Effect of the Preparation Conditions on the Structure,Porosity, and Stability of Mesoporous Materials of the MCM-41 Type

The effect of the addition of metal salts and their complexes on the structure, porosity, and stability of MCM-41, added to the reaction mixture or during removal of the template from the mesophases after synthesis, was investigated. It was established that additions of inorganic salts reduce the compression of the structure during thermal removal of the template. The relation between the compression effect and the hydrolytic stability of MCM-41 is examined. __________ Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 41, No. 4, pp. 225–230, July–August, 2005.     

Influence of the composition of the reaction mixture and the synthesis conditions on the formation of mesomorphous substances in the presence of glucose oxidase

The possibility of synthesizing mesoporous substances in silicate and aluminosilicate systems in the presence of combinations of glucose oxidase and cetyltrimethylammonium bromide has been demonstrated. Highly crystalline mesoporous molecular sieves of type MCM-41 with a high aluminum content were obtained from the aluminosilicate system with a reaction mixture pH close to neutral. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Prospekt Nauki, Kiev 252039, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 35, No. 3, 190–193, May–June, 1999.     

Characteristics of molecular sorption on template containing mesoporous molecular sieves of type MCM-41

Template containing materials of type MCM-41 have properties of microporous substances. On absorption into the micropores of such materials the dependence of the characteristic absorption energies on the molecular mass of the sorptive is extreme, and the specific absorption volume decreases with increased molar volume of the sorptive. A model is proposed to explain the peculiarities of the absorption properties of the template containing materials. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine 31 Prospekt Nauki, Kiev 252039, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 35, No. 6, 367–372, November–December, 1999.     

Synthesis,characterization and catalytic activities of bimetallic modified MCM-41 for epoxidation of styrene

Mesoporous molecular sieves MCM-41 modified by bimetal (Zr and Ti) ions with ordered hexagonal arrangement were prepared by direct synthesis under microwave–hydrothermal conditions at 403 K. FT-IR, N₂ adsorption–desorption, scanning electron microscope, high-resolution transmission electron microscope, element mapping, X-ray photoelectron spectroscopy, diffuse Reflectance UV–Visible Spectra etc. were used to characterize as-prepared materials. The results showed that Zr and Ti were introduced into MCM-41 and bonds of Zr–O–Si and Ti–O–Si were formed in framework of the MCM-41. Moreover, their structures with ordered arrangement were still retained. The microwave–hydrothermal method might shorten the synthesis time from days to hours and the as-prepared catalyst had a high catalytic activity and selectivity for the liquid-phase epoxidation of styrene.     

Investigation of the mechanism of methane formation in the fischer-tropsch synthesis on a Co/SiO2·ZrIV catalyst

Methane is formed in the Fischer-Tropsch synthesis under real conditions both through intermediates leading to chain propagation and by hydrogenation of surface carbon. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Prospekt Nauki 31, 252039 Kiev, Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, No. 1, pp. 41–43, January–February, 1996.     

Effect of polyether diamine on gas permeation properties of organic-inorganic hybrid membranes

The quantitative incorporation and high dispersion of platinum nanoparticles into MCM-41 has been carried out by the coordination between Pt(IV) ion and APTMS-anchored MCM-41. Before and after calcination of Pt/APTMS/MCM41 samples, the Pt content in samples was evaluated from home-made photoacoustic spectrometer (PAS). The PAS bands at 350 nm and 450 nm can be assigned to d–d transition bands of Pt complexes. By increasing the concentration of Pt solution, the PAS intensity of Pt/APTMS/MCM41 was increased proportionally up to 1.0×10⁻² M, and remained constant above 1.0×10⁻² M. It can be attributed to the saturation of Pt content within Pt/APTMS/MCM41. The Pt content in the saturated Pt/APTMS/MCM41 was 8.5 wt% (the theoretical value), 9.7 wt% (measured by EDX) and 9.2 wt% (measured by ESCA), respectively. This indicates that the content of Pt precursor within MCM-41 could be controlled by the concentration of Pt precursor solution. The PAS intensity of calcined Pt/APTMS/MCM41's in H₂ flow was increased up to 1.0×10⁻² M and remained nearly constant above 1.0×10⁻² M. Therefore, we suggest that the formation of Pt complexes with APTMS-anchored MCM-41 made it possible to incorporate quantitatively Pt nanoparticles in the range of 0.5–9.2 wt% within MCM-41 channels.     

Effect of titanium on the structure and properties of mesoporous MCM-41 molecular sieves

Mesoporous MSM-41 titanium silicate molecular sieves with high titanium content were synthesized. The hexagonal structure along with high specific surface and pore volume are retained up to Si/Ti≥5. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Prospekt Nauki, Kiev 252039, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 35, No. 3, pp. 177–182, May–June, 1999.     

