Preparation of large-pore mesoporous nanocrystalline TiO2 thin films with tailored pore diameters

A novel and facile synthesis route to large-pore mesoporous nanocrystalline anatase thin films with tunable pore diameters in narrow distribution of sizes ranging from 8.3 to 14 nm is reported, using triblock copolymer as the template and Ti(OBu(n))4 as the inorganic precursor. The obtained materials were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption. A reasonable formation mechanism is also presented in this work.     

Formation of porous carbon materials with in situ generated NaF nanotemplate

Porous carbon materials with pore sizes from 3 to 200 nm were synthesized by reacting hexafluorobenzene with Na liquid at 623 K. NaF crystals, a byproduct formed in the reaction, acted as nanotemplate to assist the pore formation. By employing hexafluorobenzene to react with Na incorporated within the channels (diameter 200 nm) of anodized aluminum oxide (AAO) membranes at 323-623 K, the carbon material can be fabricated into aligned porous nanotube arrays (ca. 250 nm in diameter, ca. 20 nm in wall thickness, ca. 0.06 mm in length, and ca. 3-90 nm in pore diameter). These materials were characterized by X-ray diffraction, scanning and transmission electron microscopy, X-ray energy dispersive spectroscopy, electron diffraction, thermal gravimetric analysis, and nitrogen physical adsorption experiments.     

Self-supported particle-track-etched polycarbonate membranes as templates for cylindrical polypyrrole nanotubes and nanowires: an X-ray scattering and scanning force microscopy investigation

Self-supported particle-track-etched polycarbonate membranes with nearly perfect cylindrical pores are used for the preparation of similarly perfect cylindrical polypyrrole nanowires and nanotubes. A complete investigation of the structural properties that result at different stages of the preparation route of polypyrrole nanowires and nanotubes is based on a combination of real and reciprocal space techniques. Nanoporous membranes with nominal pore size ranging from 5 to 150 nm and pore density up to 10(9) pores/cm(2) made from 21-microm-thick polycarbonate films are used. Polypyrrole nanotubes or nanowires are synthesized inside the pores. A real-space picture of the nanomaterial results from scanning force microscopy (SFM) on ultrathin sections made in two directions to obtain structures in the sample surface as well as perpendicular to the surface. From a model-based fit to the small-angle and ultra-small-angle X-ray scattering (SAXS/USAXS) data, the geometric pore structure is obtained and compared to values determined with scanning electron microscopy (SEM). Nanopores, nanowires, and nanotubes are described by uniform solid cylinders or hollow tubes, which are oriented highly parallel to each other and exhibit a small size distribution. Below a critical pore diameter, solid nanowires are produced whereas above this limit hollow nanotubes result.     

有序介孔二氧化硅对正丁醛的吸附性能

合成了一系列具有不同孔结构与性质的有序介孔二氧化硅材料SBA-15、MCM-41、SBA-16、KIT-6,同时通过改变水热温度制备了不同孔径大小的SBA-15,并利用小角X射线散射、透射电镜、扫描电镜和氮气吸附-脱附等手段,对其介孔结构进行了表征.以正丁醛为探针分子,考察了其对有机醛的吸附,并与Y-沸石的吸附性能做了对比.结果表明,材料的介孔比表面积与其对正丁醛的吸附量成正比,吸附等温线符合Langmuir模型,属于单层吸附,具有最大介孔比表面积的MCM-41对正丁醛的吸附量最大(484 mg·g-1).最后将SBA-15添加到卷烟滤嘴中,实验结果表明,SBA-15能显著降低卷烟烟气中巴豆醛的释放量.     

