介孔SiO2孔道结构对聚酰胺反渗透复合膜性能的影响

在界面聚合过程中,通过添加改进水热方法制备的球形介孔SiO2纳米材料,制备了改性的聚酰胺反渗透复合膜。使用扫描电镜、X射线衍射和氮气吸附-脱附等手段对制备的介孔SiO2纳米材料进行表征;采用反渗透膜评价装置、原子力显微镜、扫描电镜(SEM)和静态接触角仪器等手段对复合膜的性能和结构进行测试和表征;并对比了相同粒径大小的实心SiO2和介孔SiO2对膜渗透性能的影响。结果证明:成功合成了一种具有孔径分布均匀、粒径均一、比表面积较大、分散性较好的介孔SiO2纳米球形颗粒;SEM表征结果证实纳米材料在膜表面分布均匀,膜表面亲水性能提高,粗糙度变大;膜性能测试结果证实了介孔SiO2的添加使得膜在维持较高截留率的前提下,具有更高的水通量;同时,通过对比相同尺寸的实心SiO2作为添加材料,证实了介孔SiO2的孔道结构更有利于水分子的传输。当介孔SiO2添加质量为0.06%时,水通量由23L/(m2·h)提高至39L/(m2·h),对氯化钠的截留仍然维持在98%以上。     

Observation of quantum confinement effect on ZnO embedded mesoporous silica

Nonionic surfactant as liquid organic template and tetraethoxysilane as silica precursor were used for the synthesis of mesoporous silica with ordered arrangement of nanopores (diameters are about 1-6 nm). The synthesized mesoporous silica was used as the template for the synthesis of ZnO nanoparticles using zinc acetylacetonate as ZnO precursor. The as synthesized ZnO incorporated in the mesoporous silica nanocomposite were analyzed using X-ray diffraction, TEM and Photoluminescent spectrum. ZnO introduction has no extensive influence on the mesoporous structure of silica. Quantum confinement effects are observed in the case of ZnO nanoparticles embedded in mesoporous silica. The particle size of ZnO is about 3.2 nm. The band gap is broadening to 3.47 eV.     

The size-controllable synthesis of nanometer-sized mesoporous silica in extremely dilute surfactant solution

10–60 nm-sized mesoporous silica particles with ordered or worm-like pore structures were controllably synthesized in extremely dilute surfactant solution, and the lowest concentrations of TEOS and CTAB were 12.45 mM, 1.52 mM, respectively. The synthesis of nanometer-sized Al-incorporated mesoporous silica particles (Al-MS) was also performed under the similar conditions. Compared to the mesoporous silica without doping of aluminum, those Al-incorporated silica particles have a certain textural mesoporosity. The results indicate that the size and pore structure of mesoporous silica can be adjusted by changing the concentration of reactants. The mesoporous silica nanoparticles, including Al-MS, were characterized by transmission electron microscopy (TEM), small-angle X-ray diffraction (SAXRD), as well as nitrogen adsorption/desorption techniques. It was suggested that the formation of the mesoporous silica nanoparticles could be attributed to the deposition of self-assembled silicate micelles.     

Palladium supported on functionalized mesoporous silica as an efficient catalyst for Heck reaction

Pd nanoparticles supported in functionalized mesoporous silica were prepared. Mesoporous silica support was modified with [3-(2-aminoethyl aminopropyl)] trimethoxysilane. Palladium ions were grafted onto the functionalized mesoporous silica and reduced with hydrazine hydrate to obtain the Pd nanoparticles supported on functionalized mesoporous silica. The Pd loading in the nanocomposite of Pd supported on the functionalized mesoporous silica is 4.30 wt%. CO chemisorption analysis on the nanocomposite shows a Pd dispersion as high as 35% and a Pd surface area of 156 m²/g. The surface area, pore size, and pore volume decrease slightly with the incorporation of the Pd nanoparticles into the functionalized mesoporous silica. Pd supported on the functionalized mesoporous silica with controlled molar ratio of amino groups to palladium exhibits an excellent catalytic activity and low Pd leaching for the Heck carbon-carbon coupling reaction. The catalyst can be reused for at least six recycles in air with only a minor loss of activity.     

