Ultrasonic-assisted ultra-rapid synthesis of monodisperse meso-SiO2@Fe3O4 microspheres with enhanced mesoporous structure

A core–shell-type of meso-SiO₂@Fe₃O₄ microsphere was synthesized via an ultrasonic-assisted surfactant-templating process using solvothermal synthesized Fe₃O₄ as core, tetraethoxysilane (TEOS) as silica source, and cetyltrimethyl ammonium bromide (CTAB) as templates. The samples were characterized by FT-IR, XRD, TEM, N₂ adsorption–desorption technology, and vibrating sample magnetometer (VSM). The results show that as-prepared meso-SiO₂@Fe₃O₄(E) and meso-SiO₂@Fe₃O₄(C) microspheres, treated by acetone extraction and high temperature calcination, respectively, still maintain uniform core–shell structure with desirable mesoporous silica shell. Therein, the meso-SiO₂@Fe₃O₄(E) microspheres possess a distinct pore size distribution in 1.8–3.0 nm with large specific surface area (468.6 m²/g) and pore volume (0.35 cm³/g). Noteworthily, the coating period of this ultrasonic-assisted method (40 min) is much shorter than that of the conventional method (12–24 h). The morphology of microspheres and the mesoporous structure of silica shell are significantly influenced by initial concentration of CTAB (C_CTAB), ultrasonic irradiation power (P) and ultrasonic irradiation time (t). The acceleration roles of ultrasonic irradiation take effect during the whole coating process of mesoporous silica shell, including hydrolysis-condensation process of TEOS, co-assembly of hydrolyzed precursors and CTAB, and deposition of silica oligomers. In addition, the use of ultrasonic irradiation is favorable for improving the homogeneity of silica shell and the monodispersity of meso-SiO₂@Fe₃O₄ microspheres.     

Development of high protonic conductors based on amorphous mesoporous alumina

The proton conductivity of amorphous mesoporous alumina synthesized with various pore sizes was examined. A systematic dependence of conductivity upon pore size was observed, with increased conductivity as the pore size increased. The highest conductivity, 0.004 S·cm^− 1, was obtained at 303 K and 90% relative humidity (RH). The RH dependence of the water content was determined. Proton mobility was investigated by ¹H-NMR. At 30% RH, the width of the ¹H-NMR line decreased with increasing pore size, suggesting an increase in proton mobility. At 90% RH, the increase of the ¹H-NMR sharp peak is accordant with the increase in conductivity as the pore size increased.     

Stability and characterization of mesoporous molecular sieve using natural clay as a raw material obtained by microwave irradiation

Mesoporous molecular sieve was synthesized via microwave irradiation method, and using natural clay, sodium silicate and aluminum chloride as raw materials and cetyl trimethyl ammonium bromide (CTAB) as a template agent under alkaline condition. The samples were characterized by various analytic and spectroscopic tools such as XRD, FT-IR, TEM, TG-DSC and N₂ physical adsorption, respectively. The results show that the synthesized sample has typical mesoporous structure and exhibits good mesoporous ordering. On the other hand, the as synthesized sample after calcination at 550 °C for 10 h has a surface area of 576.0 m²/g and an average pore size of 4.83 nm. Furthermore, the synthesized mesoporous molecular sieve still exhibits good mesoporous ordering after calcination at 750 °C for 3 h or hydrothermal treatment at 100 °C for 10 days.     

α-Al_2O_3介孔材料导热特性的模拟

本文针对α-Al2O3有序介孔材料的导热特性开展分子动力学模拟分析.提出了一种保证电中性的孔道结构构造方法;采用逆非平衡分子动力学方法(muller-plathe法),选取Matsui势为作用势,模拟计算了Al2O3介孔晶体材料在不同环境温度下沿孔道轴向方向的热导率;并借助全面实验分析法,设计了模拟条件,以考察孔径和孔隙率对热导率的影响.模拟结果显示:介孔Al2O3热导率先随温度的升高呈上升趋势,并在200—400 K之间取得极值;而后在400—1400 K范围内,热导率随温度的升高几乎呈线性下降.孔隙率一定时,随孔径增大,介孔Al2O3材料比表面积降低,界面散射的抑制作用减弱,使材料热导率略有上升;孔径一定时,随孔隙率上升,孔道壁面声子数减少,材料热导率下降明显;相对于孔径因素,材料孔隙率对声子导热影响更大.     

