EXAFS study on the sulfidation behavior of Pd, Pt and Pd–Pt catalysts supported on amorphous silica and high-silica USY zeolite

The sulfur tolerance of monometallic Pd, Pt and bimetallic Pd–Pt catalysts supported on slightly acidic ultra-stable Y (USY) zeolite (SiO₂/Al₂O₃ = 390) and on non-acidic silica, having mesopores with a pore diameter of 3 or 10 nm, were investigated using the CO adsorption method and the extended X-ray adsorption fine structure (EXAFS) method. Well-dispersed noble metal particles supported on USY zeolite and silica with an average pore diameter of 3 nm showed high surface sulfur tolerance and high catalytic hydrogenation activity, although bulk phase sulfidation simultaneously occurred. The synergistic effects of sulfur tolerance were significant in the bimetallic Pd–Pt particles supported on USY zeolite and silica with an average pore diameter of 3 nm. On the other hand, on silica with an average pore diameter of 10 nm, the surface sulfur tolerance of low dispersed noble metals was the lowest, although its bulk phase sulfur tolerance was the highest. The Pd K-edge and Pt L_III-edge EXAFS spectra indicated a strong interaction between the well-dispersed noble metal particles and the supports of the USY zeolite and silica with an average pore diameter of 3 nm. This distorted structure may increase the sulfur tolerance of noble metals, though some surface and bulk phase sulfidation simultaneously occurred.     

Formation of Porous SiC Ceramics by Pyrolysis of Wood Impregnated with Silica

Biomorphous β-SiC ceramics were produced at 1400°C from pine wood impregnated with silica. This one-step carbothermal reduction process decreases the cost of manufacturing of SiC ceramics compared with siliconization of carbonized wood in silicon vapor. The synthesized sample exhibits a 14 m²/g surface area and has a hybrid pore structure with large 5–20 μm tubular macropores and small (<50 nm) slit-shaped mesopores. SiC whiskers of 20–400 nm in diameter and 5–20 μm in length formed within the tubular pores. These whiskers are expected to improve the filtration by removing dust particles that could otherwise penetrate through large pores. After ultrasonic milling, the powdered sample showed an average particle size of ∼30 nm. The SiC nanopowder produced in this process may be used for manufacturing SiC ceramics for structural, tribological, and other applications.     

Influence of Sintering Temperature on Pore Structure and Apatite Formation of a Sol–Gel-Derived Bioactive Glass

The aim of this work was to investigate the influence of sintering temperature on the porous morphology, pore-size distribution, and apatite formation of sol–gel-derived porous bioactive glasses. For this purpose, three porous bioactive glasses were prepared by thermal phase separation cotemplate method in sol–gel process followed by sintering at 600°, 800°, and 1000°C. Pore structure of samples was characterized by various methods. The in vitro apatite formation test was carried out in simulated body fluid. The results showed that sintered bioactive glasses at 600°C exhibited a bimodal pore size distribution, mesopores, and nanopores (8–100 nm), macropores (100 nm–1 μm), and nanoscale pore walls (about 100 nm in width). The increase of sintering temperature induced the presence of a submicrometer pore-size distribution (300 nm–3 μm) with nanoscale pore walls (about 200 nm in width) and a morphological transformation from particle-like pore walls to dense pore walls. Depending on this porous structure, as-synthesized samples exhibited faster apatite formation capability.     

Synthesis and hierarchical pore structure of biomorphic manganese oxide derived from woods

Biomorphic manganese oxides on two different wood templates (fir and paulownia) were fabricated by infiltration with nitrate and subsequently calcination. X-ray diffraction (XRD) test and microscopy observation (FESEM and TEM) were employed to characterize the phase and structure of biomorphic manganese oxides. The pore structure of the resulting products was studied through mercury intrusion and nitrogen adsorption measurement. Infrared (IR) adsorption properties were investigated by Fourier Transmission Infrared (FTIR). The final oxide products contain hierarchical pore structure from μm to nm scale, and also show unique pore size and distribution with hierarchy on nanoscale derived from the specific wood template, the changeable connectivity of nanoscale pore channel controlled by calcinations temperature. The rise of temperature leads to diminishing of average pore diameter and volume but more uniform pore size distribution and higher degree of pore connectivity. The overall collapse in IR adsorption spectra of biomorphic manganese oxides with the rise of calcination temperature is related to the effect of nanoscale pore structure especially the increasing of pore connectivity.     

