苯基化硅胶的物理结构和表面性质的研究

本文利用苯基三氯硅烷和硅胶表面羟基反应制备了苯基化硅胶。测定了苯基化硅胶的物理结构、水蒸气吸附等温线、润湿热、差热分析(DTA)和红外光谱(IR)。结果表明,所有苯基化硅胶的真密度(dT)、比表面(S)和比孔体积(V)均减少, 而表观密度(dA)增加, 但苯基化对不同硅胶的平均孔半径(r)有不同的影响; 苯基化硅胶对水蒸气吸附, 对水、苯和环己烷的润湿热均显著减少; 苯基化硅胶的热稳定性大于甲基化硅胶, 甲基化硅胶的表面是高度憎水的, 但苯基化硅胶的憎水性则很弱。     

酯化硅胶的物理结构和表面性质的研究

本文利用正庚醇或正辛醇与硅胶表面羟基反应制备了酯化硅胶。测定了酯化硅胶的物理结构、水蒸气吸附等温线、润湿热、差热分析和红外光谱。结果表明: (1)所有酯化硅胶的真密度(dT)、比表面(S)和比孔体积(V)均减少, 而有观密度(dA)增加, 但平均孔半径(r)变化不大; (2)酯化硅胶是憎水的, 其对水蒸气吸附, 以及对水和环己烷的润湿热均显著减少; (3)酯化硅胶的表面酯基在空气中于235-350℃破坏; (4)酯化反应是可逆的, 硅胶表面酯基在水中大约可水解41-47%。     

改性固体表面的吸附作用——甲基化硅胶的热稳定性和吸附性能

本文利用三甲基氯硅烷与硅胶表面羟基反应的方法制备了甲基化硅胶。测定了亲水硅胶和甲基化硅胶的热处理对其自四氯化碳中吸附乙酸的等温线的影响,并配合有热重分析(TG)和红外光谱(IR)的测定。结果表明:(1)甲基化后的硅胶对乙酸的吸附能力大大下降;(2)甲基化硅胶的热处理温度达500℃时吸附能力完全恢复到甲基化前的硅胶的水平,甲基化层明显开始破坏的温度为450℃;(3)甲基化硅胶高温处理后吸附能力得以恢复的主要原因是重新形成表面自由羟基。     

硅胶自环己烷中吸附环己酮和苯甲酸

用经不同温度处理的亲水硅胶(表面总羟基浓度不同)和甲基化硅胶(只含有缔合羟基或不同表面浓度的自由羟基的硅胶)为吸附剂, 测定了自环己烷中吸附环己酮和苯甲酸的等温线, 以及几种硅胶样品的红外光谱图, 探讨了表面自由羟基和缔合羟基在溶液吸附中的作用.     

凝胶渗透色谱多孔硅胶吸附问题的研究

本文以端基为羟基的聚二甲基硅氧烷为测试样品,甲苯为淋洗液,研究了凝胶色谱柱填料多孔硅胶的表面羟基含量等与吸附效应的关系。说明采用对硅胶进行表面处理和在淋洗液中加入吸附抑制剂的方法,不能避免吸附。建议采用端基封闭剂(如三甲基氯硅烷)处理聚合物的活性端基——羟基的方法,解决吸附问题。     

不同金属盐改性对硅胶的水蒸气吸附性能影响

用不同的金属盐溶液对中孔硅胶进行了改性,并进行了吸附水蒸气动力学实验.讨论了改性硅胶的吸湿性与离子半径之间的关系及吸附速率与平均孔径的关系.实验结果表明:(1) CaCl2,LiCl,MgCl2,ZnCl2改性硅胶,可以使硅胶的吸湿性能明显增加.其中用CaCl2改性的硅胶的吸湿量最大,其平衡吸湿量是未改性硅胶的3倍;(2) 用CaCl2溶液改性的中孔硅胶其吸湿量已接近微孔硅胶的吸湿量,但其吸附速率明显大于微孔硅胶的吸附速率;(3) 用CaCl2和ZnCl2的混合溶液改性硅胶对其吸湿量的提高没有明显效果.     