Key factor affecting the structural and textural properties of ZSM-5/MCM-41 composite

ZSM-5/MCM-41 micro/mesoporous composite materials were synthesized by the hydrothermal technique with alkali-treated ZSM-5 zeolite as source of silica and aluminum and characterized by various physico-chemical techniques such as X-ray diffraction (XRD), nitrogen sorption at 77 K, transmission electronic microscopy (TEM), FTIR spectroscopy and NH₃ temperature programmed desorption (TPD) techniques. The effect of concentration of CTAB in the synthesis of these solids has been investigated, the mesopore volume, surface area and surface acidity decrease with increasing the concentration of CTAB. Increasing the CTAB concentration causes the recrystallization of zeolite ZSM-5 and it disadvantage the formation of mesoporous materials MCM-41. The catalytic activity of ZSM-5/MCM-41 materials has been evaluated in the Friedel–Crafts acylation of anisole with benzoyl chloride as alkylating agent. The results revealed the reaction to be influenced by surface area, pore volume and surface acidity.     

Sonochemical synthesis,structural, magnetic and grain size dependent electrical properties of NdVO4 nanoparticles

NdVO₄ nanoparticles are successfully synthesized by efficient sonochemical method using two different structural directing agents like CTAB and P123. The phase formation and functional group analysis are carried out using X-ray diffraction (XRD) and fourier transform infra red (FT-IR) spectra, respectively. Using Scherrer equation the calculated grain sizes are 27 nm, 24 nm and 20 nm corresponding to NdVO₄ synthesized by without surfactant, with CTAB and P123, respectively. The TEM images revealed that the shape of NdVO₄ particles is rice-like and rod shaped particles while using CTAB and P123 as surfactants. The growth mechanism of NdVO₄ nanoparticles is elucidated with the aid of TEM analysis. From electrical analysis, the conductivity of NdVO₄ nanoparticles synthesized without surfactant showed a higher conductivity of 5.5703 × 10⁻⁶ S cm⁻¹. The conductivity of the material depends on grain size and increased with increase in grain size due to the grain size effect. The magnetic measurements indicated the paramagnetic behavior of NdVO₄ nanoparticles.     

Mesopore size dependence of the ionic diffusivity in alumina based composite lithium ionic conductors

Ordered-mesoporous Al₂O₃ was synthesized by a sol–gel method using neutral copolymer surfactants as structure-directing agents. The pore size was controlled over the 3–15 nm range by the use of various surfactants. Composites composed of the synthesized mesoporous Al₂O₃ and a lithium ion conductor (LiI) were prepared. The maximum dc electrical conductivity, 2.6 × 10^− 4 S cm^− 1 at 298 K, was observed for 50 LiI·50 Al₂O₃ composite with 4.2 nm average mesopore size, which was considerably higher than the previously reported LiI-alumina composites. A systematic dependence of conductivity upon pore size was observed, in which conductivity increased with decreasing pore size, except for samples with a pore size of 2.8 nm. The lithium ion diffusion coefficient determined by the ⁷Li pulsed field gradient nuclear magnetic resonance (PFG-NMR) showed excellent agreement with the measured conductivity calculated by the Nernst-Einstein equation. On the other hand, lithium migration activation energies obtained by quasielastic neutron scattering (QENS) and ⁷Li NMR spin-lattice relaxation time (T₁) were considerably smaller than those obtained from electrical conductivity and PFG-NMR. This could be explained by the ion migration mechanism in heterogeneous composites and a possible enhancement of conductivity in mesoscopically confined spaces.     

Fabrication and application of highly ordered mesoporous Co3O4, NiO, and their metals

Highly ordered mesoporous Co₃O₄, NiO, and their metals were synthesized by nanocasting method using there corresponding mesoporous SBA-15 silica as a template. The obtained porous metal oxides have high surface areas, large pore volume, and a narrow pore size distribution. The N₂-adsorption data for mesoporous metal oxides have provided the BET area of 257.7 m² g⁻¹ and the total pore volume of 0.46 cm³ g⁻¹. The mesoporous metals were employed as a catalyst in the synthesis of (S)-3-pyrrolidinol from chiral (S)-4-chloro-3-hydroxybutyronitrile, and a high yield to (S)-3-pyrrolidinol-salt was obtained on the mesoporous Co metal catalyst.     

