Comparative studies of p6m siliceous mesostructures by powder X-ray diffraction and nitrogen adsorption

Two-dimensional mesostructures with p6m symmetry such as MCM-41 and SBA-15 are the subject of intensive studies by using nitrogen and argon adsorption, transmission electron microscopy, and powder X-ray diffraction/scattering techniques. The latter may involve the X-ray diffraction (XRD) or small angle X-ray scattering (SAXS) measurements. The XRD/SAXS patterns for the aforementioned ordered mesostructures often exhibit four or more reflections, the most intensive one, 1 0 0 peak, and three less intensive peaks, 1 1 0, 2 0 0, 2 1 0. So far, analysis of these patterns was usually limited for the evaluation of the unit cell parameter and the identification of the observed peaks. In this work we present an attempt to analyze the XRD/SAXS patterns by including not only the position of observed peaks but also their intensity. It is shown that the intensity of these peaks, especially 1 1 0 peak, depends on the ratio of the pore diameter to the unit cell parameter. In particular, this dependence was studied for the intensity ratio of 1 1 0 and 2 0 0 peaks assuming 2 0 0 peak as a reference reflection because of its nearness to 1 1 0 peak (which minimizes the influence of other factors than the structural ones on the 1 1 0/2 0 0 intensity ratio analysis) and similar intensity to that of 1 1 0 peak. The values of the 1 1 0/2 0 0 intensity ratio were determined for many MCM-41 and SBA-15 samples and analyzed in relation to the pore width/unit cell ratio, where the pore width was estimated on the basis of nitrogen adsorption data or by the XRD/SAXS structure modeling. Comparative analysis of this intensity ratio for numerous MCM-41 and SBA-15 samples allows for a quick estimation of the pore width and provides some information about hexagonality of mesopores in these materials.     

Synthesis and characterization of MCM-41 decorated with CuO particles

CuO particles have decorated on the external surface of MCM-41 by in situ introducing cupric nitrate during the hydrothermal synthesis followed by the calcination. The textural and structural properties of CuO/MCM-41 are compared with those of pure MCM-41. The results show that CuO particles are about 40 nm in size and are not agglomerated. The addition of cupric nitrate to the synthesis gel leads to materials with somewhat reduced quality as evidenced from X-ray diffraction patterns and nitrogen adsorption measurements. CuO/MCM-41 is less ordered relative to pure MCM-41 and there are inter-aggregate pores resulting in a higher average pore diameter in the material. The formation of CuO particles on the external surface of MCM-41 and the possible reason for the less ordered structure of CuO/MCM-41 are also discussed in the present paper.     

Structural characteristics of porous polymers treated by freezing with water or acetone

The pore structure of nine polymers of different origin initial and treated in water and acetone for 24 h and then frozen by liquid nitrogen for 2 h was studied using low-temperature nitrogen adsorption. An average increase in pore volume and surface area is approximately 16 and 8%, respectively, after freezing with water and 19 and 8%, respectively, after treatment with acetone. However, for some samples, this effect is negative but for others, structural changes are significantly greater (up to 106%) than the average one. Certain treated polymers are characterized by shifted pore size distribution which is also accompanied by displacement of nitrogen adsorption energy distribution.     

Effect of the thermal and hydrothermal treatment on textural properties of Zr-MCM-41 mesoporous molecular sieve

Zr-containing mesoporous molecular sieves were synthesized by hydrothermal method using cetyltrimethyl ammonium bromide as a template and sodium silicate and zirconium sulfate as raw materials. The structure and morphology of the synthesized samples were characterized via various physicochemical methods, including X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, solid state nuclear magnetic resonance (²⁹Si MAS-NMR) techniques, thermal gravimetric-differential scanning calorimeter (TG-DSC) and N₂ physical adsorption, respectively. The effect of the different initial ZrO₂:SiO₂ molar ratio, the different thermal treatment temperature and the different hydrothermal treatment time on textural property was investigated. The experimental results reveal that the as synthesized samples possess a typical mesoporous structure of MCM-41. On the other hand, the specific surface area and pore volume of the synthesized Zr-MCM-41 mesoporous molecular sieve decrease with the increase of the amount of zirconium incorporated in the starting material, the rise of thermal treatment temperature and the prolonging of hydrothermal treatment time, the mesoporous ordering becomes poor. Also, when the molar ratio of ZrO₂:SiO₂ in the starting material is 0.1, the mesoporous structure of the Zr-MCM-41 mesoporous molecular sieve still retains after calcination at 750 °C for 3 h or hydrothermal treatment at 100 °C for 6 d, and have specific surface areas of 423.9 and 563.9 m²/g, respectively.     

