One-step preparation of FeCo nanoparticles in a SBA-16 matrix as catalysts for carbon nanotubes growth

Nanocomposites containing FeCo alloy nanoparticles dispersed in a highly ordered 3D cubic Im3m mesoporous silica (SBA-16) matrix were prepared by a novel, single-step templated-assisted sol-gel technique. Two different approaches were used in the synthesis of nanocomposites; a pure SBA-16 sample was also prepared for comparison. Low-angle X-ray diffraction, transmission electron microscopy and N2 physisorption at 77 K show that after metal loading, calcination at 500 degrees C and reduction in H2 flux at 800 degrees C the nanocomposites retain the cubic mesoporous structure with pore size not very different from the pure matrix. X-ray absorption fine structure (EXAFS) analysis at Fe and Co K-edges demonstrates that the FeCo nanoparticles have the typical bcc structure. The final nanocomposites were tested as catalysts for the production of carbon nanotubes by catalytic chemical vapour deposition and high-resolution TEM shows that good quality multi-walled carbon nanotubes are obtained.     

Nano-sized ceramic particles of hydroxyapatite calcined with an anti-sintering agent

Nano-sized crystals of calcined hydroxyapatite (HAp) having spherical morphologies were fabricated by calcination at 800 degrees C for 1 h with an anti-sintering agent surrounding the original HAp particles and the agent was subsequently removed by washing after calcination. The original HAp particles were prepared by a modified emulsion system, and surrounded with poly(acrylic acid, calcium salt) (PAA-Ca) by utilizing a precipitation reaction between calcium hydroxide and poly(acrylic acid) adsorbed on the HAp particle surfaces in an aqueous medium. In the case of calcination without PAA-Ca, micron-sized particles consisting of sintered polycrystals were mainly observed by scanning electron microscopy, indicating the calcination-induced sintering among the crystals. On the other hand, most of the crystals calcined with the anti-sintering agent were observed as isolated particles, and the mean size of the HAp crystals was around 80 nm. This result indicates that PAA-Ca and its thermally decomposed product, CaO, surrounding the HAp crystals could protect them against calcination-induced sintering during calcination at 800 degrees C. The HAp crystals calcined with PAA-Ca showed high crystallinity, and no other calcium phosphate phases could be detected.     

Effect of substituted alkyl groups on textural properties of ORMOSILs

A series of organically modified silica gels (ORMOSILs) with different alkyl groups such as methyl, ethyl, propyl, phenyl and octyl groups was investigated to determine the effect of substituted alkyl groups on the textural properties such as surface area, total pore volume, microporosity and hydrophobicity. Gelation time increased with increasing volume of alkyl groups. As-synthesized xerogels showed a systematic decrease in surface areas and total pore volumes and increase in microporosities with an increase in the volume of alkyl groups. All the ORMOSILs exhibited similar surface areas and total pore volumes after calcination at 500°C for 1 d. Increase in microporosities was observed in all the calcined xerogels. This study suggests that the primary particle sizes of pure silica cores are not affected by the size of the alkyl group, while their connectivity decreases with increasing volume of alkyl groups in the acid–base catalysed system of alkyltrimethoxysilane–tetramethylorthosilicate.     

Rapid synthesis and characterization of maghemite nanoparticles

Fe2O3-SiO2 nanocomposites were prepared by a sol-gel method using various evaporation surface to volume (S/V) ratios ranging from 0.03 to 0.2. The Fe2O3-SiO2 sols were gelated at various temperatures ranging from 50 degrees C to 70 degrees C, and subsequently they were calcined in air at 400 degrees C for 4 hours. The structure and the magnetic properties of the prepared Fe203-SiO2 nanocomposites were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), differential thermal analysis (DTA), and vibrating sample magnetometer (VSM) measurements. The gelation temperature of the Fe2O3-SiO2 sols influenced strongly the particle size and crystallinity of the maghemite nanoparticles. It was observed that the particle size of maghemite nanoparticles increased with the increasing of the gelation temperature of the sols, which may be due to the agglomeration of the maghemite particles at elevated temperatures inside the microporosity of the silica matrix during the gelation process, and the subsequent calcination of these gels at 400 degrees C resulted in the formation of large size iron oxide particles. Magnetization studies at temperatures of 10, 195, and 300 K showed superparamagnetic behavior for all the nanocomposites prepared using the evaporation surface to volume ratio (S/V) of 0.1, 0.2, 0.09, and 0.08. The saturation magnetization, Ms, values measured at 10 K were 5.5, 8.5, and 9.5 emu/g, for the samples gelated at 50, 60, and 70 degrees C, respectively. At the gelation temperature of 70 degrees C, gamma-Fe2O3 crystalline superparamagnetic nanoparticles with the particle size of 9 +/- 2 nm were formed in 12 hours for the samples prepared at the S/V ratio of 0.2.     

