模板技术制备单块介孔分子筛

模板技术与溶胶-凝胶过程结合是合成介孔分子筛的有效方法. 模板通常采用表面活性剂在一定条件下自组装形成超分子结构, 在不同条件下, 此超分子结构具有不同聚集形态, 合成出的介孔分子筛也具有不同的孔道排列方式 [1~4]. 溶胶-凝胶过程是通过硅源体的水解缩合并缓慢蒸发除去溶剂实现的. 此过程及产物受体系的pH值影响很大. 在碱性体系中制备的介孔材料通常为粉末状, 不利于实际应用, 因此人们更加重视合成具有规则外形的介孔材料 [5]. 目前报道大多是在酸性体系中制备不同形状的介孔材料 [6~12]. 有关合成单块介孔分子筛的报道较少 [13]. 最近, 王策等 [14,15]改进了通常的溶胶-凝胶过程, 预先将溶胶中的有机溶剂通过萃取加以除去, 然后实现凝胶过程. 结果表明, 采用改进的溶胶-凝胶技术能显著地加快凝胶过程, 从而制备出任意形状和尺寸的氧化物单块, 并有无裂纹、透明性好等特点. 所以, 采用改进的溶胶-凝胶技术能高效地制备出高质量的氧化物单块.      

块状TiO2气凝胶的制备及其表征

随着以溶胶-凝胶法和超临界干燥技术为基础的气凝胶制备方法的逐步完善,已不断制备出多种气凝胶[1～3].由于TiO2具有半导体特性,它常被作为光催化剂而受到重视,但是TiO2气凝胶的结构强度远比SiO2气凝胶小,在制备过程中极易碎裂粉化,所以至今未见制备块状TiO2气凝胶的报道.Dagan等[4]曾用异钛酸丁酯为母体制得TiO2气凝胶,并发现水杨酸在TiO2气凝胶存在下的光解速率是一般TiO2粉末的10倍,但获得的仅为TiO2气凝胶粉末.张敬畅等[5]以无机盐为原料,采用溶胶-凝胶法结合超临界干燥技术制备了纳米级TiO2气凝胶,也未能得到块状TiO2气凝胶材料. 本文报道以正钛酸丁酯为原料制备块状TiO2气凝胶的方法,并用TEM,SEM,XRD和IR等手段对所获得的气凝胶进行了结构表征.     

尖晶石型LiMn_2O_4的低温制备

锂锰氧化物作为锂离子电池正极材料一直引起人们很大的兴趣.其原材料成本低、资源丰富,用它作成的电极具有电压高、循环寿命长、耐过充放电性能好以及无毒性等优点.而尖晶石型LiMn2O4则是作为下一代锂离子电池最有前途的电极材料之一.经典的制备方法采用固相反应法,煅烧温度高,反应时间长,产物易团聚形成大颗粒.近年来发展了一些低温技术合成锂锰氧化物材料,如溶胶凝胶法[1],沉淀法[2],Penichi法[3]等.这些方法的煅烧温度较低,易得到颗粒小,比表面积大的锂锰氧化物.我们用溶胶凝胶法制备了纳米颗粒的尖晶石型结构的LiMn2O4,用TEM、XRD…     

超快速溶胶-凝胶法制备高纯二氧化硅单块

传统的溶胶-凝胶工艺存在几个严重的缺点,例如,凝胶时间过长(20d以上),体积收缩太大(>75%),形状和尺寸无法控制以及严重的龟裂等^[1].这些缺点限制了它在技术上的应用.     

基于溶胶-凝壳聚糖/SiO2杂化材料的安培型葡萄糖生物传感器

近年来 ,基于溶胶 -凝胶技术的有机 /无机杂化复合材料由于具有有机物的柔性和易修饰性 ,以及无机物的刚性和稳定性等 ,因此有利于保持生物分子的活性和生物传感器的研制 [1] .壳聚糖 ( CS)具有易成膜性和生物相容性 ,其在生物传感器中的研究已受到重视 [2 ] .本文通过原位溶胶 -凝胶 ( Sol- gel)技术 ,用 CS和甲基三甲氧基硅烷 ( MTOS)制备了 CS/Si O2 有机 /无机杂化材料 ,并将其用于对葡萄糖氧化酶 ( GOD)的固定 ,研制出葡萄糖生物传感器 .采用人工过氧化物酶普鲁士蓝 ( PB) [3]作为电子传递的媒介体 ,并外加一层 Nafion膜以增强…     