有序介孔二氧化硅对正丁醛的吸附性能

合成了一系列具有不同孔结构与性质的有序介孔二氧化硅材料SBA-15、MCM-41、SBA-16、KIT-6, 同时通过改变水热温度制备了不同孔径大小的SBA-15, 并利用小角X射线散射、透射电镜、扫描电镜和氮气吸附-脱附等手段, 对其介孔结构进行了表征. 以正丁醛为探针分子, 考察了其对有机醛的吸附, 并与Y-沸石的吸附性能做了对比. 结果表明, 材料的介孔比表面积与其对正丁醛的吸附量成正比, 吸附等温线符合Langmuir 模型, 属于单层吸附, 具有最大介孔比表面积的MCM-41对正丁醛的吸附量最大(484 mg·g^-1). 最后将SBA-15添加到卷烟滤嘴中, 实验结果表明, SBA-15能显著降低卷烟烟气中巴豆醛的释放量.     

SAXS and TEM Investigations on Thermoplastic Nanocomposites Containing Functionalized Silica Nanoparticles

Transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) were used to characterize the morphology of thermoplastic nanocomposites. These materials were based on a thermoplastic matrix of a copolymer of methylmethacrylate (MMA) and 2-hydroxyethylmethacrylate (HEMA) with spherical 10 nm silica particles as a filler (filler content 2, 5 and 10 vol%, respectively). Depending on the surface modification of the particles, it was possible to control the aggregation tendency of the primary filler particles. With uncoated particles large aggregates about 100 nm in size could be observed by TEM. For nanocomposites containing particles coated with methacryloxypropyltrimethoxysilane (MPTS), TEM showed that the particles were better dispersed in the polymer matrix only forming aggregates comprised of two or three primary particles. In comparison to the TEM results, the volume weighted particle size distribution calculated from SAXS for the systems with uncoated particles is monomodal and shows particle sizes in the range of primary particles whereas the systems with MPTS coated particles revealed a bimodal size distribution with particle sizes comparable to those measured with TEM. To obtain complete information about the morphology of the nanocomposites above the critical upper limit of detectable scattering vectors (particle sizes >50 nm) SAXS has to be supported by TEM, whereas in the nanosize range below the critical limit both methods exhibit an excellent correspondence.     

Fabrication of hierarchically porous silica nanospheres through sol–gel process and pseudomorphic transformation

Hierarchically porous silica nanospheres with well-defined morphology and uniform particle size had been synthesized through a multistep sol–gel method combined with pseudomorphic transformation in the presence of polyvinylpyrrolidone (PVP) and cetyltrimethylammoium bromide (CTAB) as dual template. The prepared materials were characterized by small-angle X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and nitrogen physical adsorption techniques. The preparation process and the origin of hierarchical structure were also investigated. It had been shown that the hierarchical structure of synthesized materials comprises wormlike framework mesopores with diameters of about 3 nm and bubble-like pores with diameters of 20–30 nm. CTAB and PVP behave as dual-template and are responsible for the formation of the mesopores and big pores, respectively. Not only the porous structure, but also the morphology and particle size of hierarchical materials can be adjusted by controlling the addition of PVP. In addition, the formation process of hierarchically porous silica was investigated by transmission electron microscopy, FT-IR spectra and thermo-gravimetric curves and a possible synthetic mechanism had been proposed.     

Synthesis and characterization of Mn2P2S6 single-crystal nanorods and nanotubes

Mn2P2S6 single-crystal nanorods with diameters 20-40 nm and lengths up to 1 microm and nanotubes with diameters 40-50 nm and lengths ranging between 110 and 170 nm have been prepared through a low-temperature solvothermal method. They have been characterized by X-ray diffraction, transmission electron microscopy (TEM), high-resolution (HR) TEM, electron diffraction, energy-dispersive spectrometry analysis, X-ray photoelectron spectroscopy, and Raman spectroscopy.     

