Controlling the textural parameters of mesoporous carbon materials

The mesoporous carbon materials prepared by inorganic templating technique using mesoporous silica, SBA-15 as a template and sucrose as a carbon source, have been systematically investigated as a function of sucrose to mesoporous silica composition, with a special focus on controlling the mesoporous structure, surface morphology and the textural parameters such as specific surface area, specific pore volume and pore size distribution. All the materials have been unambiguously characterized by XRD, N₂ adsorption–desorption isotherms, high-resolution transmission electron microscopy, high-resolution field emission scanning electron microscopy, and Raman spectroscopy. It has been found that the porous structure, morphology and the textural parameters of the mesoporous carbons materials, CMK-3-x where x represent the sucrose to silica weight ratio, can be easily controlled by the simple adjustment of concentration of sucrose molecules. It has also been found that the specific surface area of the mesoporous carbon materials systematically increases with decreasing the sucrose to silica weight ratio. Moreover, the specific pore volume of the materials increases from 0.57 to 1.31 cm³/g with decreasing the sucrose to silica weight ratio from 5 to 1.25 and then decreases to 1.23 cm³/g for CMK-3-0.8. HRTEM and HR-FESEM also show a highly ordered pore structure and better surface morphology for CMK-3-1.25 as compared to other materials prepared in this study. Thus, it can be concluded that the sucrose to silica weight ratio of 1.25 is the best condition to prepare well ordered mesoporous carbon materials with good textural parameters, pore structure and narrow pore size distribution.     

Carbon nanocage: a large-pore cage-type mesoporous carbon material as an adsorbent for biomolecules

Novel large pore cage type mesoporous carbons, carbon nanocages, abbreviated as CKT (carbon from KIT-5) using three dimensional large cage type face centered cubic Fm3m mesoporous silica materials (KIT-5) as inorganic templates prepared at different temperature were synthesized and characterized. The specific pore volume and the specific surface area of the carbon nanocage materials are much higher as compared to CMK-3 mesoporous carbon. Adsorption of amino acid (histidine), flavonoid (catechin), vitamin (vitamin E, α-tocopherol), endocrine disrupter (nonylphenol), and enzyme (lysozyme) over the carbon nanocage materials was also studied. Interestingly, carbon nanocage materials showed an unusual adsorption capacity of catechin in aqueous solution. The CKT carbon nanocage materials also exhibited higher adsorption capabilities of other biomolecules used in this study as compared with the CMK-3 mesoporous carbon.     

Characteristics of vanadium-substituted mesoporous silica with wormhole framework structure: effects of vanadium content

Vanadium-substituted wormhole framework structure (V-WMS) mesoporous silicas (V-WMS) with various Si/V ratios in the range of 15 and 200 were prepared at ambient temperature by neutral surfactant templating pathway. The materials were synthesized by using dodecylamine as a template and tetraethylorthosilicate as a silicon source. They were characterized by energy dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (XRD), N₂ adsorption–desorption, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared absorption spectroscopy (FT-IR) and ultraviolet-visible absorption spectroscopy. V-WMS samples shown characters of larger framework wall thickness, small crystallite domain sizes, and complementary textural mesoporosities in comparison with M41S materials. These mesoporous V-WMS samples exhibited irregularly shaped mesoscale fundamental particles which aggregated into larger particles. They also demonstrated better thermal stability than MCM-41. An absorption band of FT-IR at ca. 960 cm⁻¹ was assigned to the vibration of Si–O–V linkages. These samples also showed one strong UV–visible absorbance with overlapping maxima at about 255 nm. The results show that vanadium was incorporated into the structure of wormhole mesoporous silica (WMS). However, for V-WMS with high vanadium content (Si/V < 25), a broad shoulder in XRD pattern was observed at about 3–4°, suggesting the presence of impurity phase of vanadium species in the sample. The efforts in preparing V-WMS specimens by neutral-template synthesis route had led to new mesoporous silica molecular sieves with catalytically active vanadium centers.     