国产硅胶热稳定性的研究

本文研究直至940°,青岛细孔硅胶、粗孔硅胶、泰仁硅胶及英国细孔硅胶的热稳定性。并测定水、苯、环己烷蒸气在上述硅胶上的吸附等温线。所得结果如次: 1.经硝酸处理的纯硅胶的热稳定性较未经处理者大。后者于940°灼烧几失去所有的多孔性和活性。但相同条件下,粗孔硅胶之热稳定性较细孔硅胶大。 2.硅胶经600°以上的热处理,其吸水等温线和憎水性硅胶相同,低压下呈凹形。 3.无论细孔或粗孔硅胶,灼烧温度增高,比表面和微孔总体积减少,但硅胶之平均孔半径几不变。 4.较低温下,加热时间(直至四十四小时)不影响硅胶的吸附性能;但高温下(细孔硅胶在600°以上,粗孔硅胶在800°以上)吸附量随灼烧时间延长而减少。 5.硅胶表面经基脱水后再浸水可部分水合,但灼烧温度超过980°,则不能再水合。 6.苯蒸气在粗孔硅胶上的吸附-解吸等温线呈显著的滞后圈,而在细孔硅胶上则无。 7.据水蒸气吸附的结果,说明青岛细孔硅胶的孔性结构与英国B.D.H.细孔硅胶相似。     

囊泡状二氧化硅的合成及油气吸附性能

以正硅酸四甲酯(TMOS)为硅源,P123(EO20PO70EO20)为表面活性剂,在p H=6的磷酸缓冲体系中制备了囊泡状二氧化硅材料.利用乙醇萃取脱除模板剂P123,电镜观测结果表明所得二氧化硅具有大孔囊泡结构,N2吸附结果表明其具有高比表面积和大孔容.通过Boehm滴定法确定了硅羟基数量与吸水率呈正相关.用囊泡状二氧化硅材料与商业化活性炭(AC)和硅胶(SG)对水蒸气、正己烷和油气进行静态吸附.在自建的动态正己烷吸附装置上用对囊泡状二氧化硅材料和商业化AC和SG对正己烷进行动态吸附.吸附结果表明,囊泡状二氧化硅材料的静/动态吸附容量和稳定性都远高于商业化活性炭和硅胶.     

沸石表面有机金属化学ZSM-5外表面上

用气体分析及IR,NMR和元素分析等方法研究了真空系统中230和280℃下四丁基锗在ZSM-5沸石表面上的接枝反应,并对所得沸石的热稳定性和吸附性质进行了表征.与作者曾报道的在硅胶及丝光沸石上的反应类似,四丁基锗也能与ZSM-5沸石表面上的硅羟基发生缩合反应,在其外表面或孔口生成组成为(≡Si—O)     

硅酸及其盐的研究——ⅪⅤ.Ca~(2 ),Na~ 和K~ 与硅胶表面硅羟基的反应

硅胶,由于它的特殊表面性质,具有广泛的用途。在水溶液中它的表面为羟基所复盖,因此研究硅胶表面硅羟基的性质具有重要意义.本文用离子选择电极研究Ca~(2 ),Na~ 和K~ 在硅胶表面上的结合方式并求出反应的平衡常数. 在强碱性溶液中,硅胶与Ca~(2 )发生两种反应:一是硅胶表面硅羟基与Ca~(2 )作用;另一是硅胶溶解生成硅酸根离子,并与Ca~(2 )作用生成硅酸钙沉淀.但在中性和弱碱性条件下,硅胶与Ca~(2 )只发生表面反应,形成表面配合化合物,而不产生硅酸钙沉淀. 本实验表明:在pH=7～10,[Ca~(2 )]<10~(-2)M条件下,Ca~(2 )与硅胶表面反应时H_(rel)~ /Ca_c~(2 )≈2(Ca_c~(2 )为硅胶表面硅羟基上结合的Ca~(2 )量,H_(rel)~ 为Ca~(2 )在硅胶表面硅羟基上结合时释放出来的H~ 量).也就是说硅胶表面硅羟基结合一个Ca~(2 )就释放出两个H~ ,反应式可表示如下:     

