超临界CO2中以PEG2000为模板制备TiO2/SiO2复合材料

超临界CO2;PEG;模板;TiO2/SiO2;复合材料     

Enhanced corrosion protection performance with MWCNT dispersed epoxy coating prepared under supercritical CO2 assistance

The corrosion protection performance of epoxy coatings could be enhanced by incorporation of nanofillers such as MWCNT. However, a homogeneous dispersion of MWCNT in epoxy polymer is still a teasing challenge. Herein, we report an environmentally benign single‐step supercritical CO₂ processing method to improve the dispersion of MWCNT in epoxy matrix in order to achieve an effective anticorrosive coating. The executed approach provides a cluster‐free uniform distribution of MWCNT in epoxy matrix as characterized with UV‐visible spectroscopy, Fourier transforms infrared spectroscopy, X‐ray diffraction, and surface analysis. The anticorrosive characteristics of MWCNT/epoxy coating were studied in NaCl as well as in photodegraded dye medium through electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. We observed the remarkable corrosion of model metal substrate in photodegraded dye medium besides NaCl medium. In both mediums, the protection efficacy of MWCNT/epoxy coating was deduced from the stable impedance arcs in Nyquist plot and increased impedance modulus. The electrochemical impedance spectra were best fitted with equivalent circuits showing the higher values of pore resistance. Also, the MWCNT/epoxy coating exhibited a positive shift of corrosion potential and possessed a lower corrosion rate as compared with neat epoxy coating. More direct evidence of the excellent barrier properties for MWCNT/epoxy coating was visualized in SEM images. The obtained results implied that the superior dispersion of MWCNT into epoxy matrix significantly reduces the porosity of coating and inhibits the permeability of corrosive ions. We expect supercritical CO₂ assisted dispersion method can offer an efficient, cost‐effective, and industrially viable route to develop high performance protective coatings for varied commercialized applications.     

Metal ion extraction using newly-synthesized bipyridine derivative as a chelating reagent in supercritical CO(2).

4,4'-Bis(dihexylaminocarbonyl)-2,2'-bipyridine (BDC-Bipy) was synthesized and studied systematically as a chelating reagent for metal ions extraction in supercritical CO(2). The compound showed high extraction efficiency for Co(2+) (100%), Cu(2+) (100%), Cd(2+) (98.2%), and Zn(2+) (100%) ions and good extraction efficiency for Sr(2+) (79.4%) and Pb(2+) (89.8%) when the extraction was performed in supercritical CO(2) at 313 K and 25 MPa with the system of BDC-Bipy, deionized water and perfluoro-1-octanesulfonic acid tetraethylammonium salt. The recoveries of mixed metal ions were also measured; unfortunately, the system of extraction has no selectivity for the metal ions.     

超临界CO2中模板法制备TiO2/SiO2复合多孔材料

在超临界CO2中以颗粒状活性炭为模板,正硅酸乙酯和钛酸四正丁酯为前驱体制备了TiO2/S iO2复合多孔材料。研究了超临界状态下不同涂层温度和涂层压力对涂层率的影响,当温度为40℃时,压力在22 MPa为该温度的最佳涂层压力;固定压力为22 MPa,涂层温度为70℃为最佳涂层条件。X射线衍射(XRD)的研究结果表明,产物由锐钛矿型TiO2、金红石型TiO2以及结晶的S iO2这3种物质构成。根据产物的N2气吸附-脱附等温线计算,产物的比表面积达到144.44 m2/g,平均孔径为7 nm左右。扫描电子显微镜的分析结果证明,产物在一定程度上实现了对模板的复制,同时透射电子显微镜显示,复合材料的纳米颗粒尺寸具有良好的分散性。     

皮革的CO2超临界流体脱灰

浸灰和脱灰是皮革制造过程的重要工序。在浸灰工序中,通过高浓度石灰乳液对动物皮的长时间处理,使其纤维介质被溶解,胶原纤维得到分散。脱灰是其后续工序,目的是除去动物皮中吸附和沉积的Ｃａ2+;调节ｐＨ值至中性并使其肿胀状态得以消除;促进鞣铬剂的发渗而与胶原纤维有效结合。常规制革工艺中,铵盐被广泛用作脱灰剂,其缺点是中和作用不充分不能有效除去Ｃａ2+,Ｃａ2+与动物油脂反应会产生“钙斑”,并产生令人不愉快的氨污染环境。而硼酸、甲酸、乙酸、柠檬酸等以单独或组合方式与铵盐一道用于脱灰[1]价格昂贵,还易引起裸皮的酸肿影响皮…     

