硅藻土表面酸性质的研究

研究了几种硅藻土的表面羟基结构、表面酸性质及其孔结构，发现除浙江白土表面具有双生的硅羟基外，其他只有连生与孤立的硅羟基；硅藻土中均存在少量的Ｂ酸和Ｌ酸；硅藻土酸性质及经ＮＨ４Ｃｌ或ＨＣｌ活化后的酸性质变化与硅藻土孔结构、表面结构有关。焙烧温度升高，硅藻土酸强度增加，酸量减少。     

国产硅藻土吸附尿激酶机理的研究

在常温下, 尿激酶在浙江土和吉林土表面的吸附等温线分别为V型和II型; 焙烧后两者皆转为III型。吸附等温线类型与硅藻土表面结构、孔结构、表面ζ电位有关。在400℃焙烧的硅藻土等电点值最低, 吸附量最大; 改性后, 吸附量也发生改变。本文还测定了尿激酶在硅藻土表面的吸附形态, 其吸附等温线方程符合0/(1-0)=(Kc)^1/β, 并讨论了平衡常数K和尿激酶吸附功能链段数β随温度的变化。     

MCM-41分子筛的改性、表面结构与吸附性质的研究

用三甲基氯硅烷、二甲基二氯硅烷、甲基三氯硅烷、四氯化硅与甲基碘改性高硅MCM-41中孔分子筛。XRD,^2^9SiMASNMR,^1^3CMASNMR,以及N~2、水与环己烷吸附的表征,显示改性不同程度地改变了分子筛的表面组成与结构,减小孔径,增加孔壁厚度,因而影响吸附行为,减小吸附容量。硅烷化减少了MCM-41的表面硅羟基含量,增加其疏水性。用CH~3I改性使孔径减小1.4nm,而硅羟基含量并未显著减少。硅烷化以及用CH~3I改性可提高MCM-41分子筛的热稳定性。SiCl~4的改性作用相对不明显。样品的水及环己烷吸附容量与其表面硅羟基含量呈现不同的线性关系,揭示高硅MCM-41分子筛表面吸附中心的本性。     

制备高碳醇Cu-Fe系催化剂的比表面积、孔结构和孔径分布

用ＡＳＡＰ－２０００型物理吸附仪,研究了制备高碳醇Ｃｕ－Ｆｅ系催化剂的比表面积、孔结构、孔容积和孔径分布等．结果表明,随着焙烧温度的提高,比表面积下降;在相同的焙烧温度下,组成和沉淀过程的ｐＨ值也影响其表面积大小．催化剂的活性与反应可利用的表面积相关．根据吸附－脱附等温线,确定了催化剂的孔结构及孔径分布的变化规律．数据表明,孔径分布和孔容积对催化剂的活性至关重要,平均孔径（４Ｖ／Ａ,根据ＢＥＴ）可作为衡量Ｃｕ－Ｆｅ系催化剂活性高低的一个参数．焙烧温度的选择是使催化剂具有适宜的孔径分布和较大的孔容积,因而具有较高活性的重要条件     

硅甲基接枝改性MCM-48的结构特征及表面性质

本文利用三甲基氯硅烷与未焙烧MCM-48反应,实现对MCM-48的表面硅甲基接枝改性。结果表明:原未焙烧MCM-48孔道内的CTAB模板剂被脱除,三甲基氯硅烷与表面羟基反应,将硅甲基官能团接枝到MCM-48的内外表面。改性后MCM-48具有良好的长程有序结构,较窄的孔径分布,较大的孔体积和较高的比表面积,相对于未焙烧MCM-48,硅甲基接枝改性MCM-48的表面亲水性降低,亲油性得到提高。     

