表面硅烷化铜箔的电化学腐蚀与防护研究

用γ-氨丙基三甲氧基硅烷(γ-APS)溶液对铜箔表面硅烷化处理,采用动电位极化和电化学交流阻抗研究不同pH的γ-氨丙基三甲氧基硅烷溶液自组装铜箔电极在0.1 mol.L^-1NaCl溶液的腐蚀防护效果,采用扫描电子显微镜观察γ-氨丙基三甲氧基硅烷自组装膜的表面形貌.结果表明,γ-氨丙基三甲氧基硅烷自组装铜箔有较好的腐蚀防护效果,其中pH=7的γ-氨丙基三甲氧基硅烷溶液自组装膜的抗腐蚀效果最佳.     

多孔硅球的活化和硅烷化

经甲烷磺酸水溶液活化处理的多孔硅球与γ－氨丙基三乙氧基硅烷的反应能力较浓盐酶活化方法有显著提高；多孔硅球与γ－氨丙基三乙氧基硅烷的反应由两个步骤组成，即先室温反应然后再回流；用改进方法制备的氨丙基硅烷化多孔硅球固定化胰凝乳蛋白酶时，其酶活力满足选择催化ＤＬ－苯丙氨酸甲酯水解的需要，相同反应条件下，多孔硅球比表面积越大，氨丙基硅烷化产物氨基含量越高。     

氨丙基官能化HMS介孔分子筛的合成及表征

沿S0I0路径,以十六胺为模板剂,以3-氨丙基三乙氧基硅烷为有机硅源,通过与TEOS共水解沉淀合成了氨丙基官能化HMS介孔分子筛.采用粉末X-射线衍射分析、N2吸/脱附、扫描电镜分析、高分辨透射电镜分析、傅立叶变换红外分析以及元素分析等表征手段,对所合成的材料进行表征.氨丙基官能化HMS介孔分子筛具有worm-like孔道结构,且较为均一的孔径分布.研究了前体硅源中3-氨丙基三乙氧基硅烷含量的变化对氨丙基官能化HMS介孔分子筛的相结构及织构性能的影响.傅立叶变换红外分析表明,NH2-CH2-CH2-CH2有机基团分布在杂化HMS介孔孔道中.     

硅烷化凹凸棒石负载H5PMo10V2O40催化合成苯甲醛乙二醇缩醛

以酸活化的凹凸棒石（Pa）为原料,用3-氨丙基三乙氧基硅烷（APTES）嫁接法制备了以3-氨丙基三乙氧基硅烷（3-aminopropyl—triethoxysilane,APTES）硅烷化凹凸棒石（PaAms）为载体负载Keggin型H5PMo10V2O40杂多酸催化剂（PMoV／PaAPTES）,并用红外光谱分析、X...     

硅胶表面牛血清白蛋白分子印迹聚合物的制备及分子识别性能

报道了以氨丙基硅胶为载体,将其表面醛基化后通过亚胺键共价键合牛血清白蛋白,再用两种硅烷化试剂氨丙基三乙氧基硅烷和正辛基三甲氧基硅烷进行聚合,合成表面印迹牛血清白蛋白分子印迹聚合物的方法。本方法以共价键印迹蛋白质,用草酸洗脱。表面印迹有利于大分子蛋白质向印迹位点的扩散和再结合,合成的印迹聚合物对牛血清白蛋白的吸附率达44.5%,而其它蛋白的吸附率小于17%,显示对模板蛋白具有特异吸附能力。     

硼酸亲和杂化毛细管整体柱选择性富集蒲公英中的活性物质

以四乙氧基硅烷,N-氨乙基-3-氨丙基三乙氧基硅烷,3-甲基丙烯酰氧丙基三甲氧基硅烷作为前驱,4-乙烯基苯硼酸为单体,在毛细管中原位制备硼酸亲和杂化整体柱,该柱可在中性条件下选择性的富集顺式二羟基生物分子,实现了对蒲公英中活性成分咖啡酸及绿原酸的选择性富集。     