Structural and magnetic studies of Fe2O3/SiO2 granular nanocomposites

Fe₂O₃/SiO₂ nanocomposites were synthesized by mechanical alloying, using Fe and SiO₂ powders as precursors. After 340 h milling, the sample essentially consists of hematite and amorphous silica. TEM images show hematite particles embedded in and surrounded by an amorphous silica matrix. A broad size distribution—5–50 nm—of hematite particles is found, and other group of very small—2–3 nm—unidentified particles are observed. Room temperature Mössbauer spectra show a paramagnetic doublet, which may correspond to a non-crystalline phase in the sample (probably the small unidentified particles), and a sextet corresponding to hematite. Magnetic properties were investigated by measuring hysteresis curves at different temperatures (5–300 K) and by zero-field-cooled (ZFC) and field-cooled (FC) magnetization curves (10 mT). The hysteresis loops were well fitted by a ferromagnetic contribution. No evidence of Morin transition is found down to 5 K.     

Effect of the Si/Ce molar ratio on the textural properties of rare earth element cerium incorporated mesoporous molecular sieves obtained room temperature

Rare earth Ce-incorporated MCM-41 mesoporous molecular sieves (CeMCM-41) were synthesized via a direct and nonhydrothermal method at room temperature from sodium silicate and ammonium cerium (IV) nitrate as raw materials. Cetyltrimethyl ammonium bromide (CTAB) was used as a template. The resultant samples were characterized by means of powder X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), diffuse reflectance ultraviolet–visible spectroscopy (UV–vis) and N₂ physical adsorption, respectively. The effect of the Si/Ce molar ratio on the crystalline structure and textural properties of CeMCM-41 was also investigated. The experimental results show that ordered CeMCM-41 mesoporous molecular sieves were successfully synthesized at room temperature and the resultant mesoporous materials have specific surface areas in the range of 594–1369 m²/g and average pore sizes in the range of ca. 2.5–2.8 nm. It has been found that the structural properties are strongly related to the amounts of cerium incorporation. When the cerium content increased in the samples, the intensity of the peak (1 0 0) was gradually reduced, and the surface area and structural regularity were diminished.     

Electrodeposition of mesoporous ruthenium oxide using an aqueous mixture of CTAB and SDS as a templating agent

Mesoporous RuO₂ films were electrochemically fabricated on ITO-coated glass substrate from aqueous ruthenium chloride (RuCl₃·nH₂O) solution. To achieve highly stable mesoporous structure, an aqueous mixture of cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) was used as a templating agent.The mesoporous structure was confirmed by small angle X-ray diffraction (SAXRD) and transmission electron microscopy (TEM). The addition of small amount (10wt%) of CTAB significantly improved the stability of porous structure. The crystallinity of synthesized RuO₂ thin film was confirmed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Specific capacitance of the synthesized films was evaluated by measuring cyclic voltammetry (CV) and charge-discharge curves in 0.5 M H₂SO₄. Compared with non-porous electrode, mesoporous RuO₂ showed higher supercapacitor performance.     

Synthesis and high catalytic activity of mesoporous Co3O4 nanowires for carbon monoxide oxidation

Mesoporous Co₃O₄ nanowires were synthesized through a thermal decomposition process of an intermediate product. These nanowires have diameters of 20–35 nm and lengths ranging from 3 to 5 μm. They possess mesoporous structure with pore size of about 5.72 nm and relative high surface area of ca.66.6 m²/g. These nanowires exhibit high catalytic activity in conversion process of CO to CO₂. A possible mechanism is suggested for CO oxidation over the Co₃O₄ product.     