Fabrication of hierarchically porous spherical particles by assembling mesoporous silica nanoparticles via spray drying

A new type of hierarchically porous materials is fabricated by assembling mesoporous nanoparticles via spray drying. Well-dispersed mesostructured silica nanoparticles (MSN), whose particle size distribution was narrow in the range of 20 nm and 50 nm, were prepared by a thermal deposition method. By spray drying a MSN suspension, MSN were assembled into spherical secondary particles. After calcination, the spherical particles have two types of mesopores, mesopores of 3 nm in size inside of calcined MSN and larger inter-nanoparticle mesopores of about 15-20 nm. This hierarchical pore system should provide nanospaces for efficient mass transport of guest species with different sizes.     

Quick high-temperature hydrothermal synthesis of mesoporous materials with 3D cubic structure for the adsorption of lysozyme

Three-dimensional cage-like mesoporous FDU-12 materials with large tuneable pore sizes ranging from 9.9 to 15.6 nm were prepared by varying the synthesis temperature from 100 to 200 °C for the aging time of just 2 h using a tri-block copolymer F-127(EO₁₀₆PO₇₀EO₁₀₆) as the surfactant and 1,3,5-trimethyl benzene as the swelling agent in an acidic condition. The mesoporous structure and textural features of FDU-12-HX (where H denotes the hydrothermal method and X denotes the synthesis temperature) samples were elucidated and probed using x-ray diffraction, N₂ adsorption, ²⁹Si magic angle spinning nuclear magnetic resonance, scanning electron microscopy and transmission electron microscopy. It has been demonstrated that the aging time can be significantly reduced from 72 to 2 h without affecting the structural order of the FDU-12 materials with a simple adjustment of the synthesis temperature from 100 to 200 °C. Among the materials prepared, the samples prepared at 200 °C had the highest pore volume and the largest pore diameter. Lysozyme adsorption experiments were conducted over FDU-12 samples prepared at different temperatures in order to understand their biomolecule adsorption capacity, where the FDU-12-HX samples displayed high adsorption performance of 29 μmol g⁻¹ in spite of shortening the actual synthesis time from 72 to 2 h. Further, the influence of surface area, pore volume and pore diameter on the adsorption capacity of FDU-12-HX samples has been investigated and results are discussed in correlation with the textural parameters of the FDU-12-HX and other mesoporous adsorbents including SBA-15, MCM-41, KIT-5, KIT-6 and CMK-3.     

Structural characterization and catalytic activity of Pt dendrimer encapsulated nanoparticles supported over Al2O3 for SCR of NOx

Pt/Al2O3 and Pt-Mg/Al2O3 nano composites were successfully prepared by dendrimer templated synthesis route. The obtained dendritic nanoparticles were dispersed in alumina support and they were evaluated for SCR of NOx using methane as reductant. Thermal analysis results of uncalcined samples revealed that the oxygen can accelerate the rate of dendrimer shell decomposition. X-ray diffractograms of 500 degrees C calcined samples disclosed the amorphous nature of materials, whereas 1000 degrees C air calcined samples showed enhanced crystallinity as well as diffraction pattern corresponding to Pt and PtO. HRTEM images of Pt40-G4OH dendritic nanoparticles showed uniform particulate distribution with average particle size of 2.4 nm. The STEM results of 0.5 Pt/Al2O3 sample calcined at 500 degrees C exhibited a wide range of particles between 2 and 20 nm. This indicates the huge segregation of platinum metal particles during impregnation and subsequent calcination. Among the synthesized materials 0.5 wt% Pt/Al2O3 sample showed excellent conversion and selectivity for SCR of NOx.     

尿素-过氧化氢混合模板法合成介孔二氧化硅

以尿素-过氧化氢为混合模板、正硅酸乙酯为硅源,在酸性条件下,通过溶胶-凝胶过程合成二氧化硅介孔材料。采用煅烧法除去模板剂,用红外光谱、XRD、N2吸附-脱附、HRTEM等分析测试手段对介孔材料的结构和形态进行了表征。结果表明:与以尿素为单一模板相比,采用混合模板剂所合成介孔材料为蠕虫状,孔径分布基本保持不变、比表面积相近(分别为445、431m2/g)、孔径(分别为7.04、8.11nm)和孔体积(分别为0.783、0.874cm3/g)明显增大。     

