用吸附数据对硅胶表面的分形分析

根据一种中孔硅胶对甲酸、乙酸、丙酸和四氯化碳蒸气吸附等温线的单层区域和毛细凝结区域的数据以及自四氯化碳稀溶液中吸附系列脂肪醇的结果计算了该硅胶表面分形维数D.除了由吸附四氯化碳等温线毛细凝结区域所得D值低于2外,由其它吸附数据得出的该硅胶的分维D近似相等(D=2.06±0.05).中孔硅胶低D值可用其孔结构特性解释.     

介孔吸附剂表面分形分析

用自溶液中吸附的方法测定了介孔硅胶和活性炭的分形维数D.结果表明:(1)硅胶自四氯化碳或环已烷中吸附脂肪醇、酮、酯和含氧芳香化合物,活性炭自水中吸附芳香化合物的等温线均服从Langmuir方程.用极限吸附量n_m^s和表观分子面积σ_a,根据方程log n_m^s=-(D)/(2)log σ_a+常数,可计算出分维D. n_m^s和σ_a是根据Langmuir方程和吸附剂比表面数据求出的.(2)用液相吸附法求出的介孔硅胶的分维值与由气体吸附法求出的值相同,并均近于2.当表面曲率半径大于吸附分子大小时,吸附剂表面可是低分维的.(3)由液相吸附法得到的介孔活性炭的分维也近似为2.可能的解释是,活化作用改变了原始炭的微孔结构,使其成为介孔和大孔.介孔活性炭也可是低分维表面.     

再生催化剂表面的变维分形表征

基于分形几何理论，以失活的催化剂化催化剂的再生为研究对象，用静态重量吸附法测定了经历不同再生阶段催化剂表面的单层饱和吸附量，计算得到了不同再段催化剂表面的分形维数，考察了其表面形貌在再生过程中的变化规律，研究结果表明，整个再生过程中，催化剂表面的分形维数在2．5－3．2之间有规律的发生变化，即从再生开始到结束，表面的分形维数由小变大，再由大变小然后趋于稳定。催化剂颗粒的电镜分析结果与实验数据一致。     

薄膜表面的分形特征

在计算机上用随机数相加的方法产生了一个分形表面,对这个表面的模拟测量表明,z方向分辨率变化对分形维数测量结果影响很小,x、y方向分辨率降低时会导致测量结果统计误差增大用扫描隧道显微镜（STM）测量了沉积在三种不同基底上的Au膜的分形维数．测得Au／陶瓷的分形维数D＝2.15,Au／光学玻璃的分形维数D＝2.06．Au／载玻片上各点的分形维数较不一致．同时讨论了多图方法中各单图曲线之间不衔接的原因．     

气相色谱法测定气固表面的吸附停留时间

提出了一个用气相色谱测定气体在固体表面上吸附停留时间的方法. 经推导, 得到了测定公式.用八种烷烃及苯在硅胶上的吸附实验数据进行验证和研究, 得到了满意的结果.     

煤微孔表面的分形维数及其变化规律的研究

本文利用气体吸附数据确定了各种煤阶煤（从褐煤到无烟煤）和煤焦气化反应过程中微孔表面的分形维数及其变化规律。这有助于进一步认识煤的孔结构特征。     

污泥热解过程中焦的表面孔隙结构分形生长

主要对污水污泥在高温热解和低温热解条件下热解焦炭的表面孔隙结构特性进行了研究。结果表明,污泥热解过程中随着挥发分的析出,污泥热解焦炭的孔隙结构逐渐发达。低温和高温热解过程中挥发分的析出,使得孔径为3.75 nm的孔得到了极大的发展。通过对污泥热解焦炭的N2吸附过程进行的分形分析发现,不同停留时间低温和高温热解焦炭的表面分形维数可以分为FD-1和FD-2。其中,FD-1主要表征了较大孔(0.86 nm)的表面分形维数,FD-2则主要表征了超微孔(0.86 nm)的表面分形维数。随着热解停留时间的延长,FD-1和FD-2逐渐增大并趋于稳定。与高温热解焦炭的超微孔表面分形维数相比低温热解焦炭出现了较大的增加,而较大孔的表面分形维数则相对低温热解焦炭未见有较大的改变。     

分形理论在催化剂研究中的应用

介绍了分形和分形维数在催化剂研究中的应用.概述了催化剂研究中常用的分形维数测定方法,包括盒子维法、散射强度法和吸附法.从四个方面分析了近年来催化剂分形研究的方向和进展:分形维数与催化剂评定和筛选,催化剂分形孔结构,分形与反应动力学,模型建立.从分形维数的测量、催化剂分形生长模型以及多重分形研究三个方面对分形在催化剂方面的应用进行了评价和展望.     