The particle size effect of N-doped mesoporous carbons as oxygen reduction reaction catalysts for PEMFC

The particle size effect of N-doped mesoporous carbon was investigated for ORR activity in acid condition and for issue of a mass transfer and gas diffusion in PEMFCs. As for a non-Pt ORR catalyst, nitrogen (N)-doped ordered mesoporous carbons (OMCs) with a various particle sizes with the range of the average 20, 45 and 75 μm were synthesized by the precursor of polyaniline for the N/C species, and a mesoporous silica template was used for the physical structure for preparation of nitrogen doped OMCs. The N-doped mesoporous carbons are promoted by a transition metal (Fe) to improve catalytic activity for ORR in PEMFCs. All the prepared carbons were characterized by via scanning electron microscopy (SEM), and to evaluate the activities of synthesized doped carbons, linear sweep was recorded in an acidic solution to compare the ORR catalytic activities values for the use in the PEMFC system. The surface area and pore volume were increased as the particles decreased, which was effective for the mass transfer of the reactant for higher activity at the limiting current regions.     

Tuning mesoporous molecular sieve SBA-15 for the immobilization of α-amylase

The present work describes the immobilization of α-amylase over well ordered mesoporous molecular sieve SBA-15 with different pore diameters synthesized by post synthesis treatment (PST) hydrothermally after reaction at 40°C. The materials were characterized by N₂ adsorption–desorption studies, small angle X-ray diffraction, scanning electron microscopy and high resolution transmission electron microscopy. Since α-amylase obtained from Bacillus subtilis has dimensions of 35 × 40 × 70 Å it is expected that the protein have access to the pore of SBA-15 (PST-120°C) with diameter 74 Å. The pore dimension is appropriate to prevent considerable leaching. The rate of adsorption of the enzyme on silica of various pore sizes revealed the influence of morphology, pore diameter, pore volume and pH.     

Synthesis of porous carbon and silica spheres using PEO-PF polymer blends

In this paper, we performed a physical mixture of PEO and PF polymers (i.e. a polymer blend) as an organic template for synthesizing PF-PEO-silica homogeneous composites in a dilute silicate solution at pH = 4.0–5.0. The PF-PEO-silica composites exhibit spherical morphology, in micrometer dimension, and the sphere size is dependent on the pH value of the solution. After undergoing calcination to remove the organic part of the PF-PEO-silica composites with and without the hydrothermal treatment, porous silica spheres of different pore sizes were obtained. Due to the existence of the carbonizing PF polymer in the PF-PEO-silica composite, porous carbon spheres can be conveniently obtained from pyrolysis of the PF-PEO-silica composites under a N₂ atmosphere and HF-etching procedures. TEM images demonstrate that the mesostructures of the mesoporous silica and porous carbons are disordered.     

The influence of carbon source on the wall structure of ordered mesoporous carbons

A series of ordered mesoporous carbons (OMCs) have been synthesized by filling the pores of siliceous SBA-15 hard template with various carbon precursors including sucrose, furfuryl alcohol, naphthalene and anthracene, followed by carbonization and silica dissolution. The carbon replicas have been characterized by powder XRD, TEM and N₂ adsorption techniques. Their electrochemical performance used as electric double-layer capacitors (EDLCs) were also conducted with cyclic voltammetry and charge-discharge cycling tests. The results show that highly ordered 2D hexagonal mesostructures were replicated by using all these four carbon sources under the optimal operation conditions. Physical properties such as mesoscopic ordering, surface areas, pore volumes, graphitic degrees, and functional groups are related to the precursors, but pore sizes are shown minor relationship with them. The sources, which display high yields to carbons, for example, furfuryl alcohol and anthracene are favorable to construct highly ordered mesostructures even at high temperatures (1300 °C). OMCs prepared from non-graphitizable sources such as sucrose and furfuryl alcohol display amorphous pore walls, and large surface areas and pore volumes. The functional groups in the precursors like sucrose and furfuryl alcohol can be preserved on carbon surfaces after the carbonization at low temperatures but would be removed at high temperatures. The graphitizable precursors with nearly parallel blocks and weak cross-linkage between them like anthracene are suitable for deriving the OMCs with graphitic walls. Therefore, the OMCs originated from sucrose and furfuryl alcohol behave the highest capacitances at a carbonization of 700 °C among the four carbons due to the high surface areas and plenty of functional groups, and a declination at high temperatures possibly attribute to the depletion of functional groups. Anthracene derived OMCs has the lowest capacitance carbonized at 700 °C, and a steady enhancement when heated at high temperatures, which is attributed to the graphitization. The OMCs derived from naphthalene have the stable properties such as relatively high surface areas, few electroactive groups and limited graphitizable properties, and in turn medium but almost constant capacitances.     