乙二胺改性Co3O4-NiO复合粒子的制备及其超级电容性能研究

利用简单液相共沉淀法制得中间产物Ni(OH)2-Co(OH)2,再经煅烧得到Co3O4-NiO复合粒子;用乙二胺对Co3O4-NiO复合粒子进行改性,改性后Co3O4-NiO微粒分散性提高,形貌为片状,片与片之间相互交叉形成疏松的介孔结构。电化学测试表明Co3O4-NiO电极材料在改性后表现出优良的电化学性能,在电位窗口为0～0.4V时,单电极比电容可达1202F/g,相比改性前提高了171F/g。     

Catalytic conversion of 1,2-dichlorobenzene over mesoporous V2O5/TiO2 prepared from spray pyrolysis

Mesoporous V2O5/TiO2 particles were prepared by spray pyrolysis and applied to the catalytic oxidation of 1,2-dichlorobenzene (1,2-DCB). Two different precursors (alkoxide and nanoparticles) for the TiO2 support were used to determine the effects on the texture properties and the catalytic activity of the mesoporous V2O5/TiO2 particles. The 5 wt% V2O5/TiO2 particles had the largest surface area (173 m2/g) and 4.7 nm in average pore size. The catalytic activity of the V2O5/TiO2 particles depended strongly on the loading quantity of vanadium, whereas the P25-derived samples showed no significant change in catalytic activity with weight% of vanadium. The surface area of the V2O5/TiO2 particles prepared using the alkoxide precursor was larger than that of the particles prepared using P25 nanoparticles. The P25-derived V2O5/TiO2 particles, however, showed a higher catalytic activity compared with those alkoxide-derived, which is due to the difference in the vanadium quantity exposed to the pore surface. It was confirmed that the 10 wt% V2O5/TiO2 particles prepared by spray pyrolysis had an excellent activity for the oxidation of 1,2-DCB, particularly at temperatures below 300 degrees C.     

CaCu3Ti4O12 nanoparticles using polyvinyl pyrrolidone: synthesis and dielectric properties

Nanocrystalline CaCu3Ti4O12 powders with particle sizes of 39.28 8.12 nm were synthesized by a simple modify sol-gel using PVP (Poly-vinyl-pyrrolidone). The synthesized precursor was characterized by TG-DTA to determine the thermal decomposition and crystallization temperature which was found to be at above 500 degrees C. The precursor was calcined at 800 degrees C in air for 8 h to obtain nanocrystalline powders of CaCu3Ti4O12. The calcined CaCu3Ti4O12 powders were characterized by XRD, FTIR, SEM and TEM. Sintering of the powders was conducted in air at 1100 degrees C for 16 h. The XRD results indicated that all sintered samples have a typical perovskite CaCu3Ti4O12 structure and a small amount of CaTiO3. SEM micrographs showed the average grain sizes of 1.86 +/- 0.69 /m for the sintered CaCu3Ti4O12 ceramic prepared using the CaCu3Ti4O12 powders calcined at 800 degrees C. The sintered samples exhibit a giant dielectric constant, epsilon' of approximately 10(3)-10(4). The large low-frequency dielectric permittivity at low temperature is closely related to sub-grain boundary distribution, including conductivity effect. Furthermore, the ceramic shows three semicircles in the complex impedance plane. However, at low frequency, semicircles of sub-grain boundary and grain boundary are considered to represent collapse different electrical mechanisms. The another is ascribed to the contribution of grain. The dielectric behavior at several frequencies and temperatures of these samples can be attributed to electronic inhomogeneities present in material and can be explained based on a microstructural model.     

Aqueous Cr(VI) photo-reduction catalyzed by TiO2 and sulfated TiO2

TiO(2) and sulfated TiO(2) (SO(4)(2-)/TiO(2)) catalysts with different textural properties were prepared under different calcination temperatures and the photo-reduction of Cr(VI) to Cr(III) catalyzed by these catalysts was investigated. For the photocatalytic reduction of Cr(VI), the photocatalytic activities of the TiO(2) samples were found to be strongly dependent of the calcination temperature and TiO(2) calcined at 400 degrees C showed a higher catalytic activity compared to other TiO(2) catalysts. In contrast, sulfation of TiO(2) stabilized the catalytic activities of SO(4)(2-)/TiO(2) catalysts. At low calcination temperature, SO(4)(2-)/TiO(2) catalysts exhibited catalytic activities almost comparable with that of TiO(2) and the catalytic activities of SO(4)(2-)/TiO(2) catalysts were markedly higher than TiO(2) under high calcination temperature. In addition, the removal of surface SO(4)(2-) of SO(4)(2-)/TiO(2) catalyst led to a marked decrease of the catalytic activity for Cr(VI) photo-reduction, suggesting that the presence of surface SO(4)(2-) provided an acid environment over the catalyst surface and favored the photo-reduction of Cr(VI).     

