PEI/SiO2复合型吸附材料对脲酸吸附特性的研究

通过γ-氯丙基三甲氧基硅烷的偶联, 将聚乙烯亚胺(PEI)偶合接枝在硅胶微粒表面, 制得了对脲酸有强吸附性能的复合型医用吸附材料PEI/SiO₂. 静态吸附实验结果表明, 凭借强烈的氢键相互作用, 硅胶表面的聚胺大分子PEI对脲酸的互变异构体三羟基嘌呤具有很强的吸附能力, 等温吸附满足Freundlich吸附方程, 饱和吸附量可达84.9 mg/g; 介质的pH值对吸附作用有很大的影响, 在中性溶液中(pH＝6～7), 复合吸附材料PEI/SiO₂对脲酸具有强吸附能力, 而在酸性与碱性溶液中吸附能力都较弱; 温度对吸附性能也有影响, 升高温度吸附量增大.     

亚氨二乙酸型复合材料IDAA-PGMA/SiO2对重金属及稀土离子的吸附行为与吸附热力学

将甲基丙烯酸缩水甘油酯(GMA)接枝于硅胶微粒表面,制得了接枝微粒PGMA/SiO₂; 使亚氨二乙酸(IDAA)与接枝PGMA的环氧基团发生开环反应, 从而将亚氨二乙酸基团引入接枝微粒表面, 制得了复合螯合微粒材料IDAA-PGMA/SiO₂. 本文研究了IDAA-PGMA/SiO₂对重金属及稀土离子的螯合吸附行为, 深入地研究了吸附机理与吸附热力学. 研究结果表明: 凭借亚氨二乙酸基团与重金属离子之间的静电作用与配位螯合作用的协同, 复合微粒材料IDAA-PGMA/SiO₂对重金属离子可产生强的螯合吸附作用, 尤其对Pb²⁺离子表现出很强的螯合吸附能力, 常温下吸附容量可达0.235 g·g^-1; IDAA-PGMA/SiO₂对重金属离子的吸附过程为一放热过程, 且为焓驱动的过程, 升高温度, 吸附容量降低; 对稀土离子的吸附过程则为熵驱动的过程; 在可抑制金属离子水解的pH范围内, 介质的pH值越高, IDAA-PGMA/SiO₂的螯合吸附能力越强; IDAA-PGMA/SiO₂对重金属离子的吸附容量远高于对稀土离子的吸附容量.     

复合型螯合吸附材料PEI/SiO2对铜离子吸附性能的研究

通过γ-氯丙基三甲氧基硅烷的媒介, 将聚乙烯亚胺(PEI)偶联接枝到硅胶微粒表面, 制备了复合型螯合吸附材料PEI/SiO2;研究了PEI/SiO2对Cu2 的吸附性能. 复合型螯合吸附材料PEI/SiO2对Cu2 具有强的螯合吸附能力;等温吸附数据符合Langmuir方程, 且吸附量随温度升高而增大;pH对吸附量有很大的影响, pH 7时, 吸附量最高.     

刷状结构的阳离子性接枝微粒QPDMAEMA/SiO2对牛血清白蛋白的吸附特性

以微米级硅胶微粒为基质, 通过接枝聚合和大分子反应, 制备了具有刷状结构的阳离子性接枝微粒, 深入研究了其对牛血清白蛋白(BSA)的强吸附能力、吸附机理和吸附热力学. 首先使含叔胺基团的单体甲基丙烯酸二甲基氨基乙酯(DMAEMA)在硅胶微粒表面发生接枝聚合, 制得接枝微粒PDMAEMA/SiO₂, 然后以氯乙胺为试剂, 使接枝大分子PDMAEMA链中的叔胺基团发生季铵化反应, 获得了具有刷状结构的阳离子聚电解质的功能接枝微粒QPDMAEMA/SiO₂. 测定了微粒QPDMAEMA/SiO₂的zeta 电位, 实施了对BSA的等温吸附实验, 考察了介质pH值、离子强度及温度对吸附作用的影响, 研究了吸附热力学. 研究结果表明, 功能接枝微粒QPDMAEMA/SiO₂ 比接枝微粒PDMAEMA/SiO₂ 具有更高的zeta 电位, 在静电相互作用驱动下, 微粒QPDMAEMA/SiO₂对BSA具有很强的吸附能力. 吸附容量随介质pH值的增大呈现先增大后减小的变化趋势,当pH值等于BSA的等电点(pI=4.7)时, 具有最高的吸附容量(高达112 mg·g^-1). 以等电点为界, 离子强度对吸附容量会产生完全相反的影响作用: 当介质pH值小于BSA的等电点时, 电解质浓度增大, 吸附容量增高; 当介质pH值等于BSA的等电点时, 吸附容量几乎不随电解质的浓度发生变化. 吸附过程熵值减小而且放出热量,是一个焓驱动的吸附过程.     