Synthesis and characterization of highly ordered mesoporous YSZ by tri-block copolymer

A highly ordered mesoporous yttria-stabilized zirconia (YSZ) has been successfully prepared by evaporation-induced self-assembly method (EISA) using tri-block copolymer Pluronic F127 as a structure-directing agent and inorganic chlorides as precursors in a non-aqueous medium. The characterization of the mesoporous YSZ materials was carried out by using small angle X-ray diffraction (SAXRD), transmission electron microscopy (TEM) and N₂ adsorption/desorption. The well ordered mesoporous YSZ is thermally stable up to 600^∘C with an average pore size of 5.4 nm and specific surface area of 90 m²/g. The walls of mesoporous YSZ are composed of ∼6.5 nm nano-crystalline domains.     

Templating synthesis of ordered mesoporous carbon particles

This research reports the synthesis of spherical ordered mesoporous carbon particles using mesoporous silica particles as a template. The silica particles with ordered cubic and lamellar mesostructures were synthesized from an aerosol-assisted self-assembly process using block copolymer surfactants as the structural directing agent. Infiltrating the pores of the silica particles with a sucrose solution followed by carbonization, and silica removal results in mesoporous carbon particles with replicated mesostructures. The particles were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and nitrogen sorption techniques.     

简易模板法制备有序介孔碳及其表征

目前制备有序介孔碳的方法工艺复杂、繁琐耗时,为了简化其制备工艺,缩短实验流程,本文提出一种不需要添加额外溶剂直接制备有序介孔碳的方法。以三嵌段共聚物F127为模板剂,自制低分子量酚醛树脂为碳前体,制备了具有二维六方结构的介孔碳。采用红外光谱对酚醛树脂和F127进行表征,研究了两者之间的作用力;采用X射线衍射、透射电镜和N2吸附/脱附等手段对介孔碳结构进行表征,研究了酚醛树脂的合成温度和模板剂用量对介孔碳结构的影响。结果表明酚醛树脂合成温度为70℃,F127：PF=1时,得到的介孔碳比表面积、孔容和孔径分别为490m2/g、0.41cm3/g和4.15nm。     

Control of pore size in mesoporous silica templated by a multiarm hyperbranched copolyether in water and cosolvent

Worm-like mesoporous silica with various pore sizes has been prepared successfully templated by a multiarm hyperbranched copolyether (PEHO-star-PPO). The pore size of the resultant mesoporous materials can be controlled easily through adjusting the ratio of water to cosolvent. As the molar ratio of water to ethanol changes from 0.02 to 0.73, the pore size of the calcined materials can be enlarged from 32 to 94 Å, attributing to the aggregation behavior of the multiarm hyperbranched polymer in different systems. Moreover, the pore size of the obtained mesoporous silica can be also adjusted by selecting different kinds of cosolvent. The polarity and solubility of cosolvents are believed to be two important factors in affecting the pore size. Thus, a facile and efficient method for controlling the pore size of mesoporous silica has been developed by using hyperbranched polymers as templates.     

Synthesis and characterization of mesoporous molecular sieve nanoparticles

Mesoporous molecular sieve was prepared hydrothermally by a two-step method with materials of cetyltrimethyl ammonium bromide (CTAB), as a template, and sodium metaaluminate (NaAlO₂) and sodium silicate (Na₂SiO₃·9H₂O), as aluminum and silicon sources, respectively. The mesoporous molecular sieves are well ordered and have high thermal and hydrothermal stabilities. The as-prepared samples were characterized by powder X-ray diffraction (XRD), atomic force microscopy (AFM), transmission electron microscopy (TEM), thermogravimetry-differential scanning calorimetry (TG/DSC), Fourier transform infrared spectroscopy (FT-IR) and nitrogen adsorption experiments. Particle size distribution was in the 30–50 nm range, BET surface area was more than 800 m²/g, thermal stability was higher than 1023 K, the mesoporous structure was not entirely damaged at a calcination temperature of 1123 K and there was no clear change in ordering degree, pore size, and surface area of the mesoporous molecular sieve after hydrothermal treatment at 373 K for 10 days. The activity and selectivity of benzene hydrogenation to cyclohexane by mesoporous molecular sieve-supported Pt was up to 100%. The catalytic activity didn’t decline in a reaction period of 30 h.     