Dehydrogenation of propane in the presence of CO2 on Cr(3%)/SiO2 catalyst under supercritical conditions

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One-Step Fabrication of Thermally Stable TiO(2)/SiO(2) Nanocomposite Microspheres by Evaporation-Induced Self-Assembly

The evaporation-induced self-assembly of mixed colloids has been employed to synthesize microspheres of TiO(2)/SiO(2) nanocomposites. Small-angle neutron/X-ray scattering and scanning electron microscopy experiments reveal the hierarchical morphology of the microspheres. Although the internal structure of the microspheres, consisting of solely silica nanoparticles, gets significantly modified with time because of the reduction in the high specific surface area by internal coalescence, the same for the composite microspheres remains stable over an aging time of 1 year. Such temporal stability of the composite microspheres is attributed to the inhibition of coalescence of the silica nanoparticles in the presence of titania nanoparticles. X-ray diffraction and thermogravimetric results show the improved thermal stability of the composite grains against the anatase-to-rutile phase transition. Such thermal stability is attributed to the suppression of the growth of titania nanoparticles in the presence of silica nanoparticles. The UV-vis results indicate the confinement effect of the TiO(2) nanoparticles in the silica matrix. A plausible mechanism has been elucidated for the formation of microspheres with different morphology during self-assembly.     

Fabrication of flowerlike polymer superstructures using polymer/zeolite composites prepared with supercritical CO2

We report a route to the fabrication of unique flowerlike polymer superstructures with uniform petals at the nanoscale. In this method, polymer/zeolite composite is first prepared by loading corresponding monomer and initiator into the channels of the host zeolite with the aid of supercritical (SC) CO2, followed by thermal polymerization of monomers in the channels of the zeolite. The resultant polymer/zeolite composite is then treated with HF aqueous solution to allow the self-aggregation of the polymer and the inorganic components to form the polymeric layers and inorganic layers. Unique microscale flowerlike polymer superstructures are obtained after further treatment with HF aqueous solution. Different techniques, such as scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and thermogravimetry (TG), have been used to characterize the microflowers.     

Synthesis of ordered macroporous SiO2 in supercritical CO2 using 3D-latex array templates

Ordered macroporous SiO(2) membranes were produced by the decomposition of silicon alkoxides in supercritical carbon dioxide (scCO(2)) using 3D-latex arrays as templates.     

Spectrophotometric determination of chloride in PtAl(2)O(3)/SiO(2) catalysts with Hg(SCN)(2)Fe(3+) reagent

A method is described for the determination of chloride in PtAl(2)O(3)/SiO(2) catalysts, based on its extraction with alkali followed by reaction with Hg(SCN)(2)Fe(3+) reagent and spectrophotometric measurement at 460 nm. Beer's law is obeyed in the concentration range 5-75 mug of chloride in 25 ml of aqueous solution. The molar absorptivity is 1.99 x 10(3) l.mole(-1).cm(-1). The rapid colour development, excellent reproducibility and absence of interference from the species most often present in the catalysts are the advantages of the method.     

碳球为模板水热合成Mg-Co复合氧化物及其催化分解N2O

用自制的碳球为模板剂,尿素为沉淀剂,120℃水热合成尖晶石型Mg-Co复合氧化物（MgCo₂O₄）,在其表面浸渍K₂CO₃溶液制得K改性催化剂,用于催化分解N₂O。用X射线衍射（XRD）、N₂物理吸附-脱附、扫描电镜（SEM）、H₂程序升温还原（H₂-TPR）、O₂程序升温脱附（O₂-TPD）、X射线光电子能谱（XPS）等技术对催化剂进行结构表征,考察了钴镁离子/碳球的质量比、尿素/钴镁离子的物质的量比等制备参数对催化剂活性的影响。结果表明,钴镁离子/碳球的质量比为0.192、尿素/钴镁离子的物质的量比为2,制得的MgCo₂O₄催化剂活性较高。K改性MgCo₂O₄催化剂在400℃有氧无水、有氧有水条件下连续反应50 h,N₂O转化率分别保持在91%和62%,稳定性较好。     

Solvent-free iodination of organic molecules using the I(2)/urea-H(2)O(2) reagent system

