改性硅胶负载磷钨酸催化合成柠檬酸三丁酯

用3-氨丙基三甲氧基硅烷对硅胶进行改性,然后负载磷钨酸,制备了改性硅胶负载磷钨酸催化剂,并进行红外FT-IR分析以及热重分析。考察了改性硅胶与活化硅胶对磷钨酸的负载量以及它们催化合成柠檬酸三丁酯(TBC)的重复利用效果,结果表明:改性硅胶与活化硅胶的最大负载量分别为44.7%和16.8%,将此两种催化剂重复使用三次,平均产率分别91.1%和23.7%。设计了三因素三水平的正交试验,得到最佳反应条件:改性硅胶负载磷钨酸催化剂2.5g(负载量为43.5%),反应4h,(n柠檬酸:n正丁醇)为1:4,反应温度为140℃。产率为92.1%。     

硅胶的表面硫醇化改性及对水溶液中罗丹明B的固载

运用γ-巯丙基三乙氧基硅烷对硅胶表面硫醇化修饰改性,红外及拉曼光谱分析表明硅胶的表面硫醇化借助硅胶表面羟基与γ-巯丙基二乙氧基硅烷间的化学键联实现。实验条件下改性硅胶对水体罗丹明B的吸附性能明显提升,改性硅胶表面罗丹明B的吸附动力学符合准二级动力学模型,吸附等温线服从Langmuir等温线规律,由等温吸附计算得到的热力学函数变化表明吸附系自发、放热过程。吸附动力学、热力学及光谱表征均表明改性硅胶上罗丹明B的吸附主要为其在改性硅胶表面借助电价和共价键联的化学吸附。     

用硅烷化处理改性硅胶分离富集痕量元素

将硅胶用二氯二甲基硅烷处理后，能降低硅胶对极性物质的吸附，增加其对非极性物质或弱极性物质如５－Ｂｒ－ＰＡＤＡＰ等大多数螯合剂的吸附，同时使改性硅胶适应的ＰＨ范围扩宽，对金属离子的净化学吸附增大，使用寿命增加。     

硅胶的表面硫醇化改性及对水溶液中罗丹明B的固载

运用γ-巯丙基三乙氧基硅烷对硅胶表面硫醇化修饰改性, 红外及拉曼光谱分析表明硅胶的表面硫醇化借助硅胶表面羟基与γ-巯丙基二乙氧基硅烷间的化学键联实现。实验条件下改性硅胶对水体罗丹明B的吸附性能明显提升, 改性硅胶表面罗丹明B的吸附动力学符合准二级动力学模型, 吸附等温线服从Langmuir等温线规律, 由等温吸附计算得到的热力学函数变化表明吸附系自发、放热过程。吸附动力学、热力学及光谱表征均表明改性硅胶上罗丹明B的吸附主要为其在改性硅胶表面借助电价和共价键联的化学吸附。     

ZSM-5高硅分子筛硅烷化疏水改性的研究

以甲苯为溶剂,正辛基三乙氧基硅烷(OTS)为改性剂,进行了ZSM-5高硅分子筛疏水改性研究。通过傅立叶红外(FT-IR)、X射线粉末衍射(XRD)、N2吸附-解吸附、静态水接触角、水与正己烷的静态吸附,以及水热稳定性试验等测试了改性前后样品结构与性能。结果表明,通过硅烷化改性在ZSM-5上接枝了-Si(CH2)7CH3基团,并实现了超疏水性。当0.8g ZSM-5使用0.24g改性剂时,改性后分子筛的接触角达152°,水吸附量下降了1.49%,比表面积、孔容、孔径分别减小了62.7m2/g、0.0329cm3/g、0.42nm,孔道长程有序性有所降低,且具有较高的水热稳定性。     

二组分气体在固体上吸附的研究（Ⅲ）：丙酮—正己烷,甲苯—正己…

测定了丙酮－正己烷，甲苯－正己烷，苯－正己烷，正戊烷－正己烷４个二组分气体在硅烷化硅胶上的吸附等温线，并测定了单组分体吸附等温线，实验结果表明，二组分气体在硅烷化硅胶上的竞争吸附的强弱可以通过其且分气体在硅烷化硅胶上第一层吸附热Ｑ１数值的大小预测。     

含酰胺结构的硅胶键载二乙烯三胺螯合微粒的合成及其吸附性能

硅胶与γ-氨丙基三甲氧基硅烷(AFFS)进行硅烷化反应,然后与丙烯酸甲酯(MA)进行迈克尔加成反应引入酯基,最后与二乙烯三胺(DETA)反应生成氨基结尾的酰胺基硅胶,其结构经红外光谱、元素分析,热重分析(TG)和X射线衍射仪(XRD)表征.元素分析表明,Ⅰ、Ⅱ、Ⅲ的氨基含量分别为1.992mmol/g、1.699mmol/g、3.416mmol/g.研究了该硅胶微粒对重金属离子Ag 、Hg2 、Cu2 的吸附容量、吸附动力学、等温吸附过程等静态吸附性能.结果表明,对3种离子的吸附量分别为0.71mmol/g、0.46mmol/g,0.35mmol/g.动力学吸附过程为液膜扩散控制,吸附过程符合Langmuir或Freundlich模型.     