Porous chitin matrices for tissue engineering: Fabrication and in vitro cytotoxic assessment

A series of porous chitin matrices were fabricated by freezing and lyophilization of chitin gels cast from a 5% N,N-dimethylacetamide (DMAc)/lithium chloride (LiCl) solvent system. The porous chitin matrices were found to have uniform pore structure in the micron range. Scanning electron microscopy (SEM) revealed that the pore size of the porous chitin matrices varied according to the freezing method prior to lyophilization. By subjecting the chitin gels to dry-ice/acetone (−38 °C), the final porous chitin matrix gave pore dimensions measuring 200–500 μm with 69% porosity. A smaller pore dimension of 100–200 μm with 61% porosity was produced when the chitin gels were frozen by liquid nitrogen (−196 °C) and 10 μm pores with 54% porosity were produced when the gels were placed in a freezer (−20 °C) for 20 min. In comparison, lower porosity structures of ca. 10% porosity were obtained from both air-dried and critical point dried chitin gels. Furthermore, a low gel concentration (< 0.5%, w/w) also produced porous morphology by vacuum drying without any freezing and lyophilization. The resulting pore properties influenced the water uptake profile of the materials in water. These porous chitin matrices are found to be non-cytotoxic and to hold promise as potential structural scaffolds for cell growth and proliferation in vitro.     

Determination of Both Mesopores and Macropores in Three-Dimensional Ordered Porous Materials by Nitrogen Adsorption

Three-dimensionally ordered silica structures containing both mesopores and macropores are created using polystyrene coacervate spheres with a diameter of ca. 146 nm. The close-packed polystyrene coacervate spheres are intercalated with tetraethyl orthosilicate. The spheres are removed by calcination leaving an inverse silica replica with a spherical macropore cavity diameter of 110 nm. Due to the nature of these porous structures, pores leading into the macropore cavity are in the mesopore regime, 40 nm in diameter. The nitrogen adsorption data described in the following paper gives a pore size for both the macropore cavity and the mesopore openings leading into the cavity. The pore sizes as determined by nitrogen sorption are in good agreement with the pore sizes observed by scanning electron microscopy. Mercury intrusion porosimetry results confirm the size of the mesopore openings leading into the macropore cavity, however due to destruction of the sample upon intrusion, extrusion results can not be obtained to determine main cavity diameters. As a result, nitrogen sorption may be a viable option for determining pore sizes with these three-dimensionally ordered materials containing both mesopores and macropores.     

Synthesis of Nanoparticulate Silica Composite Membranes by the Pressurized Sol–Gel Technique

A crack-free silica composite membrane has been synthesized from a nanoparticulate silica sol (particle diameter <10 nm) by a pressurized sol–gel coating technique developed in this study. The microporous silica layers with an estimated pore radius of 0.78 nm were deposited inside the pores (average pore size of 0.1 μm) of slip cast a-alumina support tubes. The microstructure of the coated layer was controlled by adjusting sol properties and pressurizing conditions. The room-temperature intrinsic permeability of N₂ through the silica membrane layer after heat treatment at 200°C is about 4.9 × 10⁻¹² mol·m/m²·s· Pa, and the mechanism of gas transport is Knudsen flow. The thermal stability of the silica composite membrane is excellent up to 500°C.     

粉煤灰-水泥浆体的孔体积分形维数及其与孔结构和强度的关系

采用压汞法对不同龄期粉煤灰-水泥浆体的孔分形结构进行了实验研究，测定了复合浆体孔体积分形维数，探讨了孔体积分形维数与孔隙率，孔表面积、平均孔径、孔分布及宏观力学性能的关系。实验结果表明：粉煤灰-水泥浆体的孔结构具有明显的分形特征，孔体积分形维数在3．3～3．5之间；孔体积分形维数越大，浆体的孔径越小、孔隙率越低，孔表面积越大，小于20nm的微孔越多，大于100nm的大孔越少，而且复合体系的抗压及抗折强度也越高。     

Synthesis of Biomorphous Nickel Oxide from a Pinewood Template and Investigation on a Hierarchical Porous Structure

The hydrothermal synthesis of biomorphous nickel oxide (NiO) with pine template and nickel nitrate precursor is reported here. The morphology, porosity and connectivity of porous products in different length scales were characterized by field emission scanning electron microscopy, X-ray diffraction and nitrogen adsorption measurements. Their porous structures were found to be hierarchical from 1 up to 25 μm (in micrometer scale) and from 2 nm to 60 nm (in nanometer scale). Furthermore, depending on the heat-treatment temperatures, the porosity of the pine-templated NiO can be designed.     