γ-氨丙基硅氧烷与八甲基环四硅氧烷乳液共聚合的研究

合成了γ-氨丙基七甲基环四硅型氧烷和γ-氨丙基甲基二乙氧基硅烷。研究了它们与八甲基环四硅氧烷在阳离子乳化剂及阴离子型乳化剂存在下的乳液共聚合反应。探讨了催化剂量、单体浓度、氨丙基含量及温度等对聚合的影响。     

聚γ-(β-氰乙基)胺丙基硅氧烷铂配合物的合成与催化性能

γ-氨丙基三乙氧基硅烷与丙烯腈反应，得到γ-(β-氰乙基)胺丙基三乙氧基硅烷。后者用气相法二氧化硅固载，再与氯亚铂酸钾反应，合成了聚γ-(β-氰乙基)胺丙基硅氧烷铂配合物。研究了它对不饱和烃与三乙氧基硅烷的硅氢加成反应的催化特性。     

聚γ—（β—氰乙基）胺丙基硅氧烷铑配合物的合成与催化性能

γ－氨丙基三乙氧基硅烷与丙烯腈加成，得到γ－（β－氰乙基）胺丙基三乙氧基硅烷。后者依次与气相法二氧化硅、三氯化铑作用，合成了聚γ－（β－氰乙基）胺丙基硅氧烷铑配合物。它对烯烃与三乙氧基硅烷的硅氢加成反应具有良好的催化活性。     

γ-脲丙基三乙氧基硅烷的制备及表征

采用γ-氨丙基三乙氧基硅烷与尿素进行亲核取代反应,合成了γ-脲基丙基三乙氧基硅烷;通过对工艺条件的优化制备得到了纯度高达99%以上的产品并采用红外光谱及核磁进行了表征。     

Molecular macrocluster formation on silica surfaces in phenol-cyclohexane mixtures

The adsorption of phenol, an aromatic compound with a hydrogen-bonding group, onto a silica surface in cyclohexane was investigated by colloidal probe atomic force microscopy (AFM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and adsorption isotherm measurements. ATR-FTIR measurements on the silica surface indicated the formation of surface macroclusters of phenol through hydrogen bonding. The ATR-FTIR spectra were also measured on the H-terminated silicon surface to observe the effect of the silanol groups on the phenol adsorption. The comparison of the ATR-FTIR spectra for both the silicon oxide and H-terminated silicon surfaces proved that the silanol groups are necessary for the formation of phenol clusters on the surface. The surface force measurement using colloidal probe AFM showed a long-range attraction between the two silica surfaces in phenol-cyclohexane mixtures. This long-range attraction resulted from the contact of the adsorbed phenol layers for the phenol concentrations below 0.6 mol %, at which no significant phenol clusters formed in the bulk solution. The attraction started to decrease at 0.6 mol % phenol due to the exchange of the phenol molecules between the clusters in the bulk phase and on the surface. The surface density of phenol in the adsorbed layer was calculated on the basis of the long-range attraction and found to be much smaller than the liquid phenol density. The plausible structure of the adsorbed phenol layer was drawn by referring to the crystal structure of the bulk phenol and orientation of the phenol molecules on the surface, estimated by the dichroic analysis of ATR-FTIR spectroscopy. The investigation of the phenol adsorption on the silica surface in a nonpolar solvent using this novel approach demonstrated the effect of the aromatic ring on the surface packing density.     

Adsorptive voltammetry of 2-(5-bromo-2-pyridyl)azo-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol on a carbon paste electrode in the presence of organic cations and polycation.