三种钢基疏水表面微观形貌的分形特征及其对润湿性的影响

采用化学刻蚀与低表面能物质修饰相结合的方法, 通过调控刻蚀时间在304不锈钢、 X80管线钢和45#钢表面构造不同的微观形貌; 借助扫描电子显微镜采集不同材料表面的微观形貌, 并采用接触角测量仪测量其润湿性能; 应用Matlab软件编程计算分形参数. 结果表明, 3种材料构造的疏水表面均具有分形特征, 且最佳刻蚀时间为30 min, 此时多重分形谱子集维数最大值最靠左, 对应的奇异性指数最小, 表征表面微观形貌的分形维数也达到最大值; 分形维数与接触角线性拟合效果优良, 接触角随分形维数的增大而增大.     

鳙鱼心中电子载体泛醌化合物的研究

鳙鱼（Ａｒｉｓｔｉｃｈｔｈｙｓｎｏｂｉｌｉｓ）心脏提取物经硅胶柱色谱分离、制备薄层色谱纯化，得到二种泛醌化合物，用ＮＭＲ、ＩＲ、ＭＳ、ＵＶ、ＨＰＬＣ、ＴＬＣ等现代测试技术测定其化学结构为２，３－二甲氧基－５－甲基－６－１０聚异戊二烯基－１，４－苯醌（Ⅰ）和一种未见报道的新泛醌酯——２，３－二甲氧基－５－甲基－６－甲酯基－八聚异戊二烯基－１，４－苯醌（Ⅱ）。     

Fractal Study of Mesoporous Structure in Water Molecular Condensed System

Bis-(4-stearoylaminophenyl) ether (BSADE) can aggregate and self-assemble in water. Transmission electron microscopy (TEM) indicated that the morphology of BSADE aggregates in water was entanglement and thin fiber-like, and that a three dimensional network structure was formed. Water molecules were entrapped in this three dimensional network structure and formed a new type of condensed system (so-called water molecular gel). Water molecular gel is a typical mesoporous material which can be characterized by the fractal dimension D. Using gas adsorption method along with measurement of porosity and specific surface area, the fractal dimension D of the complicated pores was 2.1-2.2 for this water molecular gel. Using viscosity method and the Cayley fractal tree, the fractal dimension D of the fiber-like three dimensional network was determined to be 1.98. The formation process of water molecular gel can be described as nucleation followed by a repeated growing and branching cycle.     

Fractal dimensions of silica gels generated using reactive molecular dynamics simulations

We have used molecular dynamics simulations based on a three-body potential with charge transfer to generate nanoporous silica aerogels. Care was taken to reproduce the sol-gel condensation reaction that forms the gel backbone as realistically as possible and to thereby produce credible gel structures. The self-similarity of aerogel structures was investigated by evaluating their fractal dimension from geometric correlations. For comparison, we have also generated porous silica glasses by rupturing dense silica and computed their fractal dimension. The fractal dimension of the porous silica structures was found to be process dependent. Finally, we have determined that the effect of supercritical drying on the fractal nature of condensed silica gels is not appreciable.     

Adsorption of triton X-100 on silica gel: effects of temperature and alcohols

Adsorption of Triton X-100 (TX-100) on silica gel has been studied as a function of temperature (308–328 K) and composition for mixtures of water with ethanol or t-butanol. The adsorption capacity of silica gel for TX-100 decreases with increase in alcohol content. Adsorption isotherms of TX-100 on silica gel are four-region and were analyzed using the ARIAN (adsorption isotherm regional analysis) model. Data in regions 2, 3 and 4 were fitted to the Temkin, bilayer and reverse desorption isotherms, respectively. The results show that adsorption of TX-100 on silica gel in water and alcohol-water binary mixtures occurs mainly through formation of monolayer surface aggregates or low bilayer coverage.      

表面印迹法制备钴(Ⅱ)离子印迹硅胶及性能

采用表面印迹技术, 以Co(Ⅱ)离子作为印迹离子, 二乙烯三胺基丙基三甲氧基硅烷为功能分子, 硅胶为支撑物, 环氧氯丙烷为交联剂, 在硅胶表面制备Co(Ⅱ)离子印迹硅胶材料, 利用红外光谱仪、扫描电镜和热重分析仪等进行了表征, 采用平衡吸附法研究了印迹硅胶材料的吸附性能和选择识别能力. 结果表明, 印迹硅胶材料和非印迹硅胶材料的最大吸附量分别为35.2和6.5 mg/g; 印迹硅胶材料对Co(Ⅱ)离子的吸附行为符合Langmuir模型; 20 min即可达到吸附平衡; 当pH=3.9~7.8时, 印迹硅胶材料保持了较好的吸附容量; 印迹硅胶材料对Co(Ⅱ)离子具有较强的选择性识别能力; 重复使用时性能稳定.     