Fluorescent monodisperse spherical particles based on mesoporous silica containing rhodamine 6G

Fluorescent monodisperse spherical silica (SiO₂) particles with a regular mesoporous structure containing encapsulated Rhodamine 6G (R6G) dye have been synthesized. The as-synthesized particles have been coated with SiO₂ and SiO₂-CTAB (cetyltrimethylammonium bromide, C₁₆H₃₃N(CH₃)₃Br) shells in order to prevent uncontrolled release of the dye from pores. The kinetics of R6G release from the pores of silica particles has been studied. It has been found that the particles synthesized by adding CTAB and R6G to the reaction mixture, as well as the particles coated with the SiO₂-CTAB shell, are characterized by the maximum duration of dye release from the pores, which is probably associated with the formation of chemical bonds between R6G and CTAB molecules.     

Influence of Fe ions in characteristics and optical properties of mesoporous titanium oxide thin films

Fe-doped mesoporous titanium dioxide (M-TiO₂-Fe) thin films have been prepared on indium tin oxide (ITO) glass substrates by sol–gel and spin coating methods. All films exhibited mesoporous structure with the pore size around 5–9 nm characterized by small angle X-ray diffraction (SAXRD) and further confirmed by high resolution transmission electron microscopy (HRTEM). Raman spectra illustrated that lower Fe-doping contributed to the formation of nanocrystalline of M-TiO₂-Fe thin films. X-ray photoelectron spectroscopy (XPS) data indicated that the doped Fe ions exist in forms of Fe³⁺, which can play a role as e⁻ or h⁺ traps and reduce e⁻/h⁺ pair recombination rate. Optical properties including refractive indices/n, energy gaps/E_g and Urbach energy width/E₀ of the thin films were estimated and investigated by UV/vis transmittance spectra. The presence of Fe content extended the light absorption band and decreased the values of n, implying enhanced light response and performance on dye-sensitized solar cells (DSSC). The optimum Fe content in M-TiO₂-Fe thin films is determined as 10 mol%, for its compatibility of well crystalline and well potential electron transfer performance.     

Size-dependent freezing of n-alcohols in silicon nanochannels

We present a study on the phase behavior of several linear n-alcohols (heptanol, nonanol and undecanol) in their bulk state as well as confined in mesoporous silicon. We were able to vary the mean pore radii of the nanochannels from r = 3.5  nm to 7 nm and to determine the respective temperatures of the freezing and melting transitions using infrared and dielectric spectroscopy. The smaller the chain length the lower the freezing point, both in the bulk and in the confined state. Under confinement the freezing temperature decreases by up to 28 K compared to the bulk value. In accordance with the Gibbs-Thompson model the lowering is proportional to the inverse pore radius, ΔT _fr ∝ 1/r. Moreover, the ratio of freezing temperature depression to melting temperature depression is close to the theoretical value of ΔT _fr /ΔT _melt = 3/2. The spectra also indicate a structural change: while the solid bulk alcohols are a polycrystalline mixture of the orthorhombic β- and monoclinic γ-form, geometrical confinement forces the alcohol-chains into the more simple orthorhombic structure. In addition, a part of the material does not crystallize. Such an additional amorphous phase seems to be a logical consequence of the size mismatch between molecular crystals and irregular shaped pores.     

Synthesis and characterization of mesoporous ZnS with narrow size distribution of small pores

Pure, nanocrystalline cubic ZnS forming a stable mesoporous structure was synthesized at room temperature by a non-toxic surfactant-assisted liquid–liquid reaction, in the 9.5–10.5 pH range of values. The appearance of an X-ray diffraction (XRD) peak in the region of very small angles (∼ 2°) reveals the presence of a porous material with a narrow pore size distribution, but with an irregular arrangement of the pores, a so-called worm hole or sponge-like material. The analysis of the wide angle XRD diffractograms shows the building blocks to be ZnS nanocrystals with cubic structure and average diameter of 2 nm. Transmission electron microscopy (TEM) investigations confirm the XRD results; ZnS crystallites of 2.5 nm with cubic (blende) structure are the building blocks of the pore walls with pore sizes from 1.9 to 2.5 nm, and a broader size distribution for samples with smaller pores. Textural measurements (N₂ adsorption–desorption isotherms) confirm the presence of mesoporous ZnS with a narrow range of small pore sizes. The relatively lower surface area of around 100 m²/g is attributed to some remaining organic molecules, which are filling the smallest pores. Their presence, confirmed by IR spectroscopy, seems to be responsible for the high stability of the resulting mesoporous ZnS as well. PACS  61.46.Df; 68.37.Lp; 78.67.-n; 81.05.Ea; 81.07.Bc     

