nanopowders doped with neodymium were investigated. Nanopowders of GGG:Nd were prepared by modified sol‐gel method using acetic acid as complexing agent. This way permitted to incorporate large amounts of dopant (up to 10 %) without destroying garnet structure. Small single crystals of Nd:GGG were grown by a μ‐pulling down method and spectroscopic features of nanopowders and their single crystal counterparts were compared. It has concluded that the Nd³⁺ ions are located preferentially in the same type of sites in crystal lattices of GGG:Nd nanopowders and their single crystal counterparts. In addition, it follows from the perfect agreement of emission wavelengths and line width recorded for nanopowders and single crystal samples that the crystal lattice of GGG in nanopowders is not distorted. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

纳米银溶胶和微腔型光纤SERS基底的制备及其性能比较

通过化学法制备了纳米银溶胶基底和微腔型光纤表面增强拉曼散射(SERS)基底,其中光纤SERS基底的微腔结构是通过氢氟酸(H F)腐蚀得到的.实验采用湿法检测,首先将纳米银溶胶基底与罗丹明6G(R6 G)混合,找到增强效果最强时的裸光纤微腔结构,在此结构的基础上采用溶胶自组装法制备银纳米颗粒包覆的光纤SERS基底,通过控...     

硅溶胶粒度与分布对高硅铝比镁碱沸石合成的影响机理

以硅溶胶为硅源,在不同碱度的溶液中对其进行前处理,制得不同粒度与分布的硅溶胶母液,并以此为原料合成了高硅铝比镁碱沸石分子筛(FER zeolite).通过激光粒度分析仪(LPSA)、傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、扫描电子显微镜/能量色散X射线光谱(SEM-EDS)和X射线荧光(XRF)等对母液和产物进行了表征,考察了碱度对硅溶胶粒度特性和分子筛晶化过程以及产物性质的影响.结果表明,随着碱度增加,硅溶胶母液的粒径逐渐增大,对应于溶液中更多的Q³硅单元向Q²硅单元转变.在低碱度下,高聚合度的Q³硅单元倾向于使晶化过程遵循固相转化机理,生成大片纯相镁碱沸石,且产物的相对结晶度和固体收率均较高;而在高碱度下,大量活性的Q²硅单元则易于使凝胶成块,晶化过程遵循液相转化机制,产物尺寸较小且含有杂晶,相对结晶度和固体收率均较低.     

溶胶-凝胶光学薄膜的激光损伤研究

采用溶胶-凝胶工艺制备了SiO2与ZrO2单层介质膜,用输出波长1.06μm,脉宽15ns的电光调Q激光系统产生的强激光进行辐照实验。观察了光学薄膜经强激光辐照后的损伤情况,讨论了溶胶 凝胶光学薄膜在强激光照射下的损伤机理,提出了溶剂替换、紫外光处理、添加有机粘接剂等提高溶胶 凝胶光学薄膜激光损伤阈值的方法。     

杂化溶胶改性紫外光固化胶粘剂的研究

以自制的杂化溶胶对紫外光固化丙烯酸酯胶粘剂进行改性,得到了具有高粘接强度,对丙酮、乙醇、氯仿等具有明显的耐溶剂性的紫外光固化胶粘剂。实验发现：活性稀释剂中含有较多的羟基、羧基时,此胶粘剂对玻璃的粘接强度较高;胶层粘接力随杂化溶胶用量的增加先增大,后减小,当杂化溶胶中的固体质量为光敏树脂的60％时,胶粘剂的剪切强度达到最大（12MPa）。