Effects of electrospun polyacrylonitrile-based carbon nanofibers as catalyst support in PEMFC

This paper reports novel results regarding the effects of electrospun carbon nanofibers (e-CNF) as a catalyst support by comparison with the commercial Vulcan XC-72R (denoted as XC-72R) as granular particles. The e-CNF was synthesized by stabilizing and carbonizing the electrospun PAN-based fibers. The e-CNF showed an average diameter of 250 nm with a rough surface and was partially aligned along the winding direction of the drum winder. The characteristic morphology was fundamentally dependant on the shape of the carbon materials. The average pore size of the e-CNF was 2.36 nm, while that of the XC-72R was 10.92 nm. The morphology of e-CNF was developed by shallow pores with rough surfaces due to the effects of electrospinning and carbonization, while that of the XC-72R was largely developed by mesopores rather than micropores due to the granular shape. Compared to XC-72R, the performance of the MEA prepared by e-CNF was excellent, owing to the morphology and the enhanced electrical conductivity. The Pt utilization of Pt/e-CNF was 69%, while that of Pt/XC-72R was 35%.     

Synthesis and characterization of LTA zeolite with uniform intracrystal mesopores directed by bridged polysilsesquioxane monomer

An ordered mesoporous LTA zeolites (MLTA) have been synthesized in presence of the bridged polysilsesquioxane monomer (BS-1) as mesoporogen. The relatively well-defined small-angle X-ray diffraction peaks and nitrogen sorption isotherms with narrow pore size distribution centered at around 2.2 nm both indicated the presence of uniformly mesopores in MLTA samples. The scanning electron microscopy and transmission electron microscopy observations further confirmed that the uniform and partially interconnected intracrystal mesopores were randomly distributed throughout the globular particles with rugged surfaces. Interestingly, removal of the BS-1 resulted in uniform mesopore diameters that are nearly consistent with the molecular size of BS-1 (1.8 nm). ²⁹Si MAS NMR revealed that the BS-1 was linked to MLTA zeolite crystal surface through 2 Si–O bonds and 3 Si–O bonds before calcinations. Nitrogen sorption analysis showed that the mesoporosity in MLTA samples could be adjusted by adding different amounts of BS-1 in starting gels. Relative to conventional mesoporous materials, one obvious feature of MLTA is that the resultant mesopores were structured by the bridged polysilsesquioxane monomer instead of commercial polymers or micelles, which broad the routes in synthesizing of various mesoporous materials with controllable pore size distribution, adjustable mesopore volume, and large surface area.     

Synthesis and simple method of estimating macroporosity of methyl methacrylate–divinylbenzene copolymer beads

Macroporous methyl methacrylate–divinylbenzene copolymer beads having diameter ～ 300 μm were synthesized by free radical suspension copolymerization. The macroporosity was generated by diluting the monomers with inert organic liquid diluents. The macroporosity was varied in the range of ～0.1 to ～ 1.0 mL/g by varying a number of porosity controlling factors, such as the diluents, solvent to nonsolvent mixing ratios when employing a mixture of the two diluents, degree of dilution, and crosslinkage. Increase in pore volume from 0.1 to 0.45 mL/g resulted in a sharp increase in mesopores having diameters in the range of 3–20 nm whereas the macropores remained negligible when compared with mesopores. Increase in pore volume from 0.45 to 1 mL/g resulted in a sharp increase in macropores, whereas mesopores having diameters in the range of 3–20 nm remained almost constant. The mesopores having diameters in the range of 20–50 nm showed an increase with the increase in pore volume throughout the whole range of pore volume studied. Macroporosity characteristics, i.e., pore volume (V_m), surface area (SA), and pore size distributions were evaluated by mercury penetration method. Statistical analysis of the data obtained in the present study shows that the macroporosity characteristics can be estimated with a reasonable accuracy from the pore volumes, which in turn are determined from the densities of the copolymers. These results are explained on the basis of pore formation mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Modifications of the C–S–H Gel by Hydration at 40°C of Belite Cements from Coal Fly Ash Class C