Coagulation/phase separation process in the silica/inorganic salt systems (1)—observation of state transformation—

The authors investigated the transformation of state of silica particles and inorganic salts during the calcination of solid mixtures of silica/potassium halide (KX), which separated the mixture components producing microporous structures, at temperatures below the melting point of either materials. The silica sol (SiO₂—Na₂O)/KX solid was examined at high temperatures using thermal analysis, X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The data suggest the crystalline inorganic salt component transformed into an amorphous state ca. 100–200°C lower than its melting point, while the silica particle component coagulated, spontaneously separating the two components (coagulation/phase separation). Upon cooling, the inorganic salt was dispersed in water, resulting in porous silica with a narrow pore size distribution. However, at calcination temperatures above 800°C, formation of silica crystal existed as a separate domain without creating porous structures.     

Studies on the dehydration of glycerol over niobium catalysts

The dehydration of glycerol over nanosize niobium catalysts was conducted in a stainless steel autoclave reactor. The catalysts were prepared by the calcination of niobium oxalate between 200 and 700 degrees C. Catalysts were characterized by N2 Physisorption, XRD and TPD of ammonia to investigate the effect of the calcination temperature and water on catalytic performance, catalysts' structures and acidity. Acrolein was mainly produced about 51-71% with useful by-products such as acetaldehyde and methanol. Amorphous Nb2O5 catalysts calcined at 200-400 degrees C significantly showed higher conversion of glycerol than the crystallized Nb2O5 catalyst calcined at 500-700 degrees C. Also the conversion of glycerol and selectivity of acrolein was increased with increasing the acidity of catalyst, which can be controlled by calcination temperature.     

Decolorization of KN-R catalyzed by Fe-containing Y and ZSM-5 zeolites

Decolorization of an anthraquinone dye, Reactive Brilliant Blue KN-R by hydrogen peroxide was examined using Fe-containing Y and ZSM-5 zeolites as heterogeneous catalysts. Catalysts were prepared by ion-exchange and coprecipitation methods, and calcined at different temperatures. The surface morphologies, crystalline phases, and chemical-state of the catalysts were characterized by scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Influences of reaction conditions, such as dye concentration, catalyst dosage and solution pH, were evaluated and the relations between catalytic capacity and surface microstructures were discussed. The results showed that Fe-containing Y and ZSM-5 zeolites generally exhibited similar or better catalytic efficiency compared with homogeneous Fenton reagent, with Fe-containing ZSM-5 being more efficient. Synthesis method and calcination temperature affected catalytic efficiency and the stability of catalysts. Fe-containing ZSM-5, which was prepared by coprecipitation and calcined at 450 degrees C, displayed the greatest decolorization capacity. Under the conditions of initial pH 2.5, 30.0 mmol/L H(2)O(2) and 4.0 g/L catalyst, 250 mg/L KN-R could be decolorized over 90% within 20 min.     

Permeation of solvents through disk type rice husk silica membrane modified with alkyl silylation reagents

Rice husk silica (RHS) which was obtained with thermal treatment of rice husk has the size of approximately 10 micrometer with 4-5 nm pore. RHS can be mold to a disk type membrane. The membrane may have submicron pore originated from the space among the particles, and the nano pores of the rice husk silica (RHS pore). Even it is difficult to adjust the size of the pores, we can suggest that the membrane shows different permeability for the organic/inorganic solvents if the affinity between the surface of the pores and the permeating molecule is changed. In this study, we investigated the permeation of the typical solvents such as water, ethanol and toluene to the RHS membranes sintered at 1100 degrees C, 1150 degrees C and 1200 degrees C and modified with triethoxymethyl silane (CH3)Si(C2H5O)3, diethoxydiemethyl silane (CH3)2Si(C2H5O)2 and ethoxytriemethyl silane (CH3)3Si (C2H5O). The result showed that permeability of original membranes for water (e.g., 1100 degrees C, 2.87 x 10(-3) mol/m2 s Pa) was larger than ethanol (1100 degrees C, 5.51 x 10(-4) mol/m2 s Pa) and toluene (1100 degrees C, 3.09 x 10(-4) mol/m2 s Pa) at the sintering temperatures. For the silane modified membranes, the permeability for water decreased drastically while those for ethanol and toluene increased.     