Third-order optical nonlinearity of cadmium sulfide nanoparticles loaded in mesostructured silica materials

Cadmium sulfide nanoparticles have been successfully incorporated in three forms of CTAB-templated mesoporous silica materials: one is the mesoporous silica spheres suspended in ethanol solution, the other is the mesoporous silica spheres spin-coated on glass slide, and the third is the dip-coated mesoporous silica thin film. The mesostructures were characterized by XRD and TEM, respectively. Linear optical properties were investigated using UV-visible spectra, and the diameter of the incorporated CdS nanoparticles was measured to be around 3.1 nm. Z-scan technique manifested that these three composites exhibited distinct third-order optical nonlinearities due to the different preparation techniques. Reverse saturation absorption could be detected in the CdS-loaded mesoporous silica spheres suspended in solution, while those dispersed on glass slide presented saturation absorption. The difference in nonlinear absorption of the two mesoporous silica sphere samples could be attributed to defect-related transitions. On the contrary, the CdS-loaded mesoporous silica thin film showed self-defocusing behavior with no nonlinear absorption signals. Compared to that of the CdS nanoparticles with larger size previously reported, the intrinsic microscopic third-order nonlinear optical susceptibility of those incorporated in CTAB-templated mesoporous thin film was increased as predicted by the quantum theory, and the third-order optical nonlinearity was further determined to arise from intraband transitions induced by quantum confinement.     

Aerosol-assisted synthesis of thiol-functionalized mesoporous silica spheres with Fe3O4 nanoparticles

Thiol-functionalized mesoporous silica spheres having Fe3O4 nanoparticles are fabricated in one-pot by aerosol-assisted synthesis. A TEM image shows that Fe3O4 nanoparticles are successfully embedded within the mesoporous silica spheres. SEM images and SAXS profiles reveals that the encapsulating Fe3O4 nanoparticles do not affect the ordering of a mesoporous structure. The spherical morphologies are also well retained. The presence of cage-type mesopores with uniform size is confirmed by N2 adsorption-desorption isotherms and TEM observations. The spray-dried thiol-functionalized particles with Fe3O4 nanoparticles effectively adsorb mercury (II) ions due to their strong interaction to thiol groups embedded in the framework. The particles with the amount of Fe3O4 nanoparticles (3.5 wt%) show a saturated magnetization (over 1.0 emu/g). This magnetic property is useful for practical collection with magnet.     

Mesoporous‐Silica‐Coated Up‐Conversion Fluorescent Nanoparticles for Photodynamic Therapy

Near‐infrared (NIR)‐to‐visible up‐conversion fluorescent nanoparticles have potential to be used for photodynamic therapy (PDT) in deep tissue because NIR light can penetrate thick tissue due to weak absorption in the optical window. Here a uniform layer of mesoporous silica is coated onto NaYF₄ up‐converting nanocrystals, with a large surface area of ≈770 m² g^?1 and an average pore size of 2 nm. A photosensitizer, zinc phthalocyanine, is incorporated into the mesoporous silica. Upon excitation by a NIR laser, the nanocrystals convert NIR light to visible light, which further activates the photosensitizer to release reactive singlet oxygen to kill cancer cells. The photosensitizer encapsulated in mesoporous silica is protected from degradation in the harsh biological environment. It is demonstrated that the photosensitizers loaded into the porous silica shell of the nanoparticles are not released out of the silica while they continuously produce singlet oxygen upon excitation by a NIR laser. The nanoparticles are reusable as the photosensitizers encapsulated in the silica are removed by soaking in ethanol.     