Introduction of iodine under solvent-free conditions into several aromatic compounds activated toward electrophilic functionalization was found to proceed efficiently using elemental iodine in the presence of a solid oxidizer, the urea-H(2)O(2) (UHP) adduct. Two types of iodo-functionalization through an electrophilic process were observed: iodination of an aromatic ring, and side-chain iodo-functionalization in the case of arylalkyl ketones. Two reaction routes were established based on the required substrate : iodine : oxidizer ratio for the most efficient iodo-transformation, and the role of UHP was elucidated in each route. The first, requiring a 1 : 0.5 : 0.6 stoichiometric ratio of substrate to iodine to UHP, followed the atom economy concept in regard to iodine and was valid in the case of aniline, 4-t-Bu-phenol, 1,2-dimethoxy benzene, 1,3-dimethoxy benzene, 1,2,3-trimethoxy benzene, 1,2,4-trimethoxy benzene, 1,3,5-trimethoxy benzene, 1-indanone and 1-tetralone. The second reaction route, where a 1 : 1 : 1 stoichiometric ratio of substrate : I(2) : UHP was needed for efficient iodination, was suitable for side-chain iodo-functionalization of acetophenone and methoxy-substituted acetophenones. Moreover, addition of iodine to 1-octene and some phenylacetylenic derivatives was found to proceed efficiently without the presence of any oxidizer and solvent at room temperature.     

Preparation and Formation Mechanism of Porous TiO2 Films Using PEG and Alcohol Solvent as Double-Templates

Porous nanocrystalline TiO₂ anatase thin films have been synthesized on glass substrates via a sol-gel dip-coating method. The coating sol was obtained by suppressed hydrolysis of Ti(OC₄H₉)₄ through the addition of complexing molecules as stabilizers in an alcohol solution containing polyethylene glycol (PEG). Chemical changes taking place during the sol-gel process were discussed based on IR spectra analysis. A model concerning the pore formation was established to explain the role of PEG and solvent with core-shell configuration as double-templates. The structural characteristics of porous TiO₂ films were found to greatly depend on the concentration and molecular weight of PEG, the types of stabilizing agents and solvents. The pore size of the films was tunable in the range of 10–500 nm and their surface area varied from 51 to 72 m²·g^–1.     

Thermal behaviors of poly(ethylene terephthalate)/SiO2 nanocomposites prepared by cryomilling

The thermal behaviors of poly (ethylene terephthalate) (PET)/SiO₂ nanocomposites prepared by cryomilling were studied, by comparing with the cryomilled PET and the raw PET. Cryomilling induced amorphization of crystalline PET matrix and the decrease of PET molecular weight. Cryomilled PET/SiO₂ nanocomposites have two abnormal phenomena in the DSC 1st heating thermogram due to the stored energy induced by cryomilling. During DSC cooling process, the dispersed nanometer SiO₂ particles play a role of nucleating agent in PET matrix, and the hot crystallization ability of PET/SiO₂ nanocomposites improves a lot. Besides, the heat stability of cryomilled PET/SiO₂ nanocomposites improves more much during reheating. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1351–1356, 2006     

Carbon nanotube/poly(2,4-hexadiyne-1,6-diol) nanocomposites prepared with the aid of supercritical CO2

Poly(2,4-hexadiyne-1,6-diol)(poly(HDiD)) was coated on the outer walls of carbon nanotubes (CNTs) with the aid of supercritical CO(2), resulting in poly(HDiD)/CNT nanocomposites, which possess optical properties originated from poly(HDiD).     

Reaction of silanes in supercritical CO2 with TiO2 and Al2O3

Infrared spectroscopy was used to investigate the reaction of silanes with TiO2 and Al2O3 using supercritical CO2 (Sc-CO2) as a solvent. It was found that contact of Sc-CO2 with TiO2 leads to partial removal of the water layer and to the formation of carbonate, bicarbonate, and carboxylate species on the surface. Although these carbonate species are weakly bound to the TiO2 surface and can be removed by a N2 purge, they poison the surface, resulting in a lower level of reaction of silanes with TiO2. Specifically, the amount of hexamethyldisilazane adsorbed on TiO2 is about 10% of the value obtained when the reaction is performed from the gas phase. This is not unique to TiO2, as the formation of carbonate species also occurs upon contact of Al2O3 with Sc-CO2 and this leads to a lower level of reaction with hexamethyldisilazane. This is in contrast to reactions of silanes on SiO2 where Sc-CO2 has several advantages over conventional gaseous or nonaqueous methods. As a result, caution needs to be applied when using Sc-CO2 as a solvent for silanization reactions on oxides other than SiO2.     