磁性Fe3O4@SiO2@ZrO2对水中磷酸盐的吸附研究

合成了以Fe₃O₄为核,以SiO₂为壳的磁性纳米微粒（Fe₃O₄@SiO₂）,并采用沉淀沉积法将ZrO₂包覆到材料表面。通过XRD、TEM、XPS和N₂吸附/脱附等手段对材料进行表征,结果表明材料Fe₃O₄@SiO₂@ZrO₂上沉积了氧化锆纳米颗粒,具有超顺磁性,可在外加磁场作用下实现从水中快速分离。同时系统研究了材料对水中磷酸盐的吸附行为,结果表明沉积ZrO₂使得材料对磷酸盐表现出良好的吸附性能,并且随着沉积量的增大吸附量增加。吸附等温线可用Freundlich方程拟合。吸附动力学可用拟二级动力学模型拟合,吸附速率随初始浓度增加而减缓。磷酸盐吸附量随溶液pH值的增大而减小,但几乎不受离子强度影响。     

活性炭的孔径分布对CH4和CO2的吸附性能的影响

采用不同炭化温度和活化温度,以椰壳作为前驱体制备了系列结构性能相同,表面吸附基团相似,不同孔结构的活性炭。分别采用密度函数理论(DFT)吸附法和BJH估算了系列活性炭的孔径分布。结果表明,随炭化温度和活化温度的升高系列活性炭中微孔量先增加后减少。当炭化温度为700 ℃,活化温度为800 ℃时,制备的活性炭微孔量达到最大。随炭化温度和活化温度的升高,系列活性炭的中孔依次增加。考查了CH₄,CO₂在系列活性炭上的吸附性能。结果表明该系列活性炭对CO₂有很强的吸附能力,在常温常压下对CO₂的吸附量均高于1.0 mmol·g^-1;系列活性炭对CH₄的吸附能力有较大的差异,在对CO₂具有最大吸附量的活性炭上对CH₄具有最小的吸附量。采用变压吸附法测试了该系列活性炭在25 ℃时对n_CH4∶n_CO2=9∶1的混合气体的分离性能。结果表明炭化温度为700 ℃,活化温度为800 ℃时制备的活性炭对CH₄-CO₂混合气具有最好的分离效果,是变压吸附分离CH₄,CO₂混合气的优异吸附剂。     

SiO2-CeO2复合氧化物的制备及抛光性能

采用正硅酸乙酯溶胶-凝胶法制备纳米SiO₂，并与氯化铈溶液混合，用氨水沉淀法制备了SiO₂-CeO₂复合氧化物。利用XRD、SEM等手段对其物相类型、外观形貌、颗粒大小、表面电位等物理性能进行了表征，测定了它们对3种光学玻璃的抛光速率。结果表明：合成复合氧化物具有立方萤石型结构，由Sherrer方程计算的晶粒D_XRD(200)小于100 nm甚至10 nm。随着SiO₂复配量的增加和煅烧温度的降低，晶粒度减小，比表面增大；激光粒度分析仪测定的中位粒径D₅₀在2～3 μm之间，且随SiO₂复配量的增加呈增大趋势，但随煅烧温度的变化在800 ℃时出现极小值，而此时的ζ电位的负值最大，对3种玻璃的抛光速率也最大。证明抛光速率与表面电位及相应的悬浮性、颗粒大小有直接关系。随着SiO₂复配量的增加，复合氧化物的ζ电位负值及对3种玻璃的抛光速率均增大。因此，在CeO₂中复配SiO₂是提高抛光速率的有效方法，此时，最佳的煅烧温度为800 ℃。     

ZnCr双金属层状材料对废水中酸性红14的吸附性能

采用共沉淀法制备性能优异的层状材料锌铬水滑石(Zn_xCr-LDHs, x=2, 3, 4), 并探究各种因素对吸附酸性红14(AR14)的影响。XRD、ICP、FTIR及BET表征结果表明:合成的Zn_xCr-LDHs晶型良好且稳定, 具备介孔结构。实验结果表明:最佳吸附剂为Zn₃Cr-LDHs, 比表面积为101 m²·g^-1, 对AR14的最大吸附容量为484.63 mg·g^-1。同时, 降低溶液pH值和提高溶液温度均可促进AR14的吸附。该吸附过程分别符合准二级动力学模型和Freundlich等温吸附模型。结合Materials Studio 5.5软件模拟, 推测该吸附机理主要以表面吸附为主, -SO₃^-基团是反应点。     