Studies of intrawall porosity in the hexagonally ordered mesostructures of SBA-15 by small angle X-ray scattering and nitrogen adsorption

Ordered mesoporous silicas (OMSs) such as SBA-15 (p6mm symmetry group) synthesized in the presence of block copolymers containing poly(ethylene oxide) blocks possess irregular complementary pores in the walls of ordered mesopores. The X-ray scattering caused by this complementary porosity contributes to the background of the SAXS patterns. This work shows the possibility of using the SAXS data for the study of intrawall channels interconnecting ordered cylinders in SBA-15. The proposed SAXS analysis was tested by using a series of SBA-15 samples obtained at different temperatures of hydrothermal treatment (from 60 to 180 °C). The structural modelling of the SAXS patterns recorded for a series of SBA-15 samples was performed by using the continuous density function (CDF) technique in combination with the derivative difference minimization (DDM) method of full-profile refinement. This method is well suited for extraction of the background curves from the SAXS patterns. The resulting smooth background curves were analyzed by the well-known method in the SAXS theory used for evaluation of heterogeneity distributions, which in this case characterize the intrawall complementary porosity. A relatively good agreement has been observed between the data obtained by SAXS and nitrogen adsorption analysis. The SAXS analysis is sufficiently sensitive for examination of heterogeneous microporosity in SBA-15 materials. The average diameter of intrawall pores for the SBA-15 sample obtained at 60 °C was only about 1.4 nm. However, this diameter increased with the increasing temperature of hydrothermal treatment; namely, it was 1.5, 1.8, 2.6, 2.6, 3.5 and 5.2 nm for the SBA-15 samples hydrothermally treated at 80, 100, 120, 140, 160 and 180 °C, respectively.     

Stability and textural properties of cobalt incorporated MCM-48 mesoporous molecular sieve

Transition metal cobalt incorporated MCM-48 mesoporous molecular sieves (CoMCM-48) with different Co contents were synthesized hydrothermally at 120 °C for 24 h by directly adding fluoride ions to the initial gel. The resulting materials were characterized by means of XRD, TEM, FT-IR, UV-vis, TPR and N₂ physical adsorption, respectively. The effect of various factors, such as the Si/Co molar ratio, calcination temperature and hydrothermal treatment time, on the crystalline structure and textural properties of CoMCM-48 was investigated in detail. The results show that the CoMCM-48 mesoporous materials with high specific surface area were successfully synthesized. A small amount substitution of Co for Si in MCM-48 did not significantly change the textural properties while the higher cobalt incorporated leads to decrease of the surface area and deterioration of structural regularity. Furthermore, the resulting CoMCM-48 still retained the cubic mesoporous framework even after calcination at 800 °C for 4 h or hydrothermal treatment at 100 °C for 24 h.     

Adsorption in cylindrical pores: Mixed lattice-site/off-site Monte Carlo simulations in pores with heterogeneous wall structure

We present results of grand canonical Monte Carlo simulations of adsorption in cylindrical pores with rough surface modeled by lattice-site approach. Each site is characterized by two parameters: structural and energetic, which locally modify the structure and energy properties of the surface. There are three types of sites, randomly distributed over the wall: attractive, neutral and repulsive with respect to the smooth pore model. The results presented here show how this model affects the mechanism of adsorption and how it changes the forms of adsorption isotherm. We compare our numerical results with the experimental data of adsorption of a simple fluid (CH₄, T = 77 K) in cylindrical silica pore of diameter d = 4 nm (MCM-41 material).     