Novel nanofluids based on mesoporous silica for enhanced heat transfer

Nanofluids, which are liquids with engineered nanometer-sized particles suspensions, have drawn remarkable attraction from the researchers because of their enormous potential to enhance the efficiency in heat-transfer fluids. In the present study, water-based calcined mesoporous silica nanofluids were prepared and characterized. The commercial mesoporous silica (MPSiO₂) nanoparticles were dispersed in deionized water by means of pH adjustment and ultrasonic agitation. MPSiO₂ nanoparticles were observed to have an average particle size of 350 ± 100 nm by SEM analysis. The concentration of MPSiO₂ was varied between 1 and 6 wt%. The physicochemical properties of nanofluids were characterized using various techniques, such as particle size analyzer, zeta-potential meter, TEM, and FT-IR. The thermal conductivity was measured by Transient Plane Source (TPS) method, and nanofluids showed a higher thermal conductivity than the base liquid for all the tested concentrations.     

Iron oxide nanoparticles stabilized inside highly ordered mesoporous silica

Nanosized iron oxide, a moderately large band-gap semiconductor and an essential component of optoelectrical and magnetic devices, has been prepared successfully inside the restricted internal pores of mesoporous silica material throughin-situ reduction during impregnation. The samples were characterized by powder XRD, TEM, SEM/EDS, N₂ adsorption, FT-IR and UV-visible spectroscopies. Characterization data indicated well-dispersed isolated nanoclusters of (Fe₂O₃) _n , within the internal surface of 2D-hexagonal mesoporous silica structure. No occluded Fe/Fe₂O₃ crystallites were observed at the external surface of the mesoporous silica nanocomposites. Inorganic mesoporous host, such as hydrophilic silica in the pore walls, directs a physical constraint necessary to prevent the creation of large Fe₂O₃ agglomerates and enables the formation of nanosized Fe₂O₃ particles inside the mesopore     

One-pot synthesis of hybrid nanospheres with multistructure for selective adsorption of Hg<Superscript>2+</Superscript>

Novel complex nanospheres with core/shell structure for selective adsorption of Hg²⁺ have been prepared by a simple one-pot method. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) images showed the nanospheres had perpendicularly thiol-functionalized mesoporous SiO₂ hybrid shell and Fe₃O₄@SiO₂ core (Fe₃O₄@nSiO₂@mSiO₂–SH). XRD patterns of as-synthesized nanospheres confirmed the observation of the SEM and TEM. The size of the nanospheres is about 100 nm. Based on the analysis of N₂ sorption–desorption isotherm, the surface area and pore volume of the adsorbent are 861 m²/g and 0.48 cm³/g, respectively. The saturation magnetization value for Fe₃O₄@nSiO₂@mSiO₂–SH is as high as 6.87 emu g⁻¹. The nanospheres showed more accessible active sites and high dispersibility in water, exhibited excellent performance for selective Hg²⁺ adsorption, had a stable structure, and could be recycled easily with magnet.     

In situ growth of silver nanoparticles in mesoporous silica by spray pyrolysis

Silver-dispersed mesoporous silica was in situ synthesized in aerosol phase. The solidification of silica was catalyzed in the presence of the silver, which increased the order and d values of the mesophase at given reactor temperature. Silver nanoparticles grew confined in the pores when the atomic % of silver to Si was below 10 and the pore wall turned to be impermeable above 400 °C. Silver permeated through the pore wall below 400 °C to grow freely in the carrier gas. The mesophase deteriorated using spray pyrolysis above 800 °C due to the further densification of silica, or above 10 at.% of silver due to the excessive growth within the phase. The highest dispersion of silver ~4 nm in diameter with the highest order of the mesoporosity was obtained at 600 °C with 5 at.% silver. Calcination following the spray pyrolysis further densified the silica phase to freeze the growth of silver particles as well as lower the d value of the mesophase.