以硅胶为载体通过3—胺丙基三甲氧基硅烷偶联剂制备季铵盐类水溶性杀菌剂的方法研究（Ⅰ）

采用硅胶作为制备水溶性季铵盐杀菌剂的原料,以γ-胺丙基三甲氧基硅作为联接硅胶和杀菌活性官能团的偶联剂,在硅胶上键合γ－胺基三甲氧基硅烷的最佳反应条件为：使用二甲苯作反应溶剂,80℃反应6h以上,硅烷与硅胶的重量比为1：1左右,固载硅烷的硅胶叔胺化条件为：使用甲苯和二甲苯作反应溶剂,100℃反应4h以上,甲酸与甲醛的体积比为1：1,使用所研制的中间体制备的水下溶性杀剂量用在2mg/ml时杀菌率达到97％。     

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.     

果胶改性硅胶复合材料的制备及其对亚甲基蓝的吸附性能

以废弃柚子皮中提取的果胶改性硅胶表面,制备出新型的果胶改性硅胶复合材料——P-硅胶,研究了P-硅胶对水中亚甲基蓝染料的吸附性能。利用红外光谱对材料进行表征,并通过分光光度法考察了用量、p H值、吸附时间、温度及实际水样对P-硅胶吸附亚甲基蓝性能的影响。硅胶经果胶改性后,其对亚甲基蓝的吸附容量由31.6 mg·g-1增至41.7 mg·g-1,吸附性能明显提高;P-硅胶对亚甲基蓝的吸附容量随着p H值、温度的升高而增大,碱性条件有利于吸附。结果显示:当p H 7.0,P-硅胶用量为5 mg,吸附时间为2 h,吸附温度为50℃时,制备出的P-硅胶对亚甲基蓝染料溶液的吸附容量最大可达59.2 mg·g-1。动力学研究显示,P-硅胶对亚甲基蓝的吸附能够在120 min内迅速达平衡,吸附行为符合准二级动力学方程,表明该吸附过程以化学吸附为主。吸附等温线研究表明,与Freundlich模型相比,实验数据拟合更符合Langmuir吸附等温模型。P-硅胶对环境水样中亚甲基蓝的去除率可达90%以上。     

Apatite-Silica Gel Composite Materials Prepared by a New Alternate Soaking Process

Novel apatite/silica composite materials were synthesized by modifying the surface of silica gel beads or plates with apatite. An alternate soaking process, which involves alternate soaking in a CaCl₂/tris-HCl aqueous solution (pH 7.4) and a Na₂HPO₄ aqueous solution, was utilized to prepare a composite of silica gel and apatite. The characteristics of apatite formed on the surface of silica gel have been studied using X-ray diffraction, Fourier-transform infrared spectrophotometry (FT-IR) and scanning electron microscopy (SEM). Data clearly showed surface modification of silica with the crystalline apatite. Pore volume and specific total surface area, which were measured using nitrogen gas adsorption apparatus, were decreased after apatite deposition on the surface of silica gel beads, whereas the external surface area was increased drastically. The alternate soaking process made it possible to prepare apatite/silica gel composites in a remarkably short period of time, i.e. several hours.     

Thermal decomposition of immobilized compounds for the generation of gaseous standard mixtures containing ammonia and amines

The thermal decomposition of phthalamic acid derivatives chemically bonded to the surface of silica gel was examined and utilized for the generation of single-component gaseous standard mixtures of ammonia, methylamine, diethylamine and triethylamine. The conditions of the thermal decomposition (temperature, time, diluent gas flow rate) were optimized to ensure complete liberation and rapid elution of the compounds from the bed of modified silica gel. The total amounts of these four compounds that can be released from unit mass of the modified silica gel are in the range of several mg.     