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.     

Mesoporous titania-alumina mixed oxide: A preliminary study on synthesis and application in selective catalytic reduction of NOx

Titania-alumina mixed oxide was synthesized hydrothermally using tetrapropylammonium hydroxide (TPAOH) as the template. The dried, calcined and palladium loaded samples were characterized for particle morphology, weight loss, nitrogen adsorption/desorption at liquid nitrogen temperature, texture and metal dispersion. The Pd loaded material was tested for NO reduction in a fixed bed catalytic reactor using a simulated gas mixture closely resembling lean burn engine exhaust. Scanning electron microscopy of the dried and calcined samples revealed a well developed tubular fibrous network of titania-alumina. Thermogravimetry (TG) of the dried sample indicated about 16% weight loss due to decomposition of an oxy-hydroxide structure of the material, mostly boehmite, which was confirmed by X-ray diffraction (XRD) measurements. The boehmite phase changed to poorly crystalline γ-alumina upon calcination where as titania remained as anatase. BET specific surface area, adsorption-desorption isotherms and BJH pore size distributions indicated formation of a mesoporous structure. The surface area of the dried material increased when calcined at 600 °C but the pore size distribution patterns for the dried, calcined and palladium dispersed materials remained unchanged. These observations along with TG and XRD analyses suggest that a thermo-resistant, mesoporous, high surface area, crystalline titania-alumina framework can be prepared using the hydrothermal synthesis route. A peak NOx conversion of 75% with the palladium dispersed catalyst indicates high catalytic activity, possibly due to high dispersion of Pd confirmed by CO chemisorption studies.     

Physico-chemical properties of titania nanotubes synthesized via hydrothermal and annealing treatment

Titania nanotubes are synthesized via hydrothermal treatment of TiO₂ powders in NaOH solution at 110 °C for 90 h, followed by annealing at 400 °C. The morphology of nanotubes is characterized by field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). Microscopic observations on the transformation process indicate that the nanotubes retain their shapes after the annealing process. The crystalline structure and composition are examined by X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDX). The results confirm the absence of impurity peaks and the crystal structure change from nanotubes to anatase phase after annealing treatment. The average specific surface area of the particles is probed using gas adsorption-desorption measurements. The prepared tubular samples exhibit greater specific surface areas and higher pore volumes than the precursor. Moreover, it is apparent that the hydrothermal treatment modifies the optical properties of the titania samples and red-shifts the UV absorption to a band gap energy of 3.04 eV after annealing treatment.     

Preparation of activated carbons from used tyres by gasification with steam and carbon dioxide

Activated carbons were prepared from waste tyres by gasification with steam and carbon dioxide and their characteristics were investigated. A two-stage activation procedure (pyrolysis at 800 °C in N₂ atmosphere, followed by steam or carbon dioxide activation) was used for the production of activated samples. The effect of the activation temperature (750-900 °C) and the activation time (1-3 h) on the surface characteristics of the prepared carbon was investigated. Carbons produced to different degrees of burn-off were characterized by means of their nitrogen adsorption isotherms at 77 K. In both sets of experiments, the mesopore, micropore volume, and BET surface area increased almost linearly with the degree of activation. For burn-off values lower than 53%, the steam activation produced carbons with a narrower and more extensive microporosity and higher BET and external surface area than the carbon dioxide activation. As the activation proceeds (burn-off > 53%), a strong development of the mesoporosity in the carbons was observed and the micropores size distribution revealed broader micropores, that is, a more heterogeneous distribution.     