The adsorption of ion-association complexes on a carbon paste electrode (CPE) was investigated by cyclic voltammetry using an electroactive hydrophobic anion probe. The redox reactions of 2-(5-bromo-2-pyridyl)azo-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol (5-Br-PAPS), the analytical probe, were irreversible. The reduction of the azo group and the oxidation of the phenol were observed at -0.1 V and 0.9 V vs. SCE, respectively, in a 0.1 mol L(-1) H(2)SO(4) solution. The peak currents for the redox reaction increased with the concentration of the cationic surfactant and the accumulation time. The increase in the ratio of the peak current to the concentration of cationic surfactants was proportional to the hydrophobicity. The peak current for 5-Br-PAPS also increased when a polycation, polyhexamethylene biguanide hydrochloride, was added and was strongly dependent on the ionic strength and pH, in contrast to cationic surfactants.     

Biotinylation of TiO(2) nanoparticles and their conjugation with streptavidin

Photoactive TiO(2) can be used to mediate a variety of disinfection processes. It was postulated that TiO(2) particles could be directed to specific targets of interest using biotin/streptavidin linkages. Biotinylated TiO(2) nanoparticles (anatase) were obtained by treating TiO(2) nanoparticles with 3-aminopropyltriethoxysilane (APTS) in anhydrous DMSO, followed by reaction with N-hydroxysuccinimidobiotin. 29Si CP-MAS NMR, 13C CP-MAS NMR, and FTIR spectra showed that biotin was covalently bound to the TiO(2) surface. Transmission electron microscopy (TEM) demonstrated that prolonging the silanization reaction times led to increasingly thick silsesquioxane coating layers of up to approximately 10 nm. The specific surface area (SSA) of the TiO2 particles decreased from 16 m(2) g(-1) before treatment to 9.1 m(2) g(-1) after aminosilanization and to 8.4 m(2) g(-)1 after biotinylation, as measured by nitrogen adsorption. Amino surfaces modified for 4, 16, and 26 h had total amino group densities ranging from 2.9 to 26 to 66 nm(-2), respectively, whereas accessible surface amino group densities ranged from 2.7 to 10 to 17 nm(-2) as shown from nitrogen adsorption, polyelectrolyte titration, conductometric titration, and biotin assays. Not all the amino groups were accessible for biotinylation: the densities of active biotin were found to be 2.1, 7.0, and 11.5 nm(-2). The ability of the attached biotin to bind to streptavidin was demonstrated by confocal microscopy with the use of fluorescently labeled streptavidin-FITC. Although streptavidin was readily able to bind to biotinylated TiO(2) particles, it did not act as a strong flocculating agent for the biotinylated TiO2 particles. The implications of these observations, with respect to particle accessibility to tethered streptavidin, are discussed.     

Immobilization of trivalent actinides by sorption onto quartz and incorporation into siliceous bulk: investigations by TRLFS

The adsorption of Cm(III) on quartz is studied by time resolved laser fluorescence spectroscopy (TRLFS) in the pH range from 3.75 to 9.45. The raw spectra are deconvoluted into three single components. The first one has a peak maximum at 593.8 nm and can be attributed to the Cm(III) aquo ion with an emission lifetime of 68+/-3 micros. The second one corresponds to an adsorbed species and has a peak maximum at 601.4 nm and an emission lifetime of 123+/-10 micros. The peak maximum of the third component is shifted to higher wavelength (603.6 nm) while the lifetime remains constant. Additionally, the adsorption of Am(III) on quartz is investigated in batch experiments. Based on the spectroscopic data a sorption mechanism is suggested. In addition, the obtained Am uptake data and the Cm-TRLFS data are modeled simultaneously using a single site Basic Stern model in combination with the charge distribution concept of Pauling. The finally suggested model consists of two bidentate surface complexes where the second one is the product of hydrolysis of the first sorption species. In a separate set of experiments the influence of silicic acid at different concentrations on the Cm(III) speciation in a quartz system is investigated by TRLFS. In suspension silicic acid at low concentration (3.5x10(-4) mol/L) has no influence on the Cm(III) speciation. At high concentration (3.5x10(-2) mol/L) the Cm(III) speciation is definitely influenced. The results at higher concentration indicate the formation of Cm(III)/silicic acid complexes and the incorporation of Cm(III) into siliceous bulk. This is confirmed by measurements at a quartz single crystal surface. Moreover, these measurements indicate the formation of quartz/Cm(III)/silicic acid ternary complexes at the mineral surface.     