ZnCr双金属层状材料对废水中酸性红14的吸附性能

采用共沉淀法制备性能优异的层状材料锌铬水滑石(Zn_xCr-LDHs, x=2, 3, 4), 并探究各种因素对吸附酸性红14(AR14)的影响。XRD、ICP、FTIR及BET表征结果表明：合成的Zn_xCr-LDHs晶型良好且稳定, 具备介孔结构。实验结果表明：最佳吸附剂为Zn₃Cr-LDHs, 比表面积为101 m²·g^-1, 对AR14的最大吸附容量为484.63 mg·g^-1。同时, 降低溶液pH值和提高溶液温度均可促进AR14的吸附。该吸附过程分别符合准二级动力学模型和Freundlich等温吸附模型。结合Materials Studio 5.5软件模拟, 推测该吸附机理主要以表面吸附为主, -SO₃^-基团是反应点。     

Ni/SiO2-Al2O3催化乙酰丙酸加氢制γ-戊内酯

采用溶胶-凝胶法制备了一系列不同Al₂O₃含量的SiO₂-Al₂O₃复合氧化物,以该系列复合氧化物为载体,采用等体积浸渍法制备了Ni负载量15%（重量百分比）的催化剂,用于催化乙酰丙酸加氢制γ-戊内酯.采用N₂物理吸附、X射线衍射（XRD）、H₂程序升温还原（H₂-TPR）、H₂程序升温脱附（H₂-TPD）、NH₃程序升温脱附（NH₃-TPD）和吡啶吸附红外（Py-IR）等手段对催化剂进行了表征.结果表明,不同载体催化剂的活性组分分散度及表面酸性质存在明显差异,显著影响了催化剂吸附、活化H₂与C=O键的能力,进而影响了催化剂的乙酰丙酸加氢活性.其中,Ni/SiO₂-Al₂O₃催化剂上的L酸中心能够促进C=O键的吸附、活化,与金属Ni上的H₂吸附活性位协同作用,大大提高了乙酰丙酸加氢活性.因此,具有最多L酸中心和丰富H₂吸附活性位的Ni/SiO₂-8Al₂O₃催化剂表现出最高的乙酰丙酸加氢活性,在180℃、4 MPa氢气压力下,乙酰丙酸转化率达到90.5%,目标产物γ-戊内酯选择性为100%.     

Preparation of Iminoacetic Acid-type Composite Chelating Material IAA-PEI/SiO2 and Preliminary Studies on Chelating Adsorption Property towards Heavy Metal Ions

Polyamine polyethyleneimine (PEI) was first grafted on the surfaces of micro-sized silica gel particles in the manner of the coupling graft (the manner of “grafting to”), forming the grafting particles PEI/SiO₂. Subsequently, via a polymer reaction, the nucleophilic substitution reaction between the primary and secondary amino groups of the grafted PEI macromolecule and chloroactic acid (CAA), iminoacetic acid groups were bonded onto the grafted PEI chains, and an iminoacetic acid (IAA)-type composite chelating material, IAA-PEI/SiO₂, was formed. In this work, the preparation process of IAA-PEI/SiO₂ particles was mainly researched, and the effects of the main factors on the polymer reaction, i.e., the nucleophilic substitution reaction, were examined emphatically. The adsorption behavior of IAA-PEI/SiO₂ particles towards several kinds of heavy metal ions was preliminarily evaluated. The experiments results show that it is feasible to introduce IAA groups onto PEI/SiO₂ particles via the substitution reaction between CAA and the amino groups of the grafted PEI. The reaction rate is affected greatly by the feed ratio of the amino group of PEI to CAA, so the substitution reaction between CAA and the amino groups of the grafted PEI is a bimolecular nucleophilic substitution reaction (S_N2). The reaction temperature and the used amount of acid-acceptor NaHCO₃ affect the bonding rate of IAA groups greatly. The fitting temperature was 60°C, and 1:1 of the molar ratio of NaHCO₃ to CAA was an appropriate amount of acid-acceptor NaHCO₃. Under the above optimal reaction conditions and with 3:1 molar ratio of amino group of PEI to CAA, 72% of the IAA group bonding rate (it is based on the hydrogen atoms in the primary and secondary amino groups of the grafted PEI) in 8 h can be reached. The composite chelating material IAA-PEI/SiO₂ possesses a strong chelating adsorption ability for heavy metal ions because of the increase of the ligands and formation of stable five-membered chelate rings.     