镧六方铁氧体LaxBa1-xFe12O19的制备与表征

随着电子工业的发展 ,在国防及其他领域中微波技术得到普遍应用 .但微波辐射对人类健康存在着不可忽视的危害 .因而研制性能优良的吸波材料不仅对国防科技的隐身技术 ,而且对保证人体健康都有着十分重要的意义 .自从 1 956年 Philips实验室研制出六方晶系结构的铁氧体以来[1] ,已有大量文献报道铁氧体磁性材料在微波吸收方面的重要作用[2～ 6] .稀土元素是具有优良磁性能的吸波材料 ,Chen等 [7]和 Roh等 [8]分别报道过掺杂稀土元素的尖晶石型及钙钛矿型铁氧体 .本文利用溶胶 -凝胶法合成了掺杂稀土元素镧的磁铅石型系列铁氧体材料 ( Lax B…     

基于杯芳烃和紫精的电刺激响应二元水凝胶

基于上缘四脯氨酸修饰杯[4]芳烃和各种紫精客体分子的相互作用, 我们构筑了一类新型的二元超分子水凝胶. 得到结果显示, 在酸性条件下, 溴化紫精盐最易于促进四脯氨酸修饰杯[4]芳烃形成水凝胶. 并且经落球法测定了所制备水凝胶的凝胶-溶胶转变温度, 采用原子力显微镜和扫描电子显微镜表征了水凝胶的微观形态, 发现紫精的侧链对水凝胶性质具有显著影响, 包括凝胶-溶胶转变温度和微观形态. 值得注意的是, 该类水凝胶不仅具有优良的电刺激响应性, 而且能够通过化学、pH和热等多种因素进行调控.     

分子印迹溶胶-凝胶材料的制备及应用

分子印迹技术是制备对特定分子具有选择性识别的聚合物的技术。分子印迹技术与溶胶-凝胶过程相结合,可设计多孔无机主体,增强分子识别能力,并具有极好的热稳定性和水解稳定性。改变溶胶-凝胶过程的条件,可制备具有最佳孔隙率和表面积,并用于分离复杂的混合物、选择性吸附富集模板分子(或目标分子)、催化、微合成器应用的分子印迹溶胶-凝胶材料。综述了溶胶．凝胶技术和分子印迹技术的特点,分子印迹溶胶-凝胶技术和分子印迹溶胶．凝胶材料的概念、基本原理、制备方法及应用。     

模板技术制备单块介孔分子筛

模板技术与溶胶 -凝胶过程结合是合成介孔分子筛的有效方法 .模板通常采用表面活性剂在一定条件下自组装形成超分子结构 ,在不同条件下 ,此超分子结构具有不同聚集形态 ,合成出的介孔分子筛也具有不同的孔道排列方式 [1～ 4 ] .溶胶 -凝胶过程是通过硅源体的水解缩合并缓慢蒸发除去溶剂实现的 .此过程及产物受体系的 p H值影响很大 .在碱性体系中制备的介孔材料通常为粉末状 ,不利于实际应用 ,因此人们更加重视合成具有规则外形的介孔材料[5] .目前报道大多是在酸性体系中制备不同形状的介孔材料 [6～ 12 ] .有关合成单块介孔分子筛的报道…     

溶胶-凝胶法修饰的一次性氯离子选择性电极的研究

溶胶-凝胶法(sol-gel)对固定试剂的种类和数量具有可调性,又具有保持性能稳定的潜在优势;一些小分子离子可以自由进出sol-gel的孔径,使得sol-gel基质内外浓度相等,因而可制备化学电极。本文通过正硅酸乙酯[TEOS]在适宜的酸催化下,水解制得电极材料,采用溶胶．凝胶掺杂技术,成功地修饰了新型氯离子选择性电极,这种电极的线性范围和AgCl-AgS2固态膜电极、     

Investigation on Structures and Properties of Shape Memory Polyurethane/Silica Nanocomposites