Bicrystalline hematite nanowires

Bicrystalline nanowires of hematite (alpha-Fe(2)O(3)) have been successfully synthesized by the oxidation of pure iron. The product was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy (TEM), high-resolution TEM in combination with focal series reconstruction, energy-dispersive X-ray spectroscopy, and electron energy-loss spectroscopy. The bicrystalline nanowires have diameters of 20-80 nm and lengths up to 20 microm. All of the investigated materials are found to be alpha-Fe(2)O(3) with a rhombohedral crystal structure. Investigations indicate that most of the bicrystalline nanowires are nanotwins with ellipsoidal heads. The orientation relationship between the nanotwins can be described as (110)(M)//(110)(T), [110](M)//[0](T). An energy-filtered TEM investigation indicates that the ellipsoidal head is iron-rich. The growth mechanism of such unique nanostructures is considered to be a solid-phase growth via surface and internal diffusions of molecules from base to tip.     

Large-area highly-oriented SiC nanowire arrays: synthesis, Raman, and photoluminescence properties

Large-area highly oriented SiC nanowire arrays have been fabricated by chemical vapor reaction using an ordered nanoporous anodic aluminum oxide (AAO) template and a graphite reaction cell. Their microstructures were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction and high-resolution transmission electron microscopy. The results show that the nanowires are single-crystalline beta-SiC's with diameters of about 30-60 nm and lengths of about 8 microm, which are parallel to each other, uniformly distributed, highly oriented, and in agreement with the nanopore diameter of the applied AAO template. The nanowire axes lie along the [111] direction and possess a high density of planar defects. Some unique optical properties are found in the Raman spectroscopy and photoluminescence emission from oriented SiC nanowire arrays, which are different from previous observations of SiC materials. The growth mechanism of oriented SiC nanowire arrays is also analyzed and discussed.     

Effects of Co-Solvent Nature and Acid Concentration in the Size and Morphology of Wrinkled Mesoporous Silica Nanoparticles for Drug Delivery Applications

Hierarchically porous materials, such as wrinkled mesoporous silica (WMS), have gained interest in the last couple of decades, because of their wide range of applications in fields such as nanomedicine, energy, and catalysis. The mechanism of formation of these nanostructures is not fully understood, despite various groups reporting very comprehensive studies. Furthermore, achieving particle diameters of 100 nm or less has proven difficult. In this study, the effects on particle size, pore size, and particle morphology of several co-solvents were evaluated. Additionally, varying concentrations of acid during synthesis affected the particle sizes, yielding particles smaller than 100 nm. The morphology and physical properties of the nanoparticles were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and dynamic light scattering (DLS). Homogeneous and spherical WMS, with the desired radial wrinkle morphology and particle sizes smaller than 100 nm, were obtained. The effect of the nature of the co-solvents and the concentration of acid are explained within the frame of previously reported mechanisms of formation, to further elucidate this intricate process.     

Large-area Sb2Te3 nanowire arrays

High-density large-area nanowire arrays of thermoelectric material Sb(2)Te(3) have been successfully prepared using electrochemical deposition into the channels of the porous anodic alumina membrane. The morphologies, structure, and composition of the as-prepared Sb(2)Te(3) nanowires have been characterized using field-emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Individual Sb(2)Te(3) nanowires are single crystalline and continuous with uniform diameters ( approximately 50 nm) throughout the entire length. The atomic ratio of Sb to Te is very close to the 2:3 stoichiometry.     

Preparation and characterisation of poly(high internal phase emulsion) methacrylate monoliths and their application as separation media

Poly(glycidyl methacrylate-co-ethyleneglycol dimethacrylate) monolithic supports were prepared by radical polymerisation of the continuous phase of water in oil high internal phase emulsions. Morphology of monolithic materials was studied by scanning electron microscopy and mercury intrusion porosimetry. The ratio of phase volume and the degree of crosslinking influenced the void size and pore size distribution of resulting polymers. Void sizes between 1 and 10 microm were observed and average pore sizes around 100 nm. Polymers with 60, 75, 80 and 90% pore volume were prepared and even samples with highest pore volume showed good mechanical stability. They were modified to bear weak-anion exchange groups and tested on the separation of standard protein mixture containing myoglobin, conalbumine and trypsin inhibitor. Good separation was obtained in a very short time similar to the separation obtained by commercial methacrylate monoliths. However, higher dispersion was observed. Bovine serum albumin dynamic binding capacity for monolith with 90% porosity was close to 9 mg/ml.     