Influence of the incorporated metal on template removal from MCM-41 type mesoporous materials

Al-modified MCM-41, La-modified MCM-41, and Ce-modified MCM-41 mesoporous materials were prepared with different molar ratios (Si/M = 10; 25; 50; 100 and 200) at room temperature. The materials were characterized using XRD, BET–BJH, and TG–DTA. The XRD showed four peaks, due to the ordered hexagonal array of parallel silica tubes, which could be indexed as (100), (110), (200), and (210), assuming a hexagonal unit cell. The surface area decreased as the concentration of the metal incorporated in the material increased. The thermal stability of the materials was around 650 °C. The CeO₂ phase made the mass transfer process more difficult, hindering Hofmann degradation and favoring oxidation.     

Vanadium(V)-doped MCM-41 synthesised by a novel one-step procedure

 A novel procedure to synthesise V-doped surfactant–templated mesoporous materials in one step using a V(V) complex is described. The resulting V(V)–MCM-41 material had a bimodal pore size distribution. Received: 25 April 2001 Accepted: 20 June 2001     

Synthesis of MCM-41 supported amino-palladium complex and its catalytic performance for heck reaction

Using MCM-41 as the supporter, a series of MCM-41 supported amino-palladium complexes has been prepared and characterized by XRD (X-ray diffraction) and XPS (X-ray photoelectron spectroscopy), etc. The XRD and XPS results indicate that the Pd coordinates with the -NH₂ groups on the MCM-41 surface, and the structure of MCM-41 has been not damaged. Its catalytic performance for Heck arylation of alkene with aryl iodide shows that the catalysts have high activity and stereoselectivity in 70–90°C. The product of Heck reaction is in E form. And the effect of the preparation condition of catalyst on the catalytic performance was examined. Translated form Chinese Journal of Organic Chemistry, 2008, 28(5) (in Chinese)     

Catalytic activity of nanosized Co-Cu oxide systems in the deep oxidation of methane

The effect of the composition of nanosized catalysts, produced by thermal decomposition of Co(II) and Cu(II) formates deposited on ZrO₂, SBA-15, and MCM-41, on their activity in the deep oxidation of methane was investigated. It was shown that the activity of the catalyst depends on the nature of the support and on the Co/Cu ratio. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 41, No. 6, pp. 331–335, November–December, 2005.     

Effects of cation composition in MCM-41 mesoporous molecular sieves on the structures of encapsulated 4-pentyl-4′-cyanobiphenyl liquid crystals

The proportions of the various states are determined by the cation composition of the matrix for liquid-crystal material encapsulated in the pore spaces of mesoporous molecular sieves of MCM-41 type having high aluminum contents. The liquid-crystal properties are retained in the encapsulated state. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 36, No. 4, pp. 257–262, July–August, 2000.     

Effect of pore expansion and amine functionalization of mesoporous silica on CO2 adsorption over a wide range of conditions

Adsorption of CO₂ was investigated over a wide range of conditions on a series of mesoporous silica adsorbents comprised of conventional MCM-41, pore-expanded MCM-41 silica (PE-MCM-41) and triamine surface-modified PE-MCM-41 (TRI-PE-MCM-41). The isosteric heat of adsorption, calculated from adsorption isotherms at different temperatures (298–328 K), showed a significant increase in CO₂–adsorbent interaction after amine functionnalization of PE-MCM-41, consistent with the high CO₂ uptake in the very low range of CO₂ concentration. The CO₂ adsorption isotherm and kinetics data showed the high potential of TRI-PE-MCM-41 material for CO₂ removal in gas purification and separation applications. With TRI-PE-MCM-41, the CO₂ selectivity over N₂ was drastically improved over a wide range of conditions compared to pure mesoporous silica. Moreover, the adsorption was reversible and fast, and the adsorbent was thermally stable and tolerant to moisture.     

Studies on the State of Fe and La in MCM-41 Mesoporous Molecular Sieve Materials by TG Analysis and Other Techniques

Siliceous MCM-41 mesoporous materials and those possessing Fe, La, Al,respectively, were synthesized using water glass as silica source. Results from thermogravimetric analysis and other techniques showed us that Fe(III) or La(III) species was incorporated into framework. Owing to Fe–O or La–O bond longer than Si–O bond, Fe(III) or La(III) species was limited to insert into framework and transformed from tetrahedrally coordinated state to octahedrally coordinated state upon calcination to remove template. This revised version was published online in July 2006 with corrections to the Cover Date.     

Sorption of hydrogen by MCM-41 molecular sieves containing nanoparticles of 3d metals or their oxides

It was shown that the sorptive capacity for hydrogen in composites based on MCM-41 molecular sieves and nanoparticles of the oxides of 3d metals or the metals themselves at 77 K and 1 atm is determined both by the surface area and by the volume of the micropores of the samples and does not depend on the nature of the 3d metal (Ni, Co, Cu) or its degree of oxidation. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 5, pp. 265–270, September–October, 2006.     