Low-cost and effective phenol and basic dyes trapper derived from the porous silica coated with hydrotalcite gel

Novel low-cost and effective adsorbents of phenol and basic dyes were made by coating amorphous silica with hydrotalcite (HT) gel followed by soaking in alkaline solution, and the surface basic-acidic properties of resulting composites were evaluated by CO(2)-TPD, Hammett indicator method and NH(3)-TPD, respectively. Both BET surface area and microporous surface area of the composites were increased after they were soaked with alkaline solution; meanwhile the center of pore size distribution was changed from 9 to 3-4 nm. These composites efficiently captured phenol in gaseous and liquid phases, superior to mesoporous silica such as MCM-48 or SBA-15 and zeolite NaY, and the equilibrium data of gaseous adsorption could be well fitted to Freundlich model. These modified silicas also exhibited high adsorption capacity forward basic dyes such as crystal violet (CV) and leuco-crystal violet (LCV), reaching the adsorption equilibrium within 1 h and offering a new material for environment protection.     

ZnCl2、KOH和HNO3改性MWCNT对苯酚的吸附行为研究

通过扫描电子显微镜、X射线衍射仪、N₂吸附分析仪及Boehm滴定法获得ZnCl₂、KOH和HNO₃化学处理对高纯多壁碳纳米管的结构和表面含氧官能团的影响,通过批处理实验考察吸附条件（吸附时间、初始浓度、温度）对处理前后的碳纳米管吸附苯酚行为的影响,并采用准一级、准二级、Evolich动力学模型和热力学方程拟合其吸附数据,分析其动力学行为、热力学行为和吸附机理。结果表明,虽然ZnCl₂、KOH和HNO₃化学处理法均未对碳纳米管BET比表面积产生显著影响,但会影响其表面化学性质（即,对于ZnCl₂和KOH化学处理降低表面羧基、内酯基含量和增大碱性官能团量,而对于HNO₃化学处理可以增大表面羧基、内酯基含量,而碱性官能团略有增加）;改性处理影响碳纳米管去除苯酚效率：由于ZnCl₂和KOH改性处理降低碳纳米管表面羧基量,故其提高了苯酚去除率,而HNO₃处理则略减小碳纳米管的苯酚去除率,可能是由于碳纳米管结构和表面化学性质共同影响所致;碳纳米管的苯酚去除率均随苯酚溶液初始浓度的增大而减小;高温不利于吸附;热力学研究发现碳纳米管吸附苯酚过程是自发的和放热的,属于物理吸附;动力学研究表明,吸附过程符合准二级动力学方程。通过ZnCl₂和KOH化学处理,可以显著提高碳纳米管对苯酚的吸附性能。     

α-Fe_2O_3空心球的水热法制备及其对苯酚的吸附性能

以铁氰化钾、磷酸二氢铵等为反应物,采用水热法合成了α-Fe2O3空心球,并用XRD,TEM,FESEM(场发射扫描电镜)、UV-Vis和低温氮吸附脱附对其进行了表征。结果表明,α-Fe2O3空心球直径在200～560nm之间,其BET比表面积为80m2·g-1,平均孔径为8.5nm。考察了反应时间、反应物用量和反应温度等对α-Fe2O3空心球形貌和大小的影响,提出了其可能的形成机理。研究了室温下α-Fe2O3空心球吸附苯酚的性能,吸附达平衡时,其吸附苯酚的量达97mg·g-1。     

Hydrogen-bonded macrocluster formation of ethanol on silica surfaces in cyclohexane(1)