Controlled synthesis of semiconductor PbWO4 nanocrystals inside silica SBA-15 materials

A new flexible approach is developed to synthesize PbWO₄ nanoparticles inside the channels of mesoporous silica SBA-15. Mesoporous SBA-15 silica with 7 nm pores was produced by a hydrothermal process and used as a hard template. PbWO₄ nanoparticles were synthesized and incorporated into the mesoporous silicate support in a low-power ultrasonication condition. The as-synthesized samples were characterized by Raman spectroscopy, diffuse reflectance UV–vis spectroscopy (UV–vis), powder X-ray diffraction (XRD), small-angle X-ray diffraction (SAXRD), nitrogen adsorption and transmission electron microscopy (TEM). It was found that PbWO₄ nanoparticles appeared among the channels of SBA-15. Blue shift was observed in UV–vis absorption spectra due to the quantum size effect of PbWO₄ nanoparticles. This preparation method is also capable of synthesis of various semiconductor nanoparticles with controlled size and morphology inside the channels of mesoporous materials.     

Preparation of copper nanoparticles on carbon nanotubes by electroless plating method

Densely distributed copper nanoparticles have been deposited on the surface of carbon nanotubes with a size of ∼10 nm by the electroless plating method. It has been found that the pretreatment of the carbon nanotubes is very important to obtain the copper nanoparticles on the carbon nanotubes; in our experiments, one-step pretreatment of mixed HNO₃ and H₂SO₄ was found effective. In order to attain nanosized copper particles, the electroless plating parameters should be closely controlled; e.g., the pH value of the plating solution, the temperature, and the concentration and titrating speed of HCOH were critical.     

Study of mesoporous silica/magnetite systems in drug controlled release

Ordered mesoporous materials like SBA-15 have a network of channels and pores with well-defined size in the nanoscale range. This particular silica matrix pore architecture makes them suitable for hosting a broad variety of compounds in very promising materials in a range of applications, including drug release magnetic carriers. In this work, magnetic nanoparticles embedded into mesoporous silica were prepared in two steps: first, magnetite was synthesized by oxidation-precipitation method, and next, the magnetic nanoparticles were coated with mesoporous silica by using nonionic block copolymer surfactants as structure-directing agents. The materials were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), N(2) adsorption, and scanning electron microscopy (SEM). The influence of magnetic nanoparticles on drug release kinetics was studied with cisplatin, carboplatin, and atenolol under in vitro conditions in the absence and in the presence of an external magnetic field (0.25 T) by using NdFeB permanent magnet. The constant external magnetic field did not affect drug release significantly. The low-frequency alternating magnetic field had a large influence on the cisplatin release profile.     

Silica nanoparticles functionalized with a thermochromic dye for textile applications

The aim of this work was the fabrication of mesoporous silica nanoparticles functionalized with thermochromic dye for further incorporation onto textiles. The nanosilicas were prepared under alkaline conditions in the presence of the surfactant hexadecyltrimethylammonium chloride and functionalized with the organosilane dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (C18-NTMS). The dye was incorporated onto the mesoporous silica nanoparticles by two different methods: co-condensation and post-grafting, i.e. by adding the dye during or after the synthesis of the nanosilica, respectively. The morphology, particle and pore size, chemical composition, and textural properties of the silica nanoparticles were characterized by scanning electron microscopy (SEM), dynamic light scattering, N₂ adsorption isotherms at ?196 °C, Fourier transform infrared spectroscopy and thermogravimetry. The silica nanoparticles prepared with and without dye presented spherical shape (by SEM) and particle size ranging from 15 to 40 nm. The infrared spectra revealed the characteristic bands of silica and organosilane (in the cases where it was used). The prepared materials presented colour change when submitted to different conditions. The thermochromic dye-functionalized nanosilicas were efficiently immobilized into cotton fabric and tests were performed to verify the washing fastness. After washing, a slight decrease on the amount of silica was noticed, but much of it remained on the textile. The functionalized textiles presented a colour change within different conditions.     