Interactions of PEI (polyethylenimine)–silica particles with citric acid in dispersions

Adsorbed polyethylenimine (PEI) of M _w 1,800 and 70,000 on silica (SiO₂) dispersions produced flocculated slurry in the pH range of 5 to 12. Adsorbed citrate widens this flocculated pH regime. It also increases the strength of the interparticle attractive force or the yield stress over the pH range of between 3 and 8. The stronger attractive force is due to particle bridging by the citrate anions bonding with positively charge sites of the adsorbed PEI layer of the interacting particles at the closest point of interaction. The higher M _w PEI being more strongly attached to the silica particle produced a stronger attractive interparticle force with adsorbed citrate anions. Via charge balance calculation using contributions from SiO₂, PEI, and citrate, the pH of zero charge was found to correspond to the pH of zero zeta potential for PEI of M _w 70,000. This suggests 100% adsorption of PEI and citrate on SiO₂. The bridging interaction was confirmed by a linear relationship between yield stress and the square of the limiting citrate charge content. Adsorbed citrate was found for the first time to play the role of a bridging agent, a result of the positive charges being located on a more flexible adsorbed layer rather than being fixed to a rigid surface.     

Photocontrolled extraction of uric acid from biological samples based on photoresponsive surface molecularly imprinted polymer microspheres

We aim to develop novel photoresponsive surface molecularly imprinted polymer (SIMP) microspheres, an SiO₂‐SIMP, for the photocontrolled extraction of uric acid from biological samples. The SiO₂‐SMIP was prepared on silica microspheres by surface polymerization and characterized by using scanning electron microscopy, transmission electron microscopy, FTIR spectroscopy, thermogravimetric analysis, nitrogen adsorption–desorption analysis, and UV‐visible spectroscopy. The SiO₂‐SMIP microspheres showed a photocontrolled uptake and release of uric acid in NaH₂PO₄ buffer upon alternate irradiation at 365 and 440 nm. The SiO₂‐SMIP microspheres were able to photocontrollably extract uric acid from complicated biological samples for concentration analysis with no significant interference encountered and it exhibited very good recognition ability and fast binding kinetics toward uric acid.     

Adsorption and desorption behavior of tetravalent zirconium onto a silica-based macroporous TODGA adsorbent in HNO3 solution

To understand the separation behavior of Zr(IV) in the partitioning process for high level liquid waste, a silica-based macroporous adsorbent (TODGA/SiO₂-P) was prepared by impregnating N,N,N′,N′-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) into a macroporous silica/polymer composite particles support (SiO₂-P). Adsorption and desorption behavior of Zr(IV) from nitric acid solution onto silica-based TODGA/SiO₂-P adsorbent were investigated by batch experiment. It was found that TODGA/SiO₂-P showed strong adsorption affinity to Zr(IV) and this adsorption process reached equilibrium state around 6 h at 298 K. Meanwhile, HNO₃ concentration had no significant effect on the adsorption of Zr(IV) above 1 M. From calculated thermodynamic parameters, this adsorption process could occur spontaneously at the given temperature and was confirmed to be an exothermic reaction. This adsorption process could be expressed by Langmuir monomolecular layer adsorption mode and the maximum adsorption capacity were determined to be 0.283 and 0.512 mmol/g for Zr(IV) at 298 and 323 K, respectively. In addition, more than 90 % of Zr(IV) adsorbed onto adsorbent could be desorbed with 0.01 M diethylenetriamine pentaacetic acid solution within 24 h at 298 K.     

Preparation and characterization of CuO/SiO2 and NiO/SiO2 with bimodal pore structure by sol-gel method

CuO/SiO₂ and NiO/SiO₂ with bimodal pore structure were prepared by sol-gel reactions of Tetra-methoxysilane (TMOS) and the respective metal nitrate in the presence of poly (ethylene oxide) (PEO) with an average molecular weight of 10 000 and the catalyst of acetic acid. In this process, the interconnected macroporous morphology was formed when transitional structures of spinodal decomposition were frozen by the sol-gel transition of silica. The addition of copper and nickel into the silica-PEO system had a negligible effect on the morphology formation. In gel formation, it was found that NiO crystalline sizes in the samples increased with decreasing Si/Ni molar ratio. It was considered that PEO interacted with both silica and nickel cations. In the CuO/SiO₂ with the presence of PEO_, CuO crystalline sizes were larger than those of NiO/SiO_2. It was considered that there was no obvious interaction between the Cu cation and PEO, most of the copper ions in wet silica gel were present in the outer solution. They easily aggregated as copper salts in the drying process of wet gel and decomposed into CuO particles in heating. While in the CuO/SiO₂ with the absence of PEO, the Cu was selectively entrapped as small particles in the gel skeleton due to the interaction between Cu aqua complex and silica gel network.     