The Thermal Stability and Adsorbability of the Mechylated Silica Gel

The methylated silica gel has been produced by the reaction between the surface silanol groups and Clsi(CH3)3 vapor.The adsorption isotherms of acetic acid from carbon tetrachloride onto silica gel and emthylated silica gel heated at various temperatures have been determined at 25℃,and the above mentioned silica gels have been studied by TC and IR.The results indicate:(1) The adsorption of acetic acid from carbon tetrachloried onto methylated silica gel decreased greatly,probably because the concentration of the free hydroxyl groups for methylated silica gel decreased greatly as the IR shows.(2) As the methylated surface was destroyed at 450℃,the adsorption ability was restored when the methylated silica gel treated at>500℃.(3) So long as the methylated silica gel was treated at high temperature,the adsorption ability could be restored owing to that surface free hydroxyl groups were reproduced.     

INVESTIGATION OF THE INTERACTIONS BETWEEN WATER AND MODIFIED SILICA GEL BY IGC AND TPD

In this work, the thermodynamic parameters for the adsorption of water vapor on untreated silica gel and silica gel treated with hygroscopic salts and silane coupling agent were determined by Inverse Gas Chromatography (IGC) in the infinite dilution region. The desorption activation energies of the water vapor on virgin and modified silica gels were estimated by using the Temperature Programmed Desorption (TPD) technique. The interactions between the water and the virgin and modified silica gels were discussed. Results showed that the thermodynamic parameters and desorption activation energy of water vapour on the silica gels increase with decreasing pore size and increasing the surface hydrophilic properties. The desorption activation energy of virgin and modified silica gels was found to increase with increasing the thermodynamic parameters. The larger the adsorption parameters and the desorption activation energy were, the interactions between water and virgin and modified silica gels were.     

Studies of surface modification of solids

The surface of silica was treated with trimethylchlorosilane (TMCS) and hexa-methyldisilazane (HMDS) respectively and the immersional heat into water, adsorption capacity for water vapor and infrared absorption spectra were measured. TMCS reacts with freely vibrating silanols while HMDS also reacts with other silanols. By treatment with silane, the silica surface is covered by the trimethylsilyl group, a maximum amount of which attains 1 meq/g (3 groups/nm²). As the amount of the trimethylsilyl group on silica increases, the immersional heat of silica into water decreases and attains a constant value of about 25 erg/cm², which is the typcial value for a hydrophobic surface. The interaction of the trimethylsilyl group with water is weak, therefore the adsorptive capacity for water vapor is lessened remarkably by treatment with silane.     

INVESTIGATION OF THE INTERACTIONS BETWEEN WATER AND MODIFIED SILICA GEL BY IGC AND TPD

1. INTRODUCTIONSilica gel is an amorphous inorganic polymer composed of siloxane (Si-O-Si) groups in the inner region and silanol (Si-OH) groups distributed on the surface [1]. Silanol groups can be easily functionalized by different chemical procedures. …     

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.     

Energetics of small molecule and water complexation in hydrophobic calixarene cavities