载铂铝交联蒙脱土（Pt／Al－CLM）的结构稳定化作用与其n－C_8芳构化性能的关系

利用ＸＲＤ、ＤＴＡ、ＩＲ考察了预焙烧对铝交联蒙脱土（Ａｌ－ＣＬＭ）结构的稳定化作用及引入铂对稳定Ａｌ－ＣＬＭ结构的协同效应；用加压连续流动微反装置研究了Ｐｔ／Ａｌ－ＣＬＭ的ｎ－Ｃ_８芳构化性能与其结构稳定性的关系。结果表明：经４００－５００℃的高温预焙烧可使Ａｌ－ＣＬＭ在浸铂过程中保持较高的层结构有序度和规整性，相应保持较大的层间域尺度，对Ａｌ－ＣＬＭ的结构具有稳定作用；引入的铂与Ａｌ－ＣＬＭ的四面体片发生相互作用，可抑制硅氧四面体的扭曲旋转，从而阻抑八面体结构羟基的脱除，具有稳定结构羟基的作用；而Ｐｔ／Ａｌ－ＣＬＭ的ｎ－Ｃ_８芳构化Ｃ_８芳烃收率与其结构的完整性、有线性、相关性。     

介孔固体超强酸催化剂的制备与结构表征

以累托土为基质 ,采用硅锆双组分交联剂和SO2 -4改性的方法 ,研制交联粘土介孔固体超强酸 (SO2 -4/SiZrR) ,借助XRD ,BET法 ,FT IR ,Hammett指示剂法 ,NH3 TPD ,Py IR和DTA等现代分析测试方法 ,表征其结构 .实验结果表明 :5 0 0℃焙烧后 ,SO2 -4/SiZrR的Hammett酸度函数Ho<-11 93 ,最可几孔径分布在 2 3nm左右 ,具有超强酸性和介孔结构 ;其超强酸中心属于L酸中心 ,是主要的催化活性中心 ;硅锆双组分交联柱能使交联粘土的热稳定性提高 ,以累托土为基质的交联粘土比以蒙脱土为基质的交联粘土热稳定性高     

三维贯穿大孔氧化铝的孔道改性、表征及转化机制

利用相分离技术制备了非晶三维贯穿大孔氧化铝初始材料,然后通过氨水水热改性处理,使其大孔形态发生了显著改变,孔壁边缘生长有尺寸为50-300 nm的片状聚集体,大孔尺寸由430 nm下降到250 nm,但仍然保持蠕虫状三维贯穿且空间分布均匀的特性。改性后的氧化铝材料经550℃焙烧转化为高结晶度γ氧化铝,比表面积达到331 m²/g,具有8.9 nm及250 nm两种集中的孔径分布,L酸度及抗压强度均有所提高。研究表明,无定形水合羟基铝离子聚合物与氨水发生再水合反应生成薄水铝石中间物,因此,可在较低的焙烧温度下转晶为γ态;大孔孔壁边缘的AlOOH晶粒受NH₄⁺模板诱导作用从里向外重排形成片状聚集体,从而改变了大孔的形态。     

二次炭化对PAN-ACF结构和性能的影响

ＰＡＮ－ＡＣＦ经二次炭化后,孔径结构及表面微结构均发生了很大的变化。本文讨论了在两个具有代表性的二次炭化温度下,ＡＣＦ的孔径结构以及表面微结构（表面性质）的变化。并初步讨论了结构变化机理。     

焙烧温度对TiO2柱撑膨润土结构、吸附及光催化性能的影响

采用酸性溶胶法合成了TiO2柱撑膨润土(Ti-Na-MMT), 采用XRD, FTIR, TG-DTA, BET和DRS等技术, 研究了焙烧温度对Ti-Na-MMT结构和处理偶氮染料废水性能的影响. 结果表明, 所制备的Ti-Na-MMT具有较好的热稳定性, 经773 K热处理后, 其结构仍基本保持不变. 随着焙烧温度的升高, 晶面间距逐渐减少. Ti-Na-MMT的比表面积、孔体积、孔径分布等特征以及TiO2晶粒粒径与煅烧温度有关; 在473 K下, 焙烧制备的Ti-Na-MMT BET的比表面积和最大孔容最大, 平均孔径和TiO2粒径最小; 随着焙烧温度的进一步升高, TiO2粒子发生团聚, 粒径变大, 从而Ti-Na-MMT的比表面积和最大孔容减小, 而其平均孔径呈增大趋势. DRS结果表明, 在473 K下焙烧制备的Ti-Na-MMT对光的吸收能力最强. 焙烧温度对Ti-Na-MMT的吸附性能和光催化活性的影响规律一致, 这表明吸附和光催化过程存在一定的协同作用. 473 K时制备的Ti-Na-MMT表现出的吸附和光催化活性均最强.     