Study of a pre-treatment process for electroless copper plating on ceramics

In this paper, a pre-treatment process for electroless copper plating on the ceramics was explored. Due to the catalytic activity of gold nanoparticles, the traditional three-step coarsening-sensitization-activation pre-treatment process has been optimized to a two-step coarsening-activation process. In our study, the following results were observed: electroless copper coating on the ceramics was formed after activating the substrate by gold nanoparticles; a more flat and compact nano-composite coating was also obtained by adding gold nanoparticles to the plating solutions. The mechanisms of pre-treatment and composite plating with gold nanoparticles were discussed.     

Synthesis and sensitivity properties of Pd-doped tin oxide nanoparticles dispersed in mesoporous silica

Pd-doped tin oxide nanoparticles dispersed in mesoporous silica were prepared by a thermal-decomposing method and characterized by isothermal nitrogen adsorption measurement, X-ray diffraction (XRD) and transmission electron microscopy (TEM). Tin oxide nanoparticles grow up slowly owing to confinement of the pores of the mesoporous silica. Due to the unique microstructure of the mesoporous silica, the obtained nanocomposite consists of a three-dimensional web of interconnected crystallites of tin oxide and exhibits electronic conductivity when enough tin oxide is assembled in the silica pores. The obtained nanocomposite has also a large specific surface area, and the tin oxide nanoparticles have a free surface in contact with the ambient air. Therefore, the samples exhibit a high sensitivity to CO gas, and have potential application.     

Magnetic hollow mesoporous silica nanospheres: facile fabrication and ultrafast immobilization of enzymes

Hollow mesoporous silica nanospheres with large pore size of around 11 nm have been synthesized by a structural difference based selective etching strategy, and the highly dispersed hydrophobic Fe3O4 nanoparticles with a particle size of 5 nm were then impregnated into hollow cores of nanospheres through these large pores by a vacuum impregnation technique. The structural characteristics of obtained magnetic composites were characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Selected Area Electron Diffraction (SAED), Ultraviolet-visible (UV-Vis) and Vibrating Sample Magnetometer (VSM). The results show that the obtained Fe3O4-hollow mesoporous silica composites exhibit superparamagnetic property with saturation magnetization value of 4.17 emu/g. Furthermore, the obtained supports show ultrafast immobilization of hemoglobin and the immobilized enzymes are not denatured, indicating that the superparamagnetic hollow mesoporous silica spheres are excellent support for immobilization of enzymes with magnetic recycling property.     

退火CdS/SiO2介孔组装体系光吸收的行为

用溶胶-凝胶法获得多孔SiO2载体，浸泡合成法得到不同复合量的CdS/SiO2块材料介孔组装体系。研究了复合量、气氛条件及退火温度对其光吸收特征的影响，发现吸收边随复合量增加往长波方向移动；在氮气和空气中退火时，随退火温度升高前者表现为红移而后者表现为蓝移，这归属于量子尺寸效应。     

Mesoporous silica-magnetite nanocomposite synthesized by using a neutral surfactant

Magnetite nanoparticles coated by mesoporous silica were synthesized by an alternative chemical route using a neutral surfactant and without the application of any functionalization method. The magnetite (Fe(3)O(4)) nanoparticles were prepared by precipitation from aqueous media, and then coated with mesoporous silica by using nonionic block copolymer surfactants as the structure-directing agents. The mesoporous SiO(2)-coated Fe(3)O(4) samples were characterized by x-ray diffraction, Fourier-transform infrared spectroscopy, N(2) adsorption-desorption isotherms, transmission electron microscopy, (57)Fe M?ssbauer spectroscopy, and vibrating sample magnetometry. Our results revealed that the magnetite nanoparticles are completely coated by well-ordered mesoporous silica with free pores and stable (～8?nm thick) pore walls, and that the structural and magnetic properties of the Fe(3)O(4) nanoparticles are preserved in the applied synthesis route.     