共缩聚法制备有序介孔氧化硅纳米螺旋纤维

在传统球状介孔氧化硅合成工作的基础上,以正硅酸乙(TEOS)和γ-巯丙基三甲氧基硅烷(MPTMS)为硅源,在水体系下利用共缩聚法一步合成出具有介孔分子筛结构特征的纳米纤维,并通过扫描电子显微镜(SEM)、小角X射线衍(XRD)、透射电子显微镜(TEM)和氮气吸附-脱附实验对样品进行了表征与分析.     

Using collagen fiber as a template to synthesize hierarchical mesoporous alumina fiber

Hierarchical mesoporous alumina fiber was synthesized by using collagen fiber as the template, and characterized by means of scanning electron microscopy, transmission electron microscopy, N2 adsorption techniques, X-ray photoelectron spectroscopy, and X-ray diffraction. The alumina fiber obtained is approximately 1-4 microm in outer diameter and 0.5-1 mm in length. The pore size distribution of the alumina fiber is narrow (2-20 nm), and its pore size is controllable by varying preparation methods. This study indicates that collagen fiber, which has hierarchical supermolecular structure, could be used as an ideal template to prepare well-defined porous metal oxide fibers.     

Nondestructive technique for the characterization of the pore size distribution of soft porous constructs for tissue engineering

Polymer scaffolds tailored for tissue engineering applications possessing the desired pore structure require reproducible fabrication techniques. Nondestructive, quantitative methods for pore characterization are required to determine the pore size and its distribution. In this study, a promising alternative to traditional pore size characterization techniques is presented. We introduce a quantitative, nondestructive and inexpensive method to determine the pore size distribution of large soft porous solids based on the on the displacement of a liquid, that spreads without limits though a porous medium, by nitrogen. The capillary pressure is measured and related to the pore sizes as well as the pore size distribution of the narrowest bottlenecks of the largest interconnected pores in a porous medium. The measured pore diameters correspond to the narrowest bottleneck of the largest pores connecting the bottom with the top surface of a given porous solid. The applicability and reproducibility of the breakthrough technique is demonstrated on two polyurethane foams, manufactured using the thermally induced phase separation (TIPS) process, with almost identical overall porosity (60-70%) but very different pore morphology. By selecting different quenching temperatures to induce polymer phase separation, the pore structure could be regulated while maintaining the overall porosity. Depending on the quenching temperature, the foams exhibited either longitudinally oriented tubular macropores interconnected with micropores or independent macropores connected to adjacent pores via openings in the pore walls. The pore size and its distribution obtained by the breakthrough test were in excellent agreement to conventional characterization techniques, such as scanning electron microscopy combined with image analysis, BET technique, and mercury intrusion porosimetry. This technique is suitable for the characterization of the micro- and macropore structure of soft porous solids intended for tissue engineering applications. The method is sensitive for the smallest bottlenecks of the largest continuous pores throughout the scaffold that contributes to fluid flow.     

Nanoporous structured submicrometer carbon fibers prepared via solution electrospinning of polymer blends

A facile means for obtaining submicrometer carbon fibers with a nanoporous structure is presented. A mixture of polyacrylonitrile (PAN) and a copolymer of acrylonitrile and methyl methacrylate (poly(AN-co-MMA)) in dimethylformamide was electrospun into submicrometer fibers with a microphase-separated structure. During the followed oxidation process, the copolymer domains were pyrolyzed, resulting in a nanoporous structure that was preserved after carbonization. The microphase-separated structure of the PAN/poly(AN-co-MMA) electrospun fibers, the morphology, and porous structure of both the oxidized and the carbonized fibers were observed with scanning electron microscopy and transmission electron microscopy. The carbon fibers have diameters ranging from several hundred nanometers to about 1 microm. The nanopores or nanoslits throughout the fiber surface and interior with diameters of several tens of nanometers are interconnected and oriented along the longitudinal axis of the fibers. This unique nanoporous morphology similar to the microphase-separated structure in the PAN/poly(AN-co-MMA) fibers is attributed to the rapid phase separation, solidification, as well as the stretching of the fibers during electrospinning. The pore volume and pore size distribution of the carbonized fibers were investigated by nitrogen adsorption and desorption.     