Preparation of uniform porous hydroxyapatite biomaterials by a new method

In this paper, a new method of preparation of uniform porous hydroxyapatite biomaterials was reported. In order to obtain uniform porous biomaterials, disk samples were formed by the mixture of hydroxyapatite (HAP) powders and monodispersed polystyrene microspheres, and then HAP uniform porous materials with different diameter and different porosity (diameter: 436 ± 25 nm, 892 ± 20 nm and 1890 ± 20 nm, porosity: 46.5%, 41.3% and 34.7%, respectively) were prepared by sintering these disk samples at 1250 °C for 5 h. The pure phase of HAP powders fabricated by the hydrothermal technology was confirmed by X-ray diffraction (XRD). The surface and size distribution of pores in HAP biomaterials were observed by scanning electron microscopy (SEM), and the pore size distribution in porous HAP biomaterials was tested by mercury intrusion method.     

Adsorption studies of thermal stability of SBA-16 mesoporous silicas

Cage-like ordered mesoporous silicas, SBA-16, and ethane-silicas with cubic (Im3m) and (Fm3m) symmetry groups were synthesized with addition of sodium chloride by using tetraethyl orthosilicate (TEOS) as silica precursor, 1,2-bis(triethoxysilyl)ethane (BTESE) as bridged silsesquioxane and poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) triblock copolymer Pluronic F127 (EO₁₀₆PO₇₀EO₁₀₆) as template at low acid concentrations. The resulting samples were subjected to extraction in order to remove the polymeric template. The as-synthesized and extracted materials were calcined in the range of 350-900 °C to determine their thermal stability. Based on the XRD analysis and nitrogen adsorption data such as the BET specific surface area, volume of primary mesopores, pore wall thickness and pore size distributions, the SBA-16 silicas exhibit relatively high thermal stability because their mesostructural ordering was retained even up to 900 °C. However, an increase in the calcination temperature tended to decrease significantly the BET surface area, volumes of primary and complementary pores, and to less extent the pore size and pore wall thickness due to the structural shrinkage. Furthermore, the as synthesized samples subjected to a short extraction with acidic ethanol solution possessed even better thermal stability. On the other hand, calcination at 550 °C of ethane-silicas caused a complete removal of the ethane bridging groups from the periodic mesoporous organosilicas and their calcination above 800 °C led to the partial collapse of the structure.     

Studies on ordered mesoporous materials for potential environmental and clean energy applications

Two series of ordered mesoporous materials, SBA-15 silica and CMK-3 carbon were synthesized. The ordered nanostructure of these materials was confirmed by TEM and XRD analysis. Structural parameters including the specific surface area, pore volume and pore size distribution were determined on the basis of nitrogen adsorption data at 77 K. Potential applications of these materials were explored in relation to the CO₂ sequestering, methane storage and fuel desulfurization. Initial studies of both materials showed their usefulness for environmental and clean energy applications. SBA-15 modified with triethanolamine showed a very good adsorption selectivity for CO₂ while its adsorption reversibility was retained. Also, this material after CuCl deposition was useful for removal of fuel thiophenes. However, CMK-3 was shown to be promising material for storage of natural gas. As high as 41 wt.% of methane was stored in this material in the presence of appropriate amount of water.     

Synthesis and characterization of a hexagonal mesoporous silica with enhanced thermal and hydrothermal stabilities

A synthetic route was developed for a novel hexagonal mesoporous silica that has remarkably wide channel diameters and thick walls. The procedure involved the acid-catalyzed hydrolysis of tetraethylorthosilicate in a water/ethanol/isopropoanol solvent mixture while employing 1-hexadecylamine as a templating agent and mesitylene as an auxiliary agent. After removal of the template by either extraction with ethanolic hydrochloric acid or by calcination at 550 °C, the resulting mesoporous materials had surface areas of 1283 and 1211 m²/g. The channel diameters were found to be 47.2-51.1 Å, while the wall thicknesses were 20.9-21.1 Å. X-ray powder diffraction demonstrated that the novel mesoporous silica belonged to the MCM-41 structural family. Notably, they displayed higher thermal and hydrothermal stabilities, and have higher surface areas than conventionally prepared MCM-41 silica. The thickest channel walls (21.1 Å) can withstand calcination to nearly 850 °C with minimal structural damage. The calcined sample was more resistant to hydrothermal treatment in boiling water than was the solvent-extracted product but both materials showed minimal change after 25 h of hydrothermal treatment.     