Calixarenes grafted on silica are energetically uniform hosts that bind aromatic guests with 1:1 stoichiometry, as shown by binding energies that depend upon the calixarene upper rim composition but not on their grafted surface density (0.02-0.23 nm(-2)). These materials are unique in maintaining a hydrophilic silica surface, as probed by H2O physisorption measurements, while possessing a high density of hydrophobic binding sites that are orthogonal to the silica surface below them. The covalently enforced cone-shaped cavities and complete accessibility of these rigidly grafted calixarenes allow the first unambiguous measurements of the thermodynamics of guest interaction with the same calixarene cavities in aqueous solution and vapor phase. Similar to adsorption into nonpolar protein cavities, adsorption into these hydrophobic cavities from aqueous solution is enthalpy-driven, which is in contrast to entropy-driven adsorption into water-soluble hydrophobic hosts such as beta cyclodextrin. The adsorption thermodynamics of several substituted aromatics from vapor and liquid are compared by (i) describing guest chemical potentials relative to pure guest, which removes differences among guests because of aqueous solvation and van der Waals contacts in the pure condensed phase, and (ii) passivating residual guest binding sites on exposed silica, titrated by water during adsorption from aqueous solution, using inorganic salts before vapor adsorption. Adsorption isotherms depend only upon the saturation vapor pressure of each guest, indicating that guest binding from aqueous or vapor media is controlled by van der Waals contacts with hydrophobic calixarene cavities acting as covalently assembled condensation nuclei, without apparent contributions from CH-pi or other directional interactions. These data also provide the first direct quantification of free energies for interactions of water with the calixarene cavity interior. The calixarene-water interface is stabilized by approximately 20 kJ/mol relative to the water-vapor interface, indicating that water significantly competes with the aromatic guests for adsorption at these ostensibly hydrophobic cavities. This result is useful for understanding models of water interactions with other concave hydrophobic surfaces, including those commonly observed within proteins.     

Hydrophobic Effects of o-Phenanthroline and 2,2′-Bipyridine on Adsorption of Metal(II) Ions onto Silica Gel Surface

The effects of o-phenanthroline and 2,2′-bipyridine on the adsorption of metal(II) (Fe, Co, Ni and Cu) ions onto silica gel surface have been studied. The adsorption is expressed in terms of the measured concentrations of both metal and ligand at equilibrium. Each adsorption of the four metal ions is increased with the presence of the ligands. In addition, adsorption increases slowly with pH at low pH values and then increases rapidly up to near the pK_a value of silica gel (≈6.5). The adsorption of each metal ion at low pH is increased with increased ligand concentration. However, at high pH the adsorptions of Fe(II) and Cu(II) are decreased with increased ligand concentration whereas the adsorptions of Co(II) and Ni(II) are always increased. At low pH values the ligand to metal ratio adsorbed on the silica gel surface is ca. 3:1 while at high pH values it is 1:1, 2:1, and 3:1, corresponding to the initial ligand to metal ion concentration ratio. The addition of ethanol to the phenanthroline-SiO₂ solution results in a decrease in the adsorption of phenanthroline. The effect of ethanol is also observed in the Fe(II)-phenanthroline-SiO₂ system. The behavior of the adsorption is interpreted qualitatively by hydrophobic expulsion, the formation of surface complexes, and electrostatic interaction. It is concluded that hydrophobic expulsion plays an important role in the adsorption of metal ions in the presence of hydrophobic ligands on silica gel surface.     

Dynamics and isotherms of water vapor sorption on mesoporous silica gels modified by different salts

The mesoporous silica gels impregnated with different metal salts were prepared and studied. The pore structure and specific surface area of adsorbents were evaluated using nitrogen adsorption. Then, the sorption isotherms and dynamics of water vapor were carried out at 303 K and different relative humidity (RH). The temperature programmed desorption experiments were conducted to estimate the activation energy (E _d) of water desorption on the silica gels. The results showed that the sorption capacity for water decreased with the increase of the ionic radius (except the calcium ion) and that CaCl₂ and LiCl were particularly suitable for use in modification of the mesoporous silica gel to improve their sorption rates and capacities for water vapor at the lower and medium RH (RH < 80%). The larger the average pore diameter and pore volume of the initial silica gels, higher the accrual rates of the water vapor sorption rate and capacity were after modification with hygroscopic salts. The activation energy of the water desorption on the mesoporous silica gel modified by CaCl₂ were much higher than that on the silica gel modified by LiCl, because the polarizability of the Ca²⁺ was higher than that of Li⁺.