The influence of the temperature on two types of hydrated fly ash belite cement (FABC) pastes were investigated at a nanoscale (1–100 nm) by measuring the specific surface area and pore-size distribution by the sorption isotherms of nitrogen gas and the BET method, and at a microscale from the pore-size distribution measured by mercury intrusion porosimetry. The two belite cements were fabricated by the hydrothermal–calcination route of fly ash class C in NaOH 1 M solution (FABC-2-N) and demineralized water (FABC-2-W). In the case of FABC-2-W, a densification of the C–S–H gel was produced at the temperature of 40°C, which favored the formation of pores ∼3 nm in diameter leading to higher surface area values, compared with the C–S–H gel formed at 20°C. At a microscale, the temperature led to an increase of capillary porosity (>0.05 μm) at a later age of hydration and, consequently, a decrease of compressive mechanical strength. In the case of FABC-2-N, the densification of the gel was less evident, but the increase of capillary porosity (pores of diameter >0.05 μm) was higher. Significant direct linear quantitative correlations were found among these nanostructure characteristics of the C–S–H gel and macrostructural engineering property such as the compressive mechanical strength, for the two FABC-2-W and FABC-2-N cements under normal conditions. At 40°C, the correlations were not so clear probably due to another microstructural factor such as the increase of the larger capillary porosity (>0.05 μm).     

Mesoporous silica fibers prepared by electroblowing of a poly(methyl methacrylate)/tetraethoxysilane mixture in N,N-dimethylformamide

Electroblowing and sol–gel reaction were combined to prepare mesoporous silica fibers. Poly(methyl methacrylate) (PMMA), a simple commercial polymer with weak hydrogen bonding to silica, was demonstrated to be valuable in improving the electrospinnability and as a porogenic agent. Compared with that in electrospinning, the jet stream in electroblowing was more stable and the resultant fibers were more uniform. The electroblown fibers were characterized by infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy and nitrogen adsorption and desorption isotherms. The phase separation behavior and mechanism for the formation of the amorphous mesoporous structure were discussed. Although there was no covalent bonding between PMMA and silica, macrophase separation was completely prevented in the electroblown fibers and the pore size in the calcined silica fibers ranged from 10 to 20 nm. However, the previously reported electrospun silica fibers, in which surfactants or polymers with strong hydrogen or covalent bonding to silanol groups were used as structure directing agents, had average pore sizes below 10 nm. The present study offers a facile method for the preparation of highly mesoporous silica fibers with large mesopores.     

微通道内双重孔结构SiO2微球的制备

利用微流控技术制备双重孔结构SiO₂微球具有微观结构和宏观形貌可控的优点。在同轴环管微通道中,通过pH和温度变化引发快速凝胶过程制备得到了具有双重孔结构的SiO₂微球,考察了有机相溶剂性质、有机相流速以及凝胶温度等因素对微球宏观形貌以及微观结构的影响规律。实验结果表明,制备得到的SiO₂微球粒径在300～600 μm可调,比表面积可以达到1000 m²·g^-1,介孔孔径在4～10 nm之间,大孔孔径在400～1500 nm之间。实验发现有机相流速的增大会导致微球粒径的减小,提高三辛胺对盐酸的萃取速率,加快二氧化硅溶胶粒子的凝胶过程,更易生成松散的网状大孔结构。较高的凝胶温度会增大SiO₂微球介孔的孔容和孔径。     

Cracking behavior of asphaltene in the presence of iron catalysts supported on mesoporous molecular sieve with different pore diameters