修饰硅胶表面印迹牛血红蛋白及其识别性能的研究

本文选用马来酸酐修饰后的硅胶作为载体,丙烯酰胺为功能单体,N,N’-亚甲基双丙烯酰胺为交联剂,牛血红蛋白为模板分子,采用氧化还原悬浮聚合法,合成了具有选择性识别的牛血红蛋白分子印迹聚合物。并用红外光谱(IR)、扫描电子显微镜(SEM)对聚合物进行了表征,结果表明载体表面成功接枝了分子印迹聚合物薄层。同时,选择性吸附实验表明分子印迹聚合物的具有良好的识别性能,能成功的实现水溶液中牛血红蛋白的富集。     

Synthesis and Characterization of Microporous Silica Prepared with Sodium Silicate and Organosilane Compounds

Microporous silica gels were prepared in the pH range of 3–4 using sodium silicate as a silica source. Surface polarity of these gels was modified by grafting hydrophobic groups into the silica gel matrix with the help of hydrophilic solvents (acetone, acetonitrile, ethanol and methanol) and alkoxysilane compounds containing nonhydrolyzable alkyl groups. The porous framework and hydrophobicity of the silica gels were evaluated using nitrogen adsorption/desorption and water adsorption measurement techniques. All the measured isotherms were found to be type I which is indicative of microporosity. The surface area and microporosity of these samples were estimated by analyzing the measured nitrogen adsorption/desorption data using BET, Langmuir and Dubinin-Radushkevich (D-R) adsorption isotherms. The micropore size distribution was determined from their nitrogen adsorption isotherms using the slit-pore model of the Horvath-Kawazoe equation. Silica gels with high surface area (over 500 m²/g) as well as high microporosity (over 0.2 cc/g) were obtained at gelation pH of 3.50 from the water-solvent system.     

The Adsorption of Methanol Vapors on Silica Gel Si-100 and Its Surface Containing Different Concentrations of Chemically Bonded Fluoride Ions

Synthesis of two types Si-100 silica gel with different concentrations of chemically bonded surface fluoride ions (2 and 4 μmol m⁻² ) was performed. Using gravimetric methods, adsorption isotherms of methanol as a function of its pressure in gas phase were measured for these adsorbents. It was found the strong surface deactivation of silica gel in relation to methanol with the increase of bonded fluoride ions concentration. This revised version was published online in August 2006 with corrections to the Cover Date.     

A Gas Chromatographic Analysis of Light Hydrocarbons on a Column Packed with Modified Silica Gel

IntroductionAnalysis of light hydrocarbons achieved by gas-solid chromatography is important in petrochemical industry, environmental protection and some other areas. A variety of columns have been used, including conventional packed column1, Al2O3 and graphitized carbon black PLOT column2, 3 and silica gel SCOT column4. Al2O3 PLOT column is excellent for the analysis of light hydrocarbons. Conventional packed column also has its own advantages, such as easy column preparation, resistanc…     

热处理对憎水硅胶吸附水蒸气的影响

用甲基氯硅烷蒸气或溶液处理硅胶,均可制成憎水硅胶。关于憎水硅胶的吸附性能和热稳定性的研究,文献中时有报道。本文主要探讨以下3个问题:(1)在水蒸气吸附中,硅胶表面自由羟基和缔合羟基究竟哪种起主要作用;(2)从吸附水蒸气等数据讨论硅胶表面有机基团—OSi(CH_3)_3的热稳定性;(3)用二甲基二氯硅烷(DMCS)和三甲基氯硅烷(TMCS)处理的憎水硅胶,哪种硅胶的热稳定性较高。这些基本问题,不仅具有学术意义,对研究氧化物表面改性也有参考价值。     

Effects of the degree of surface modification on the rheological responses of precipitated silica suspensions in benzyl alcohol

Two types of precipitated silica powders modified by poly (dimethylsiloxane) (PDMS) were suspended in benzyl alcohol and their rheological properties were investigated as a function of silica volume fraction, φ. The suspensions were classified into sol, pre-gel, and gel states based on the increase in φ. An increase in the degree of surface modification by PDMS caused gelation at higher φ. Plots of apparent shear viscosity against shear rate in the sol and pre-gel states of highly modified silica suspensions showed weak shear thickening behavior, while the same plots for silica suspensions with a low modification level exhibited shear thinning behavior. The dynamic moduli of hydrophobic suspensions in the pre-gel and gel states were dependent on the surface modification: the storage modulus G′ was larger than the loss modulus G″ in the linear region and these moduli increased with increasing φ, irrespective of the silica powder. The linear region of the φ range for the precipitated silica suspensions was wider than that for the fumed silica powders modified by PDMS suspended in benzyl alcohol, while the G′ value in the linear region for the precipitated silica suspensions was less than those for the fumed silica suspensions.     

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.