In this study, high performance shape memory polyurethane (SMPU)/silica nanocomposites with different silica weight fraction including SMPU bulk, 3%, 4.5%, 6%, 7.5%, 10%, were prepared by sol‐gel process initiated by the solid acid catalyst of p‐toluenesulfonic acid (PTSA). Field emission scanning electron microscopy (FE‐SEM) and transmission electron microscopy (TEM) observation show that the silica nanoparticles are dispersed evenly in SMPU/silica nanocomposites. Tensile test and dynamic mechanical analysis (DMA) suggest that the mechanical properties and the glass transition temperature (T_g) of the nanocomposites were significantly influenced by silica weight fraction. Thermogravimetric analysis (TGA) was utilized to evaluate the thermal stability and determine the actual silica weight fraction. The TGA results indicate that the thermal stability can be enhanced with the hybridization of silica nanoparticles. Differential scanning calorimetry (DSC) was conducted to test the melting enthalpy (ΔH) and the results suggest that the ΔH was markedly improved for the SMPU/silica nanocomposites. Thermomechanical test was conducted to investigate the shape memory behavior and the results show that the shape fixity is improved by hybridization of silica and good shape recovery can be obtained with the increasing of cycle number for all the samples.     

离子液体限域于硅胶纳米孔道中的电化学行为研究(英文)

通过溶胶-凝胶法制备了硅胶包载咪唑类离子液体修饰电极,研究其与体相离子液体不同的伏安行为;另一方面,制备不同离子液体含量为15% ~ 28%的包载离子液体硅胶和涂覆离子液体硅胶,用电化学阻抗研究其在20 ^oC到80 ^oC下电导率的变化情况. 异常的电化学行为主要表现在：1)硅胶包载离子液体导致Fc/Fc⁺电对的半波电位正移63.5 ~ 200 mV;2)当离子液体限域于硅胶纳米孔道中时,离子液体的电化学稳定性变差;3)包载离子液体硅胶的电导率要比涂覆离子液体的电导率高29.6% ~ 136%. 由此推断,可能是由于离子液体充满硅胶孔腔和孔道从而形成了纳米网状的离子液体导电介质. 这些结果表明,硅胶包载离子液体不仅可以作为修饰电极的优良载体,而且也有助于理解离子液体限域于硅胶纳米孔道中的限域效应.     

Hybird Membrane with High Proton Conductivity and Selectivity Based on SPEEK for Direct Methanol Fuel Cells

Composite membranes based on sulfonated silica/sulfonated poly(ether ether ketone)(SPEEK) were prepared by means of sol-gel method so as to gain a high conductivity and reasonable methanol permeability.The sulfonated silica is generated in situ via the hydrolysis of sulfonated 3-anminopropyl triethoxysilane(KH550) synthesized newly from 3-aminopropyl triethoxysilane and 1,4-butane sultone.The membrane with a silica mass fraction of 5% exhibits a conductivity of 0.187 S/cm at 80 °C and a methanol coefficient with 9.72×10-7 cm2/s.The composite membranes show improved condutive ability and better selectivity that can be promisingly used in direct methanol fuel cell.     

溶胶凝胶法制备CdS/SiO2量子点玻璃的研究

通过溶胶凝胶转变过程制备了硫化镉／二氧化硅量子点复合玻璃材料（硫化镉在复合材料中的最大掺杂质量比可达到30％）；并针对两种催化剂对复合体系的不同影响对这一类体系的物理化学性质进行了较为系统的研究．复合体系的溶胶凝胶转变点可通过对复合溶胶粘度随时间变化的观测而确定．TEM法与低频Raman散射法的测定表明实验制备的样品中CdS颗粒基本为nm级的球形粒子。其CdS颗粒粒径随CdS含量增加而增大。随CdS／SiO2量子点玻璃材料中CdS颗粒粒径的减小，其吸收光谱中的吸收边界与常规尺寸颗粒的吸收光谱边界相比有明显的蓝移，体现出显著的量子效应．适宜的热处理过程对复合材料中CdS颗粒粒径的减小和量子效应的增强起着有利的作用．     

超快速溶胶-凝胶法制备高纯二氧化硅单块＊

An ultra-fast sol-gel process has been developed to get high content silica materials,in which,the solvent tetrahydrofuran(THF) for hydrolysis of precursor tetraethyl orthosilicate,was removed through solvent extraction to obtain bulk sol.The bulk sol can be molded in different shapes such as discoid,pellet,octagon,cylinder,and half-sphere.They solidified and gelled in a very short time in the presence of lithium salt.Measurements show that the silica monoliths possess volume shrinkage of 52%,high silica content of 82.4% and transmittance of 70% in the UV/Vis region,and are crack-free indefinitely.     