Changes in density and surface tension of water in silica pores

 The density and surface tension of water in small pores of silicas have been investigated. These physical properties of water in the pores were calculated from a comparison of pore volumes and pore radii which were estimated from adsorption and desorption isotherms of nitrogen and water. Below a pore radius of about 5 nm both the density and the surface tension of water in the pores were smaller than those of the bulk liquid and decreased with a decrease in pore size. The density of water in the pores decreased with an increase in the concentration of surface hydroxyl groups. Similarly the surface tension of water in the pores is influenced by the surface hydroxyl groups. Anomalous changes in the density and surface tension of the water in the pores are attributed to the interaction of water molecules with surface hydroxyl groups and hydrogen-bond formation among water molecules. Received: 20 April 1999 Accepted in revised form: 17 November 1999     

Effects of thermal treatment on the surface properties of a wide pore silica gel

A mesoporous silica gel Davidson 59 was thermally treated in vacuo, in the temperature range 20–1000°C. Effects of thermal treatment on the water contents, nitrogen surface areas, pore structure and heats of immersion in water were investigated and discussed. The temperatures selected were 20, 110, 200, 290, 380, 480, 510 and 1000°C. These temperatures were found to cover all the various textural changes resulting from the heat effect.It could be shown that the heats of immersion in water depend primarily on the water content of the sample and are proportional, at least qualitatively to the number of hydroxyl groups on the surface and their availability for interaction with liquid water. The interesting result obtained is that a second factors is involved, namely the pore structure of the adsorbent. A qualitative parallelism exists between the normalized heat of immersion per unit area, and the average pore radius. Apparently the packing of water molecules in narrow pores leads to a decrease in the heat of immersion due to repulsion between the permanent dipoles of the molecules. In narrower pores, the heat of immersion in water is smaller than in wide pores.     

Proton Conduction in Nanopore-Controlled Silica Glasses

The proton conduction in the sol–gel-derived silica glasses was discussed to be related with the pore structure. The porous glasses with the pore size of 2 to 20 nm in diameter were prepared by the sol–gel method of Si-alkoxides. The proton conduction is promoted by the dissociation of proton from the hydroxyl bonds and the proton hopping through water molecules. The conductivities follow the Arrhenius equation and the activation energy decreases with increasing the logarithm of the product of proton and water concentration. The pore size plays an important role to absorb the water in pores, resulting into the determination of proton transfer. The glass having ～5 nm diameter is more appropriate for the fast proton-conduction. The preparation of pore-controlled glass films exhibiting high conductivity is also described.     

Adsorption of water in finite length carbon slit pore: comparison between computer simulation and experiment

The effects of surface dimensions and topology on the adsorption of water on a graphite surface at 298 K were investigated using the grand canonical Monte Carlo (GCMC) simulation. Regarding the surface topology, we specifically considered the functional group and its position on the surface. The hydroxyl group (OH) is used as a model for the functional group. For describing the interaction of water, we used the potential model proposed by Muller et al., and the simulated isotherms of water in slit pores are found to depend on the position and concentration of the functional group. The onset of adsorption shifts to lower pressure when the concentration of functional group increases or when the functional group is positioned at the center of the graphene surface. The configuration of a group of functional groups also affects the adsorption isotherm. In all cases investigated, we have found that the hysteresis loop always exists, and the loop size depends on the concentration of the functional group and its position. Finally, we tested the molecular model of water adsorption on a functional graphite pore against the experimental data of a commercial activated carbon. The agreement is found to be satisfactory when the model porous solid is composed of pores having width in the range between 10 and 20 A and functional groups positioned at the center of the graphitic wall.     

Enhanced Dye Adsorption by Microemulsion-Modified Calcined Diatomite (μE-CD)