Mesoporous silica spheres from colloids

A novel method has been developed to synthesize mesoporous silica spheres using commercial silica colloids (SNOWTEX) as precursors and electrolytes (ammonium nitrate and sodium chloride) as destabilizers. Crosslinked polyacrylamide hydrogel was used as a temporary barrier to obtain dispersible spherical mesoporous silica particles. The influences of synthesis conditions including solution composition and calcination temperature on the formation of the mesoporous silica particles were systematically investigated. The structure and morphology of the mesoporous silica particles were characterized via scanning electron microscopy (SEM) and N2 sorption technique. Mesoporous silica particles with particle diameters ranging from 0.5 to 1.6 microm were produced whilst the BET surface area was in the range of 31-123 m2 g-1. Their pore size could be adjusted from 14.1 to 28.8 nm by increasing the starting particle diameter from 20-30 nm up to 70-100 nm. A simple and cost effective method is reported that should open up new opportunities for the synthesis of scalable host materials with controllable structures.     

Room temperature synthesis of hollow CdMoO(4) microspheres by a surfactant-free aqueous solution route

Hollow cadmium molybdate microspheres have been successfully prepared via a template-free aqueous solution method with the assistance of NaCl at room temperature. The structure and morphology of the CdMoO(4) hollow microspheres were characterized by X-ray diffraction, field-emission scanning electron microscopy, and transmission electron microscopy. The microspheres have diameters of 3-6 microm and hollow interiors of 2-3 microm. The shell is composed of numerous single-crystalline nanorods with diameters of 30-120 nm and lengths of 1-2 microm which are radially oriented to the center. A certain concentration of NaCl plays a key important role in the formation process of hollow microspheres, which might provide a suitable chemical environment to favor the formation of hollow CdMoO(4) microspheres. A possible NaCl-induced Ostwald ripening process is proposed for the formation of hollow CdMoO(4) microspheres on the basis of scanning electron microscopy observation of intermediate products at different precipitation stages.     

The influence of mercury contact angle, surface tension, and retraction mechanism on the interpretation of mercury porosimetry data

The use of a semi-empirical alternative to the standard Washburn equation for the interpretation of raw mercury porosimetry data has been advocated. The alternative expression takes account of variations in both mercury contact angle and surface tension with pore size, for both advancing and retreating mercury meniscii. The semi-empirical equation presented was ultimately derived from electron microscopy data, obtained for controlled pore glasses by previous workers. It has been found that this equation is also suitable for the interpretation of raw data for sol-gel silica spheres. Interpretation of mercury porosimetry data using the alternative to the standard Washburn equation was found to give rise to pore sizes similar to those obtained from corresponding SAXS data. The interpretation of porosimetry data, for both whole and finely powdered silica spheres, using the alternative expression has demonstrated that the hysteresis and mercury entrapment observed for whole samples does not occur for fragmented samples. Therefore, for these materials, the structural hysteresis and overall level of mercury entrapment is caused by the macroscopic (> approximately 30 microm), and not the microscopic (< approximately 30 microm), properties of the porous medium. This finding suggested that mercury porosimetry may be used to obtain a statistical characterization of sample macroscopic structure similar to that obtained using MRI. In addition, from a comparison of the pore size distribution from porosimetry with that obtained using complementary nitrogen sorption data, it was found that, even in the absence of hysteresis and mercury entrapment, pore shielding effects were still present. This observation suggested that the mercury extrusion process does not occur by a piston-type retraction mechanism and, therefore, the usual method for the application of percolation concepts to mercury retraction is flawed.