Synthesis and characterization of porous media produced by a sol-gel method

Mesoporous silica materials were synthesized by sol-gel method using tetraethoxysilane (TEOS) as precursors and surfactants i.e., cetyltrimethyl ammonium bromide (CTAB), sodium dodecyl sulfate (SDS), and polyoxyethylene cetyl ether (Brij 56) as templates. Surfactant templates were completely removed by calcination to form mesoporous structure. The effects of type and amount of surfactants on the characteristics of samples were studied. The textural characteristics such as surface area, pore volume, pore size, and pore size distribution were determined by nitrogen sorption isotherms. Fourier transform infrared (FTIR) spectroscopy was employed to qualitatively identify the chemical functionality and to confirm the removal of surfactant template. Scanning electron microscope (SEM) and transmission electron microscope (TEM) were used to directly observe surface morphology and mesoporous structure, respectively. The adsorption capacity of the synthesized adsorbent for toluene vapor was examined. We found that the pore volume and pore size of mesoporous materials affected the adsorption capacity. The sample prepared with high content of CTAB under basic condition (pH ∼7) yielded large pore volumes and pore sizes and subsequently possessed the high adsorption capacity for toluene vapor.     

Fast preparation of ordered crystalline mesoporous titania with high thermal stability and photo oxidation performance

Ordered mesoporous titania with crystalline anatase walls has been synthesized through fast evaporation-induced self-assembly method in a non-aqueous solution that only needs a 30 h synthetic period. The ordered mesostructure and crystalline anatase frameworks are characterized by the low-angle and wide-angle X-ray diffraction (XRD) and transmission electron microscopy (TEM). The ordered titania mesostructure is thermally stable to 733 K, and the corresponding N₂ adsorption–desorption analysis exhibits that it has a surface area of 246 m²/g and a narrow pore distribution centered at 3.7 nm. Crystalline mesoporous titania exhibits the higher catalytic performance in photooxiding α-methylstyrene to acetophenone.     

Mesoporous silica supported cobalt oxide catalysts for catalytic removal of benzene

Two types of mesoporous silica SBA-15 with different pore diameter were synthesized with an ageing temperature of 373 K and an ageing temperature of 308 K, respectively; in addition, mesoporous silica with amorphous structure was synthesized by adding organosiloxane as part of the silica source during the synthesis procedure. Mesoporous silica and conventional alumina supported cobalt oxide catalysts were prepared by incipient wetness impregnation method. These materials were characterized by FT-IR, nitrogen adsorption–desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM) and Temperature programmed reduction (TPR) techniques, and the activity of the supported cobalt oxide catalysts for deep oxidation of benzene were evaluated in a fixed-bed reactor. It seems that the pore diameter of the silica increase with the elevation of the ageing temperature. Mesoporous silica supported cobalt oxide catalysts are more active than conventional alumina supported ones. Cobalt oxide can be relatively better dispersed on the surface of mesoporous silica which has larger pore diameter and surface areas. Meanwhile, more silanol groups exist on the surface of amorphous silica, which could induce a strong interaction with the supported cobalt oxide species, leading to poor activity for benzene oxidation.     