Impregnated silica nanoparticles for the reactive removal of sulphur mustard from solutions

High surface area (887.3m(2)/g) silica nanoparticles were synthesized using aerogel route and thereafter, characterized by N(2)-Brunauer-Emmet-Teller (BET), SEM and TEM techniques. The data indicated the formation of nanoparticles of silica in the size range of 24-75 nm with mesoporous characteristics. Later, these were impregnated with reactive chemicals such as N-chloro compounds, oxaziridines, polyoxometalates, etc., which have already been proven to be effective against sulphur mustard (HD). Thus, developed novel mesoporous reactive sorbents were tested for their self-decontaminating feature by conducting studies on kinetics of adsorptive removal of HD from solution. Trichloroisocyanuric acid impregnated silica nanoparticles (10%, w/w)-based system was found to be the best with least half-life value (t(1/2)=2.8 min) among prepared systems to remove and detoxify HD into nontoxic degradation products. Hydrolysis, dehydrohalogenation and oxidation reactions were found to be the route of degradation of HD over prepared sorbents. The study also inferred that 10% loading of impregnants over high surface area and low density silica nanoparticles enhances the rate of reaction kinetics and seems to be useful in the field of heterogeneous reaction kinetics.     

Synthesis of hollow spheres with mesoporous silica nanoparticles shell

Hollow spheres with mesoporous silica nanoparticles shell were synthesized with the use of cetyltrimethylammonium bromide (CTAB) and polystyrene (PS) hollow spheres as dual templates. The key to this study is that the uneven surface of the template provides nucleation sites for mesoporous nanoparticles, resulting in the formation of hollow spheres with mesoporous silica nanoparticles shell. The final products with hierarchical mesopores can be obtained through a simple one-step approach.     

Ultrasonic-assisted synthesis and magnetic studies of iron oxide/MCM-41 nanocomposite

Iron oxide nanoparticles were stabilized within the pores of mesoporous silica MCM-41 amino-functionalized by a sonochemical method. Formation of iron oxide nanoparticles inside the mesoporous channels of amino-functionalized MCM-41 was realized by wet impregnation using iron nitrate, followed by calcinations at 550 °C in air. The effect of functionalization level on structural and magnetic properties of obtained nanocomposites was studied. The resulting materials were characterized by powder X-ray diffraction (XRD), high-resolution transmission electron microscopy and selected area electron diffraction (HRTEM and SAED), vibrating sample and superconducting quantum interface magnetometers (VSM and SQUID) and nitrogen adsorption–desorption isotherms measurements. The HRTEM images reveal that the most of the iron oxide nanoparticles were dispersed inside the mesopores of silica matrix and the pore diameter of the amino-functionalized MCM-41 matrix dictates the particle size of iron oxide nanoparticles. The obtained material possesses mesoporous structure and interesting magnetic properties. Saturation magnetization value of magnetic iron oxide nanopatricles stabilized in MCM-41 amino-functionalized by in situ sonochemical synthesis was 1.84 emu g⁻¹. An important finding is that obtained magnetic nanocomposite materials exhibit enhanced magnetic properties than those of iron oxide/MCM-41 nanocomposite obtained by conventional method. The described method is providing a rather short preparation time and a narrow size distribution of iron oxide nanoparticles.     

Mesoporous silica nanoparticles carrier for urea: potential applications in agrochemical delivery systems

Nanotechnology-based agrochemical delivery systems would ensure efficient and economical utilization of these very important agricultural inputs. In this study, mesoporous silica nanoparticles with particle diameters of -150 nm and pore sizes of -2.5 nm were synthesized via liquid crystal templating mechanism. Urea, as a model agrochemical molecule, was entrapped in the mesopores of the siliceous material by simple immersion loading using aqueous urea solutions. About 15.5% (w/w) of urea was loaded inside the pores mainly by physisorption while the total adsorption capacity of mesoporous silica nanoparticles could reach up to 80% (w/w). Highly concentrated urea solution was found to be more effective due to high driving concentration gradient generated. Release process of the urea-loaded mesoporous silica nanoparticles in water and soil indicated a two stage sustained slow release-profile. The findings for soil release studies revealed at least fivefold improvement in the release period. By the ability to entrap urea guest molecules into its mesopores and release them in a controlled manner, mesoporous silica nanoparticles demonstrated its great potential as a nanocarrier for agrochemicals.