Spherulite growth rates of in situ prepared poly(propylene terephthalate)/SiO2 nanocomposites

The spherulite growth rates of in situ prepared PPT/SiO₂ nanocomposites containing 2–5 wt% nano-silica were studied. Measurements of the spherulite growth rates were carried out by applying non-isothermal experiments using polarized light microscopy (PLM). Comparison with results from isothermal PLM tests showed good agreement. Isothermal crystallizations after self-nucleation were also performed using differential scanning calorimetry (DSC) and the inverse crystallization half-times were estimated. The Lauritzen–Hoffman analysis was applied by using data from both isothermal and non-isothermal PLM experiments and the DSC results. Regimes II–III transition were observed at critical breakpoint close to 195 °C. The regimes I–II transition was not so clear, because of the semi-rigid macromolecular chains of the polymers. Results using DSC data were in satisfactory agreement to those using PLM spherulite growth data.     

Characterization and biological evaluation of paclitaxel-loaded poly(L-lactic acid) microparticles prepared by supercritical CO2

In this study, paclitaxel loaded poly( L-lactic acid) (PTX-PLLA) microparticles were prepared using solution enhanced dispersion by supercritical CO2(SEDS) technique. This supercritical antisolvent technique offers the advantage of negligible organic solvent residua in the drug loaded microparticles. Scanning electron microscopy (SEM) showed that microparticles exhibited rather spherical shape and small particle size with narrow particle size distribution. X-ray diffraction (XRD) and differential scanning calorimeter (DSC) indicated that PTX was amorphously dispersed in the PLLA matrix. The drug loading and encapsulation efficiency of PTX-PLLA microparticles were 14.33% and 62.68%, respectively. In vitro cytotoxicity evaluation of PTX-PLLA microparticles against nonsmall-cell lung cancer A549 and ovarian cancer SKOV3 cell lines indicated that PTX-PLLA had superior antiproliferation activity against the A549 and SKOV3 cell lines, compared with free PTX formulations. The cellular internalization of fluorescent microparticles was evidenced by fluorescence microscope and further confirmed by transmission electron microscopy (TEM). This was attributed to the efficient intracellular accumulation of PTX via cell phagocytosis and sustained release of PTX from PLLA matrix. The anticancer activity of PTX-PLLA was associated with PTX-induced cell apoptosis such as nuclear aberrations, condensation of chromatin and swelling damage in mitochondria. The cell apoptosis index detected by flow cytometry was higher in PTX-PLLA group than in free PTX. The PTX-PLLA formulation, which was obtained through micronization of PTX and encapsulation of micronized PTX into PLLA simultaneously in the SEDS process, significantly potentiated the anticancer activity of PTX.     

Studies on TiO2/SiO2 and Pd/TiO2/SiO2 Catalysts in Photoreduction of CO2 with H2O to Methanol

The development of industry induced a massive increase in the emission of carbon dioxide into the atmosphere. A large amount of CO₂ and its general availability causes that it could be a cheap reactant in a reaction that runs in a way similar to photosynthesis in plants. Pure TiO₂ and metal doped TiO₂ are the most studied semiconductor catalysts for photoreduction of CO₂. The TiO₂/SiO₂ and Pd/TiO₂/SiO₂ catalysts were prepared and studied by temperature-programmed desorption, X-ray diffraction analysis, SEM-EDS, temperature-programmed reduction and then used for the methanol synthesis. The photoactivity of Pd/TiO₂/SiO₂ catalysts in the reduction of CO₂ with H₂O was tested at room temperature using photoreactor equipped with 16 lamps. The wavelength was characteristic of near ultraviolet. Post-reaction products were identified with gas chromatograph equipped with the flame ionization detector. Pd doping made the catalysts photoactive and the photoactivity of catalysts was changing as follows: 1%Pd/5%TiO₂/SiO₂ > 1% Pd/10% TiO₂/SiO₂ > 1% Pd/15% TiO₂/SiO₂. Optimum ultraviolet radiation time in the photoreduction of CO₂ to methanol was 7 h. An addition of Pd does not change the surface of the carrier.     

Molecularly imprinted TiO(2) thin film using stable ground-state complex as template as applied to selective electrochemical determination of mercury

Molecular recognition sites for mercury ions were imprinted in TiO₂ film using stable ground-state complex of 1-amino-8-naphtol-3,6-disodium sulfonate (ANDS) and mercury ions as template. The complex ratio between mercury ions and ANDS was estimated to be 2:1. Compared with the controlled and pure TiO₂ electrodes, the imprinted electrode revealed selectivity towards the imprinted ions. Linear calibration plots for mercury ions were obtained and the regression equation was I_p (μA) = 4.29 × 10⁻⁷ + 19.40 [Hg²⁺] with a detection limit of 3.06 × 10⁻⁹ mol/l. The imprinted electrode could be used for more than 1 month. Recoveries were calculated at both high and low concentrations, with a mean recovery of 99.6%.