Structural characteristics of silica sonogels prepared with additions of isopropyl alcohol

Wet silica gels with approximately 1.4 x 10(-3) mol SiO2/cm3 and approximately 92 vol % liquid phase were obtained from sonohydrolysis of tetraethoxysilane (TEOS) with different additions of isopropyl alcohol (IPA). The IPA/TEOS molar ratio R was changed from 0 to 4. Aerogels were obtained by supercritical CO2 extraction. The samples were analyzed by small-angle X-ray scattering (SAXS) and nitrogen adsorption. The wet gels exhibit mass fractal structure with fractal dimension increasing from D approximately 2.10 to D approximately 2.22, characteristic length xi decreasing from approximately 9.5 to approximately 6.9 nm, as R increases from 0 to 4, and an estimated characteristic length for the primary silica particles lower than approximately 0.3 nm. The supercritical process apparently eliminates a fraction of the porosity, increasing the mass fractal dimension and shortening the fractality domain in the mesopore region. The fundamental role of isopropyl alcohol on the structure of the resulting aerogels is to decrease the porosity and the pore mean size as R changes from pure TEOS to R = 4. A secondary structure appearing in the micropore region of the aerogels can be described as a mass/surface fractal structure, with correlated mass fractal dimension Dm approximately 2.7 and surface fractal dimension Ds approximately 2.3, as inferred from SAXS and nitrogen adsorption data.     

Monolith Passive Adsorbers Prepared with Hydrophobic Porous Silica Rods Coated with Hydrogel

This work focuses on the synthesis and characterization of porous silica monolith-based adsorbent materials. Materials with bimodal porosity (macro and meso) were prepared through a sol–gel process. The capacity of adsorption of organic molecules was ensured by grafting of hydrophobic organic coating on the silica surface. Alkylsilane chains or lauryl acrylate polymer were used for this purpose. The adsorption kinetic behavior of the produced materials was assessed through benzophenone adsorption studies in aqueous media. The results have shown that the macropore size of the monoliths had no effect on the adsorption capacity. The thicker organic layer prepared by polymerization of lauryl acrylate has decreased the adsorption kinetics without affecting the total adsorption capacity. The over-coating with additional external layer of hydrogel further slowed the diffusion of benzophenone thus better matches the passive-sampler requirements.     

Nitrogen Sorption Studies of Silica Particles Obtained in Emulsion and Microemulsion Media

The internal surface structures of silica aerogel particles synthesized using different catalysts in emulsion and microemulsion media have been investigated by means of N(2) adsorption and desorption isotherms. Surface fractal dimensions have been computed using different methods: Frankel-Halsey-Hill plots of the adsorption isotherms, the thermodynamic fractal isotherm equation, and a modification of the thermodynamic fractal isotherm equation. Silica aerogels synthesized in emulsion media with an acidic catalyst have a high specific surface area without micropores and show two separate ranges of scales where the surface fractal dimensions are different and constant. Silica aerogels synthesized in emulsion media with a basic catalyst have a moderate specific surface area with a high percentage of micropores and show constant surface fractal dimensions over a larger range. Silica aerogels synthesized in microemulsion media with a basic catalyst have a low specific surface area with a moderate percentage of micropores and show a moderate range of scales over which the surface fractal dimension is constant. Analyses by both the thermodynamic and modified thermodynamic methods give similar ranges of the surface fractal dimensions of the silica particles. Copyright 2000 Academic Press.     

A novel sol-gel-material prepared by a surface imprinting technique for the selective solid-phase extraction of bisphenol A

A novel and simple imprinted amino-functionalized silica gel material was synthesized by combining a surface molecular imprinting technique with a sol-gel process on the supporter of activated silica gel for solid-phase extraction-high performance liquid chromatography (SPE-HPLC) determination of bisphenol A (BPA). Non-imprinted silica sorbent was synthesized without the addition of BPA using the same procedure as that of BPA-imprinted silica sorbent. The BPA-imprinted silica sorbent and non-imprinted silica sorbent were characterized by FT-IR and the static adsorption experiments. The prepared BPA-imprinted silica sorbent showed high adsorption capacity, significant selectivity and good site accessibility for BPA. The maximum static adsorption capacity of the BPA-imprinted and non-imprinted silica sorbent for BPA was 68.9 and 34.0 mg g⁻¹, respectively. The relatively selective factor value of this BPA-imprinted silica sorbent was 4.5. Furthermore, the difference of the retention characteristics of BPA on the C₈ SPE column and BPA-imprinted silica SPE (MIP-SPE) was compared. The MIP-SPE-HPLC method showed higher selectivity to BPA than the traditional SPE-HPLC method. At last, the BPA-imprinted polymers were used as the sorbent in solid-phase extraction to determine BPA in water samples with satisfactory recovery higher than 99% (R.S.D. 3.7%).     

硅胶表面上脂肪酸蒸气吸附膜

应用Gibbs方程由甲酸、乙酸和丙酸蒸气在硅胶上的吸附等温线计算了吸附膜的表面压力(π)与每个吸附分子所占面积(σ)间的关系(π～σ图).所得曲线与不溶物在溶液表面上的结果相似,均表现出有“液态扩张膜”“转变膜”和“液态凝聚膜”.不同的是,不溶物只能形成单分子层膜,而硅胶表面上的脂肪酸吸附膜则是多分子层的.蒸气吸附膜由单层向多层的转变,恰与π～σ图上的“液态扩张膜”向“转变膜”的转变相对应.吸附焓(△H)与吸附熵(△S)的计算结果表明,在此转变附近AH和AS发生急剧变化.