Post-treatment of mesoporous material with high temperature for synthesis super-microporous materials with enhanced hydrothermal stability

Super-microporous silicon material with high hydrothermal stability denoted as MCM-48-T has been prepared from mesoporous MCM-48 by high temperature treatment. The structural and chemical property of MCM-48-T has been characterized by variety of techniques such as small-angle X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂ adsorption-desorption, infrared spectroscopy (IR) and ²⁹Si MAS NMR, etc. The results showed that Si-OH groups are forced to condense by the treatment of high temperature and the pore size of MCM-48-T is around 1.03 nm in the super-microporous range. Besides, the ratio of Q⁴/Q³ increases considerably. Compared with the original material (MCM-48), the hydrothermal stability of MCM-48-T has significantly enhanced.     

X-ray metrology for advanced silicon processes

X-ray reflectivity (XRR), X-ray fluorescence (XRF) and small angle X-ray scattering (SAXS) techniques are used to the monitoring of Cu/porous low κ processes, which are developed for the next generation (≤65 nm) integrated circuits. Sensitivity of XRR and XRF is sufficient to detect drifts of the copper barrier layer, copper seed layer and Cu CMP (chemical-mechanical polishing) processes. Their metrology key parameters comply with production requirements. SAXS allows determining the pore structure of low κ films: average pore size and pore size distribution.     

Assessment of pore structure parameters for polymer-templated mesoporous molecular sieves by means of nitrogen and argon adsorption

Pore size, wall thickness, and microporosity of polymer-templated mesoporous silica (PTMS) can be controlled by using different nonionic triblock copolymers as soft templates. The evolution of the pore structure of PTMS was studied by using nitrogen and argon adsorption at 77 K in addition to powder X-ray diffraction and transmission electron microscopy.     

Carbon dioxide-activated carbons from almond tree pruning: Preparation and characterization

Activated carbons were prepared from almond tree pruning by non-catalytic and catalytic gasification with carbon dioxide and their surface characteristics were investigated. In both series a two-stage activation procedure (pyrolysis at 800 °C in nitrogen atmosphere, followed by carbon dioxide activation) was used for the production of activated samples. In non-catalytic gasification, the effect of the temperature (650-800 °C for 1 h) and the reaction time (1-12 h at 650 °C) on the surface characteristics of the prepared samples was investigated. Carbons were characterized by means of nitrogen adsorption isotherms at 77 K. The textural parameters of the carbons present a linear relation with the conversion degree until a value of approximately 40%, when they come independent from both parameters studied. The highest surface area obtained for this series was 840 m² g⁻¹. In the catalytic gasification the effect of the addition of one catalyst (K and Co) and the gasification time (2-4 h) on the surface and porosity development of the carbons was also studied. At the same conditions, Co leads to higher conversion values than K but this last gives a better porosity development.     

Adsorption of argon and nitrogen in cylindrical pores of MCM-41 materials: application of density functional theory

Adsorption of argon and nitrogen at their respective boiling points in cylindrical pores of MCM-41 type silica-like adsorbents is studied by means of a non-local density functional theory (NLDFT), which is modified to deal with amorphous solids. By matching the theoretical results of the pore filling pressure versus pore diameter against the experimental data, we arrive at a conclusion that the adsorption branch (rather than desorption) corresponds to the true thermodynamic equilibrium. If this is accepted, we derive the optimal values for the solid-fluid molecular parameters for the system amorphous silica-Ar and amorphous silica-N₂, and at the same time we could derive reliably the specific surface area of non-porous and mesoporous silica-like adsorbents, without a recourse to the BET method. This method is then logically extended to describe the local adsorption isotherms of argon and nitrogen in silica-like pores, which are then used as the bases (kernel) to determine the pore size distribution. We test this with a number of adsorption isotherms on the MCM-41 samples, and the results are quite realistic and in excellent agreement with the XRD results, justifying the approach adopted in this paper.