DMF及热处理对常压制备Cu掺杂SiO2纳米复合气凝胶的影响

以正硅酸乙酯(TEOS)为硅源, 硝酸铜(Cu(NO3)2·3H2O)为铜源, 通过在复合溶胶体系中引入干燥控制化学添加剂(DCCA)N,N-二甲基甲酰胺(DMF)进行原位共溶胶-凝胶, 结合常压干燥工艺, 制备出具有高比表面积(560 m2·g-1)的Cu-SiO2纳米复合气凝胶(含铜质量分数为5%). 研究了DMF对凝胶时间、干燥过程和复合气凝胶形态结构的影响, 利用N2物理吸附, 全自动X射线衍射(XRD)仪, 傅立叶变换红外(FT-IR)光谱仪, 透射电子显微镜(TEM)等对样品的形貌结构进行了表征. 实验结果表明, DMF能有效防止凝胶的开裂, 抑制颗粒团簇的产生, 使所得复合气凝胶的粒径减小, 比表面积增加, 微观结构更趋完善. 高温热处理后, Cu-SiO2中的铜物种仍高度分散于骨架网络中, 复合气凝胶显示出良好的热稳定性.     

改进溶胶凝胶过程制备Cds/SiO_2量子点玻璃(英文)

改进了溶胶凝胶转变过程中金属镉盐的引入方式，首次采用与镉盐络合（配合物法）和将镉盐穹表面活性剂形成微乳（微乳法）的不同方式将镉盐均匀掺杂于硅溶胶中，并制备了硫化镉掺杂质量比为0．88～7．4Wt％硫化镉／二氧化硅量子点复合玻璃材料．其吸收光谱中的吸收边界与常规溶胶凝胶过程制备样品的吸收光谱边界相比有更明显的蓝移，体现出更为显著的量子效应．     

改进溶胶凝胶过程制备CdS/SiO2量子点玻璃

The sol-gel process has been applied successfully to the preparation of small-sized CdS-doped silica glasses. Silica glasses containing 0.887.4wt% CdS were synthesized in a process in which ethylene diamine tetra-acetic acid (EDTA) or surfactant microenmulsion is added to obtain smaller size CdS crystal with narrower size distribution. These additives can be removed after the heat treatment during the densification procedure. The optical absorption edge of CdS crystals in doped glasses obtained by new methods exhibited larger blue shifts(comparing with the bulk absorption edge value of CdS crystal) than that without addition of EDTA or surfactant microemulsion in the preparing process. Thus the quantum size effect was found to be enhanced for glasses containing CdS prepared by the improved sol-gel process.     

Investigation of tetherable distilbazolium compounds as fluorescent probes in nanostructured silica sol-gel materials

Distibazolium dyes are investigated by steady-state and time-resolved fluorescence techniques in a series of low- and high-viscosity polar solvents and in a silica sol-gel matrix. In all solvents and the sol-gel matrix, an interplay of photoinduced switching between different cis-trans isomers and solvation dynamics is observed. Even in a viscous solution (glycerol) and in silica gel, cis-trans isomerization is solvent-controlled. Whereas in glycerol the solvation results in a time-dependent fluorescence Stokes shift, the solvation-induced spectral heterogeneity in silica gel is mostly static, possibly due to a close proximity of dye molecules to the silica surfaces of the nanopores. Compared to low-viscosity solvents, where the cis-trans isomerization process takes place with a solvent-dependent rate on the timescale of about 120-150 ps, it slows down to about 1100-1400 ps in glycerol and about 1500 ps in a sol-gel matrix. Additionally, fluorescence kinetics of the dyes in the sol-gel reveals the presence of a range of different "frozen-in" conformers exhibiting a broad spectrum of lifetimes from 20 to 300 ps.     

Electroosmotically enhanced mass transfer through polyacrylamide gels

We present an internal pumping strategy to enhance solute fluxes in polymer gels. The method is based on electroosmotic flow driven by an electric field applied across a gel that has been doped with charged colloidal inclusions. This work is motivated by the need to enhance the transport in gel-based biosensor devices whose response dynamics are often mass transfer limited. In this case, polyacrylamide gel slabs were doped with immobilized, charged silica colloids, and the flux of a fluorescent tracer was measured as a function of applied field strength, the volume fraction and size of the colloidal silica inclusions, and the bulk electrolyte composition. Significant flux enhancements were achieved with applied electric currents on the order of a few mA. Control experiments indicated that the flux enhancement was not due to any distortion of the gel diffusional properties in response to the presence of the inclusions. At a constant inclusion volume fraction, the electroosmotic solute flux enhancement was strongest for the smallest particle sizes that provide the highest total surface area, consistent with the electroosmotic mechanism whereby fluid flow is generated along the solid/liquid interface.