Cracking of a mixture of petroleum asphaltene and 10 wt% Fe catalyst supported on mesoporous molecular sieve (SBA-15) possessing a hexagonal array of uniform mesopores has been studied with a fixed bed reactor at 573 K under atmospheric He. When average pore diameter of Fe/SBA-15 is varied between 4.5 and 15 nm, asphaltene conversion increases almost linearly with increasing pore diameter up to 12 nm and reaches 65%, though the increment is small beyond this value. On the other hand, yield of maltene formed is almost independent of the diameter and less than 15% but greatly improved by using pressurized H₂ in place of He. Although pore volumes of all Fe/SBA-15 catalysts decrease by mixing with feed asphaltene, the extent of the decrease is larger for the catalyst with a larger pore diameter, which shows that higher asphaltene conversion may arise from the presence of larger amounts of asphaltene molecules held inside the larger mesopores. The N₂ adsorption measurements reveal that pore structures of Fe/SBA-15 catalysts are almost unchanged after cracking and subsequent re-calcination to remove deposited coke. The X-ray diffraction analysis and temperature programmed oxidation after cracking suggest that Fe species are highly dispersed inside the mesopores and present as the sulfided phases at the outermost layer.     

Effect of surfactant on the pore structure of mesoporous carbon

Mesoporous carbons (MCs) have been synthesized by using thermosetting phenol resin (TPR) as carbon precursor and commercially nanosized silica particles as template. During the synthesis of MCs, a kind of surfactant (Pluronic-F127) was used to modify the surface property of the silica particles. The dispersion capability of the nanosized particles as well as the effect of the surfactant on the pore structure of as-prepared carbons was investigated by transmission electron microscopy (TEM) and nitrogen adsorption, respectively. Results showed that the dispersion ability of silica particles was promoted after the addition of Pluronic-F127, which resulted in the increase of surface area and pore volume of the resultant MC. Pores with the pore size of about 4 nm and 10 nm were developed by adjusting the ratio of silica to the surfactant, and when the amount of surfactant reached a proper value, only pores of about 10 nm appeared. The surfactant had three functions for the pore development of MCs: increasing mesopores of about 10 nm by improving the dispersion capacity of nanosized particles, creation of small mesopores of about 4 nm and blocking the micropores in the carbon matrix.     

In Situ Growth of β-SiC Nanowires in Porous SiC Ceramics

Polycarbosilane (PCS) was used as a precursor to prepare porous silicon carbide (SiC) ceramics with in situ growth of β-SiC nanowires. The pore size of the as-prepared porous ceramics was 1.37 μm in average, and had a narrow distribution. The nanowires with diameters ranging from ∼10 to 50 nm existed in the channels of the porous body. Their morphology, microstructure, and composition were characterized by field emission scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy, which confirmed that the nanowires had a single-crystal β-SiC structure with the 〈111〉 growth direction. A vapor–liquid–solid process was discussed as a possible growth mechanism of the β-SiC nanowires.     

Fabrication of uniform 4H-SiC mesopores by pulsed electrochemical etching

In this letter, the uniform 4H silicon carbide (SiC) mesopores was fabricated by pulsed electrochemical etching method. The length of the mesopores is about 19 μm with a diameter of about 19 nm. The introduction of pause time (T_off) is crucial to form the uniform 4H-SiC mesopores. The pore diameter will not change if etching goes with T_off. The hole concentration decreasing at the pore tips during the T_off is the main reason for uniformity.     

Preparation of structured meso–macroporous silica materials: influence of composition variables on material characteristics

Meso–macroporous silica materials with a well-ordered array of mesopores were prepared from oil-in-water emulsions. The influence of the following three composition variables on material characteristics was studied: the dispersed phase fraction of the emulsion, the concentration of silica used and the concentration of surfactant. The obtained materials were characterized via small-angle X-ray diffraction scattering, scanning electron microscopy, transmission electron microscopy, Hg intrusion porosimetry and nitrogen adsorption–desorption isotherms. A network of structured mesopores was obtained even when using a highly concentrated emulsion (volume of the disperse phase, ? ≥ 0.75). The mesopores network presented a hexagonal arrangement, with mesopore diameters between 4 and 7 nm. Non-ordered macropores, with diameters between 50 nm and 10–15 μm were also present, depending on composition variables. The isotherms were of type IV, typical of mesoporous materials, but at high p/p₀ they were the usual shape for the macroporous materials. The possibility of tailoring mesopore and macropore structures by altering in composition variables could extend the application of these materials.