In-vivo fluorescence imaging technique using colloid solution of multiple quantum dots/silica/poly(ethylene glycol) nanoparticles

This paper describes a method for producing silica particles containing multiple quantum dots (QD/SiO₂), a method for surface-modifying the particles with poly(ethylene glycol) (QD/SiO₂/PEG), and an in vivo fluorescence imaging technique using colloid solution of the QD/SiO₂/PEG particles. The QDs used were ZnS-coated CdSe_xTe_1?x nanoparticles surface-modified with carboxyl groups, and had an average size of 10.3 ± 2.1 nm. The QD/SiO₂ particles were fabricated by performing sol–gel reaction of tetraethyl orthosilicate using NaOH as a catalyst in the presence of the QDs. The produced particles formed core–shell structure composed of multiple QDs and silica shell, and had an average size of 50.2 ± 17.9 nm. Surface-modification of the QD/SiO₂ particles with PEG, or PEGylation of the particle surface, was performed by using methoxy polyethylene glycol silane. Fluorescence of QD colloid solution was not quenched even through the silica-coating and the PEGylation. Tissues of a mouse could be imaged by injecting the concentrated colloid solution into it and measuring fluorescence intensity emitted from the tissues.     

Comparison of adsorption affinity of polyacrylic acid for surfaces of mixed silica–alumina

The influence of solution pH (in the range 3–9) on the adsorption of polyacrylic acid (PAA) on the mixed silica–alumina surface (SA-3: SiO₂ 97 %–Al₂O₃ 3 % and SA-96: SiO₂ 4 %–Al₂O₃ 96 %) was investigated. The following methods were applied in experiments: spectrophotometry, viscosimetry, potentiometric titration, and microelectrophoresis, which enable determination of adsorbed amount of the polymer, thickness of its adsorption layers, surface charge density, and zeta potential of solid particles in the presence and absence of PAA, respectively. The obtained results indicate that rise of solution pH causes the decrease of PAA adsorption and the increase of its adsorption layer thickness on surfaces of both solids. Moreover, significantly higher adsorption of polyacrylic acid was obtained on the SA-96 surface. This is a result of more favorable electrostatic interactions occurring between the adsorbing polymer chains and the SA-96 surface and formation of a greater number of adsorbate-adsorbent connections through hydrogen bridges.     

Changes of zeta potential and particles size of silica caused by DPPC adsorption and enzyme phospholipase A2 presence

The changes in electrokinetic properties of silica suspensions in the presence of 1,2-dipalmitoyl-sn-glycero-3-phospshocholine (DPPC) were investigated via zeta potential, mean diameter and transmittance determinations. Silica particles were precovered with monolayer (ML) or bilayer (BL) of the phospholopid from chloroform solution (SiO₂/DPPC) or covered by DPPC adsorption from aqueous solution (SiO₂+DPPC). The zeta potential and mean diameter of SiO₂/DPPC suspension were measured as a function of NaCl concentration and due to the phospholipase A₂(PLA₂) action in 10^?3 M NaCl solution and buffer Tris at pH=8 and 9. It was found that the DPPC adsorption onto silica surface decreases its the zeta potential, however the suspensions were stable during the experiment time, probably because of steric stabilization. During PLA₂ enzyme action the changes in zeta potential were observed, which were caused by the hydrolysis products, especially palmitic acid molecules, which also had influence on the stability of these systems.     

Preparation of raspberry-like PMMA/SiO2 nanocomposite particles

Water-borne raspberry-like PMMA/SiO₂ nanocom-posite particles were prepared via free radical copolymerization of methyl methacrylate (MMA) with 1-vinylimidazole (1-VID) in the presence of ultrafine aqueous silica sols. The acid-base interaction between hydroxyl groups (acidic) of silica surfaces and amino groups (basic) of 1-VID was strong enough for promoting the formation of long-standing stable PMMA/SiO₂ nanocomposite particles when 10 mol% or more 1-VID as auxiliary monomer was used. The average particle sizes and the silica contents of the nanocomposite particles were in the ranges from 120–330 nm and 15%–20%, respectively. TEM and SEM observations indicated a raspberry-like morphology of the obtained nanocomposite particles. __________ Translated from Chemical Journal of Chinese Universities, 2005, 26(7) (in Chinese)