This study attempted to improve the adsorption performance of calcined diatomite for the removal of colour from wastewaters through modification with microemulsions. The surface area, pH_ZPC, Fourier transform infrared (FTIR) of calcined diatomite and μE-CD were studied. It is found that an increase in the BET surface area, pH_ZPC and total pore volume after modification was obtained. A decrease in average pore volume was observed after modification. This suggests that the pore opening deceased to be in the micro- and meso-pore region hence the adsorption capacity for the modified adsorbent will be enhanced by reducing the escaping of dye molecules. The influence of concentration, pH and particle size on the adsorption capacities of methylene blue (MB), hydrolysed reactive black (RB) and hydrolysed reactive yellow (RY) was investigated. It was concluded from FTIR and pH analysis that the predominant mechanism of RY molecules onto μE-CD is by an electrostatic attraction between the carboxylate anion and the dye. In the case of MB and RB, the adsorption mechanism could be a combination of different mechanisms such as electrostatic attraction, capturing by microemulsion micelles in the pores of the calcined diatomite or the hydrophobic attraction. The adsorption capacities were higher than unmodified calcined diatomite. In the case of adsorption of MB molecules, a high adsorption capacity onto μE-CD was obtained.     

Preparation and characterization of silica aerogels from diatomite via ambient pressure drying

The silica aerogels were successfully fabricated under ambient pressure from diatomite. The influence of different dilution ratios of diatomite filtrate on physical properties of aerogels were studied. The microstructure, surface functional groups, thermal stability, morphology and mechanical properties of silica aerogels based on diatomite were investigated by BET adsorption, FT-IR, DTA-TG, FESEM, TEM, and nanoindentation methods. The results indicate that the filtrate diluted with distilled water in a proportion of 1: 2 could give silica aerogels in the largest size with highest transparency. The obtained aerogels with density of 0.122–0.203 g/m³ and specific surface area of 655.5–790.7 m²/g are crack free amorphous solids and exhibited a sponge-like structure. Moreover, the peak pore size resided at 9 nm. The initial aerogels were hydrophobic, when being heat-treated around 400°C, the aerogels were transformed into hydrophilic ones. The obtained aerogel has good mechanical properties.     

煤颗粒燃烧的孔隙特性研究

以实验为基础,系统研究了典型煤种燃烧时的颗粒孔隙过程。采用低温吸附法和电子显微图像计算机法测量了煤燃烧过程中的颗粒孔隙,获得了颗粒孔径分布和孔形分布等孔隙特性,建立了煤颗粒燃烧的微孔效应和亚微孔效应理论。     

Factors influencing the transport of short-chain alcohols through mesoporous gamma-alumina membranes

The pressure-driven transport of water, ethanol, and 1-propanol through supported gamma-alumina membranes with different pore diameters is reported. Water and alcohols had similar permeabilities when they were transported through gamma-alumina membranes with average pore diameters of 4.4 and 6.0 nm, and the permeability coefficient was found to be proportional to the square of pore size, in accordance with a viscous flow mechanism. For transport through membranes with an average diameter of 3.2 nm, the behavior of water was in accordance with the viscous flow mechanism, but the permeability of the membrane for ethanol and 1-propanol was much smaller than expected and could not be explained in terms of viscous flow. Although the low permeability of the membrane with 3.2 nm pores for ethanol and 1-propanol was partly due to the presence of small amounts of water in the alcohols, the permeability coefficients were still substantially smaller when water was absent. This intrinsic difference between water and alcohol may be due to differences in molecular size, chemisorption of alcohols on the oxide pore wall, which would lead to a reduction of the effective pore size, and/or a certain degree of translational ordering of the alcohol molecules inside the membrane pores, which leads to an effectively higher viscosity and, therefore, to a higher transport resistance.     

Polarity Control at Interfaces: Quantifying Pseudo‐solvent Effects in Nano‐confined Systems

Surface functionalization controls local environments and induces solvent‐like effects at liquid–solid interfaces. We explored structure–property relationships between organic groups bound to pore surfaces of mesoporous silica nanoparticles and Stokes shifts of the adsorbed solvatochromic dye Prodan. Correlating shifts of the dye on the surfaces with its shifts in solvents resulted in a local polarity scale for functionalized pores. The scale was validated by studying the effects of pore polarity on quenching of Nile Red fluorescence and on the vibronic band structure of pyrene. Measurements were done in aqueous suspensions of porous particles, proving that the dielectric properties in the pores are different from the bulk solvent. The precise control of pore polarity was used to enhance the catalytic activity of TEMPO in the aerobic oxidation of furfuryl alcohol in water. An inverse relationship was found between pore polarity and activity of TEMPO in the pores, demonstrating that controlling the local polarity around an active site allows modulating the activity of nanoconfined catalysts.