Structure and Luminescence Properties of Eu<Superscript>3+</Superscript>-Doped Cubic Mesoporous Silica Thin Films

Eu³⁺ ions-doped cubic mesoporous silica thin films with a thickness of about 205 nm were prepared on silicon and glass substrates using triblock copolymer as a structure-directing agent using sol–gel spin-coating and calcination processes. X-ray diffraction and transmission electron microscopy analysis show that the mesoporous silica thin films have a highly ordered body-centered cubic mesoporous structure. High Eu³⁺ ion loading and high temperature calcination do not destroy the ordered cubic mesoporous structure of the mesoporous silica thin films. Photoluminescence spectra show two characteristic emission peaks corresponding to the transitions of ⁵D₀-⁷F₁ and ⁵D₀-⁷F₂ of Eu³⁺ ions located in low symmetry sites in mesoporous silica thin films. With the Eu/Si molar ratio increasing to 3.41%, the luminescence intensity of the Eu³⁺ ions-doped mesoporous silica thin films increases linearly with increasing Eu³⁺ concentration.     

弱酸性条件下SBA-16型二氧化硅介孔材料的合成与表征

引言 有序介孔材料由于具有较大的比表面积、均一可调的孔径(2～50 nm)、规则可控的形貌、较高的热稳定性和耐水解性等性能,在分离、吸附、催化、生物材料、信息材料、碳纳米管制备等领域有着广泛应用[1-3].     

Structural Characterization of Mesoporous Silica Nanofibers Synthesized Within Porous Alumina Membranes

Mesoporous silica nanofibers were synthesized within the pores of the anodic aluminum oxide template using a simple sol–gel method. Transmission electron microscopy investigation indicated that the concentration of the structure-directing agent (EO₂₀PO₇₀EO₂₀) had a significant impact on the mesostructure of mesoporous silica nanofibers. Samples with alignment of nanochannels along the axis of mesoporous silica nanofibers could be formed under the P123 concentration of 0.15 mg/mL. When the P123 concentration increased to 0.3 mg/mL, samples with a circular lamellar mesostructure could be obtained. The mechanism for the effect of the P123 concentration on the mesostructure of mesoporous silica nanofibres was proposed and discussed.     

An ordered hydrophobic P6mm mesoporous carbon with graphitic pore walls and its application in aqueous catalysis

A hydrophobic ordered mesoporous carbon with hexagonal arrays of rods was synthesized by a nanocasting process by using silica SBA-15 as a template and 2,3-dihydroxynaphthalene as a fused-aromatic carbon precursor. Impregnation of 2,3-dihydroxynaphthalene and its subsequent conversion into carbon occurred inside the mesopores of the silica template through a dehydration reaction between the surface silanols and hydroxyl groups of the carbon source and mild carbonization under inert atmosphere. After silica removal, X-ray scattering, transmission electron microscopy, pore size analysis and Raman spectroscopy showed that the resulting material was a negative replica of the silica template with a 2D-hexagonal P6mm ordered structure, possessing a large surface area (724 m² g⁻¹), a monomodal pore size distribution (3.4 nm) and a relative hydrophobic surface with graphitic pore walls. These features give the system substantial advantages to play a beneficial role in aqueous organometallic catalysis. The material appeared to be an excellent mass transfer promoter to enhance the overall reaction rate of the palladium-catalyzed cleavage reaction of water-insoluble allylundecylcarbonate (Tsuji–Trost reaction).     

Monodispersed nanoporous starburst carbon spheres and their three-dimensionally ordered arrays

Controlled syntheses of highly monodispersed nanoporous carbon spheres via a nanocasting route are described. Previously reported monodispersed super-microporous or mesoporous silica spheres with hexagonally ordered pore channels were used as sacrificial templates, and the effect of pore sizes of the templates on the porous properties of the nanocast carbon spheres was comprehensively studied. The resultant carbon spheres exhibited a unique starburst structure derived from radially-aligned pore channels in the silica template, and had a BET surface area of over 1000 m²g^?1. It was found out that the radial alignment and sufficiently large pore size of hexagonally ordered pore channels in the silica spheres were effective to enhance the degree of order of the starburst structure in the nanocast carbon spheres and that ordered nanoporous carbon spheres could be obtained even from the MCM-41-type mesoporous silica. The diameters of the nanoporous carbon spheres were controlled in the sub-micrometer range by changing the sizes of silica templates. Furthermore, three-dimensionally ordered arrays consisting of nanoporous carbon spheres were successfully fabricated via the self-assembly of mesoporous silica/carbon composite spheres and the subsequent dissolution of the silica templates.