Adsorption of ethanol onto silica surfaces from ethanol-cyclohexane binary liquids was investigated by a combination of colloidal probe atomic force microscopy, adsorption excess isotherm measurement, and FTIR spectroscopy using the attenuated total reflection (ATR) mode. An unusually long-range attraction was found between the silica (glass) surfaces in the presence of ethanol in the concentration range of 0.1-1.4 mol % at room temperature. At 0.1 mol % ethanol, the attraction appeared at a distance of 35 +/- 3 nm and turned into a repulsion below 3.5 +/- 1.5 nm upon compression. Half of the attraction range agreed with the adsorption layer thickness estimated from the adsorption excess amount by assuming that the adsorption layer was composed only of ethanol. This indicated that the observed long-range attraction was caused by the contact of opposed adsorption layers of ethanol on the silica surfaces and that the sharp increase of repulsion at shorter distance was caused by the overlap of structured ethanol clusters adjacent to the surface. ATR-FTIR spectra demonstrated that ethanol adsorbed on the silica (silicon oxide) surfaces formed hydrogen-bonded clusters (polymers). Practically no ethanol clusters were formed on the hydrogen-terminated silicon surface. These results indicated that the cluster formation involved hydrogen-bonding interactions between surface silanol groups and ethanol hydroxyl groups in addition to those between ethanol hydroxyl groups. At higher temperatures (30-50 degrees C), the range and the strength of attraction decreased owing to the decrease in the hydrogen-bonded clusters monitored by FTIR spectroscopy, reflecting the nature of hydrogen bonding. The range and the strength of the attraction also changed when the ethanol concentration increased: The long-range attraction started to decrease at 0.6 mol % ethanol at room temperature and disappeared at 1.4 mol % while the adsorption excess amount remained almost constant as did the FTIR peak intensity of the hydrogen-bonded OH group of adsorbed ethanol. In the bulk solution, ethanol clusters appeared at 0.5 mol % ethanol; thus, this change in the attraction could be accounted for in terms of the exchange of ethanol molecules between the surface clusters and bulk clusters. The novel self-assembled structure of alcohol on the surface, found in this study may be called a "surface molecular macrocluster" because the hydrogen-bonded clusters extend to distances of ca. 20 nm longer than the typical sizes of common clusters, 2-4 nm, of alcohol (e.g., ethanol).     

Interaction of phenol and dopamine with commercial MWCNTs

We report the adsorption of phenol and dopamine probe molecules, from aqueous solution with NaCl, on commercial multiwall carbon nanotubes (MWCNT) and on their carboxylated derivative. The nanotubes were fully characterized by high resolution transmission electron microscopy (HRTEM), small angle X-ray scattering (SAXS), potentiometric titration, electrophoretic mobility, and nitrogen adsorption (77K) measurements. The experimental pollutant isotherms, evaluated using the Langmuir model, showed that only 8-12% and 21-32% of the BET surface area was available for phenol and dopamine, respectively, which is far below the performance of activated carbons. Influence of the pH was more pronounced for the oxidized MWCNT, particularly with dopamine. The strongest interaction and the highest adsorption capacity occurred at pH 3 with both model pollutants on both types of nanotubes. Although the surface area available for adsorption is far lower in MWCNTs than in activated carbons, it is nonetheless substantial. In particular, delayed release of toxic molecules that are either adsorbed on the surface or trapped in the inner bore of such systems could constitute an environmental hazard. The need for further adsorption studies with regard to their environmental aspects is therefore pressing, particularly for MWCNTs in their functionalized state.     

磺酸基功能化的有序SBA-15-SO3H介孔分子筛的合成及其在苯酚叔丁基化反应中的应用

通过一步法合成了SBA-15-SO3H介孔分子筛,用XRD,TEM,低温N2吸附和吡啶吸附红外光谱等方法进行了表征,并研究了其在苯酚叔丁基化反应中的催化性能.结果表明,SBA-15-SO3H保持了母体SBA-15高度有序的六方介孔结构,具有较强的酸性和热稳定性,且在苯酚叔丁基化反应中表现较好的催化活性和2,4-二叔丁基苯酚选择性.