Gas adsorption in mesoporous micelle-templated silicas: MCM-41, MCM-48, and SBA-15

This paper reports a molecular simulation and experimental study on the adsorption and condensation of simple fluids in mesoporous micelle-templated silicas MCM-41, MCM-48, and SBA-15. MCM-41 is described as a regular cylindrical silica nanopore, while SBA-15 is assumed to be made up of cylindrical nanopores that are connected through lateral channels. The 3D-connected topology of MCM-48 is described using a gyroid periodic minimal surface. Argon adsorption at 77 K is calculated for the three materials using Grand Canonical Monte Carlo simulations. Qualitative comparison with experiments for nitrogen adsorption in mesoporous micelle-templated silicas is made. The adsorption isotherm for SBA-15 resembles that for MCM-41. In particular, capillary condensation and evaporation are not affected by the presence of the connecting lateral channels. In contrast, the argon adsorption isotherm for MCM-48 departs from that for MCM-41 having the same pore size. While condensation in MCM-41 is a one-step process, filling of MCM-48 involves two successive jumps in the adsorbed amounts which correspond to condensation in different domains of the porosity. The condensation pressure for MCM-48 is larger than that for MCM-41. We attribute this result to the morphology of the MCM-48 surface (made up of both concave and convex regions) that differs from that for MCM-41 (concave only). Our results suggest that the pore connectivity affects pore filling when the size of the connections is comparable to that of the nanopores.     

Influence of Confinement on The Phase Transition And Spectral Characteristics of Nematic Liquid Crystals

The results of nematic liquid crystal - isotropic liquid phase transition study by the method of differential scanning calorimetry for inclusion compounds - mesoporous aluminosilicate molecular sieves of MCM-41 type (including Cu-exchanged samples) with encapsulated in inner-crystalline space nematic liquid crystal (5CB), as well as IR spectroscopic data for such compounds were represented. It was shown, that the 5CB molecules are able to interact with the active centers in the MCM-41 channels forming strong enough bonds of -C≡N⋅⋅⋅H-O- type. The relative amount of 5CB molecules interacting with the walls of channels and those retaining ‘liquid crystalline’ state in binary systems of molecular sieves MCM-41 and CuMCM-41 was estimated. This conclusion was confirmed by the data obtained from differential scanning calorimetry measurements. This revised version was published online in August 2006 with corrections to the Cover Date.     

Controlling of physicochemical properties of nickel-substituted MCM-41 by adjustment of the synthesis solution pH and tetramethylammonium silicate concentration

The effect of initial synthesis solution pH and tetramethylammonium silicate concentration in the synthesis solution on the physical and chemical properties of MCM-41 was systematically investigated using N(2) physisorption, X-ray diffraction, temperature-programmed reduction, in situ Fourier transform IR, UV-vis, and X-ray absorption spectroscopies. pH and tetramethylammonium (TMA) fraction affect the porosity of MCM-41 and the reducibility of incorporated Ni cations; higher pH and TMA concentration produced more porosity with higher stability against reduction, which is attributed to more metal ions locating in the interior of the silica walls. The control of the pore diameter of mesoporous MCM-41 at the sub-nanometer scale may be accomplished by adjusting the pH and TMA fraction. pH may be used to control the surface free silanol group density and nickel reduction degree as well, and this is useful in the design of a specific catalyst for particular reactions, such as CO methanation, which requires highly dispersed, stable metallic clusters with controllable size.     

Adsorption of crystal violet dye from aqueous solution using mesoporous materials synthesized at room temperature

In this work, batch adsorption experiments are carried out for crystal violet dye using mesoporous MCM-41 synthesized at room temperature and sulfate modified MCM-41 prepared by impregnation method using H₂SO₄ as sulfatising agent. The surface characteristics, pore structure, bonding behavior and thermal degradation of both the MCM-41 samples are characterized by nitrogen adsorption/desorption isotherms, X-ray diffraction (XRD) patterns, Fourier transform infrared (FT-IR) spectroscopy and thermo gravimetric analysis (TGA). The adsorption isotherm, kinetics and thermodynamic parameters are investigated for crystal violet (CV) dye using the calcined and sulfated MCM-41. Results are analysed using Langmuir, Freundlich and Redlich-Peterson isotherm models. It is found that the Freundlich model is an appropriate model to explain the adsorption isotherm. The highest adsorption capacity achieved is found to be 3.4×10⁻⁴ mol g⁻¹ for the sulfated MCM-41. The percentage removal of crystal violet dye increases with increase in the pH for both the MCM-41 adsorbents. Kinetics of adsorption is found to follow the second-order rate equation. From the thermodynamic investigation, it is evident that the adsorption is exothermic in nature.     

Mechanism of reactions of photocatalytic synthesis of chlorohydrins

A mechanism of photocatalytic synthesis of chlorohydrins from olefins and peroxo complexes of titanium (IV) is proposed. It consists of formation of radical-containing complexes, their reactions with olefins, and decomposition of the α-oxides obtained by hydrogen chlorides. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Prosp. Nauki, 252039 Kiev, Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 33, No. 1, pp. 17–21, January–February, 1997.