Effects of thermal treatment of nanostructured trititanates on their crystallographic and textural properties

Nanostructured titanates (TTNT) with general formula Na_xH_2−xTi₃O₇·nH₂O were synthesized by hydrothermally reacting different TiO₂ anatase (distinct crystal sizes) with NaOH at 120 °C followed by washing with water or diluted acid and drying of the precipitate. The resulting powders with different sodium contents were submitted to various calcination temperatures up to 800 °C and each calcined product was characterized as for its phase structure, composition, crystallite size and textural properties, namely BET surface area, mesopore volume and pore size distribution. Thermal transformations of TTNT samples were investigated by monitoring the modifications on crystallographic (X-ray diffraction) and textural (N₂ desorption isotherms) properties, revealing the influence of the type of starting anatase and sodium content over the stability of TTNT. Moreover, a detailed study on the reduction of the interlayer distance in TTNT samples upon thermal treatment allowed corroborating the formation of an intermediate nanostructured hexatitanate, just before phase transformation into the corresponding TiO₂ polymorphs and/or titanate crystals, depending on the sodium content and calcination temperature.     

Mesoporous titania–silica composite from sodium silicate and titanium oxychloride. Part II: one-pot co-condensation method

Mesoporous titania–silica composite with large primary particles and homogeneous dispersion of Ti in the silica matrix were synthesized by the sol–gel method via a one-pot co-condensation method using cetyltrimethylammonium bromide (CTAB) as a structure-directing agent. Freshly prepared titanium oxychloride (TiOCl₂, titania precursor that is relatively stable) and sodium silicate were used as titania and silica precursors (at the initial ratio of Ti:Si = 1), respectively. The final products were obtained after removing the template by calcination and had overall ratio of Ti:Si = 2:3 (based on EDS and XRF analyses). Other characterization techniques employed include FE-SEM, TEM, FT-IR, DTGA, and nitrogen physisorption studies. The textural properties of the products were highly influenced by the molar concentration of CTAB. Materials with large primary particles (submicrometer-scale dimensions) were obtained at higher concentrations of CTAB (1.7 wt%). The porosities of the templated material were highly reduced compared to that of the untemplated material, emphasizing the influence of Ti loading in the silica matrix. Both pore size and surface area increased at a calcination temperature of 550 °C. The DTGA result showed that the composites exhibited elevated thermal stability (up to 900 °C). In summary, mesoporous titania–silica composite with desirable properties were developed via the proposed method using a relatively inexpensive silica precursor.     

Synthesis of carbon nanotubes using mesoporous Fe-MCM-41 catalysts

MWNTs (multi-walled carbon nanotubes) were made by catalytic CVD process using iron-containing mesoporous silica, Fe-MCM-41, with 4 mol% Fe loading prepared by direct synthesis route. Uniform 5 nm size Fe2O3 nano-particles impregnated onto a mesoporous silica support, SBA-15 were also prepared for CNTs synthesis. The catalysts were characterized using XRD, SEM/TEM, N2 physisorption, UV-vis diffuse reflectance and FT-IR spectroscopies. Acetylene gas was introduced as a carbon source, and the gas mixture of Ar:H2:C2H2 = 14:5:1 pyrolyzed at 750 degrees C for 60 min was found to be the optimum synthesis condition. Fe-MCM-41 due to higher dispersion of nano-sized Fe-species was efficient as catalyst for MWNTs with more uniform size distribution. Cobalt-impregnated Fe-MCM-41 (Co/Fe = 1) produced a small fraction of SWNTs of ca. 2 nm diameter mixed with MWNTs.     

Hazardous ions uptake behavior of thermally activated steel-making slag

This study concerns the utilization of waste steel-making slag, a by-product that contains mainly CaO, Fe(2)O(3) and SiO(2). The as-received slag was ground and thermally activated by temperature treatment from 110 to 1000 degrees C for 24 h. Although the as-received slag was amorphous, it became partially crystallized during grinding. These crystalline phases were larnite and iron oxide but other crystalline phases also appeared in addition to larnite after calcination. The uptake of Ni(2+), PO(4)(3-) and NH(4)(+) by the samples was investigated from solutions with initial concentrations of 10 mmol/l. The sample calcined at 800 degrees C showed the highest Ni(2+) uptake (4.85 mmol/g) whereas the highest simultaneous uptake of PO(4)(3-) (2.75 mmol/g) and NH(4)(+) (0.25 mmol/g) was achieved by calcining the material at 700 degrees C. The principal mechanism of Ni(2+) uptake is thought to involve replacement of Ca(2+) by Ni(2+). The mechanism of PO(4)(3-) uptake is mainly by formation of calcium phosphate while that of NH(4)(+) involves sorption by the porous silica surface of the samples.