Kinetic study of template removal of MCM-41 nanostructured material

The siliceous MCM-41 molecular sieve was synthesized starting from a hydrogel with the following molar composition: 4.58SiO₂:0.437Na₂O:1CTMABr:200H₂O. The cetyltetramethylammonium bromide (CTMABr) was used as structure template. A kinetic study of template removal after the syntheses was performed by Vyazovkin model-free kinetic method obtaining apparent activation energy of 166±8.2 kJ mol^-1. This revised version was published online in August 2006 with corrections to the Cover Date.     

Study of the Adsorption Properties of MCM-41 Molecular Sieves Prepared at Different Synthesis Times

The variation of surface properties of SiMCM-41 and AlMCM-41 nanoporous materials as function of synthesis time was examined. The main properties studied were: surface area, pore diameter, pore volume, mesoporous parameter, and wall thickness. Siliceous MCM-41 molecular sieves were synthesized starting from hydrogels with the following molar compositions: 4.58SiO₂:0.435Na₂O:1 CTMABr:200 H₂O for SiMCM-41, and 4.58SiO₂:0.485 Na₂O:1 CTMABr:0.038 Al₂O₃:200 H₂O, for AlMCM-41. Cetyltrimethylammonium bromide (CTMABr) was used as the structural template. The crystallographic parameters were obtained from XRD data and by nitrogen adsorption using the BET and BJH methods. The results obtained showed a significant variation of the surface properties of the MCM-41 materials as a function of the synthesis time reaching silica wall thickness of ca. 2 nm on the fourth day.     

Influence of cross profile of PE fibers on thermal properties of materials

Molecular sieves MCM-41 were synthesized from rice husk ash (RHA) as alternative sources of silica, called RHA MCM-41. The material was synthesized by a hydrothermal method from a gel with the molar composition 1.00 CTMABr:4.00 SiO₂:1.00 Na₂O:200.00 H₂O at 100 °C for 120 h with pH correction. The cetyltrimethylammonium bromide (CTMABr) was used as a structure template. The material was characterized by X-ray powder diffraction, FTIR, TG/DTG, and surface area determination by the BET method. The kinetics models proposed by Ozawa, Flynn–Wall, and Vyazovkin were used to determine the apparent activation energy for CTMA⁺ species decomposition from the pores of MCM-41 material. The results were compared with those obtained from the MCM-41 synthesized with silica gel. The synthesized material had specific surface area, size, and pore volume as specified by mesoporous materials developed from conventional sources of silica.     

Model-free kinetics applied for the removal of CTMA<Superscript>+</Superscript> and TPA<Superscript>+</Superscript> of the nanostructured hybrid AlMCM-41/ZSM-5 material

The nanostructured hybrid AlMCM-41/ZSM-5 composite was synthesized starting from a hydrogel with molar composition SiO₂:0.32Na₂O:0.03Al₂O₃:0.20TPABr:0.16CTMABr:55H₂O. The cetyltrimethylammonium bromide (CTMABr) and tetrapropylammonium bromide (TPABr) were used as templates. The above mentioned material presents morphological properties with specific characteristics, such as the surface area of the composite which is approximately half of the surface area of the conventional MCM-41. Another interesting feature is the formation of walls with the double of the density of the MCM-41 structure, which characterizes the hybrid material, resulting in a high stability material for catalytic application. The aim of this study is obtain optimized structures of the hybrid material and for this purpose variations in the synthesis time were carried out. A comparative analysis was performed including X-ray diffraction, Fourier transform infrared spectroscopy, and Thermogravimetry measurements. The model-free kinetic algorithms were applied in order to determinate conversion and apparent activation energy of the decomposition of the CTMA⁺ and TPA⁺ species from the hybrid AlMCM-41/ZSM-5.     

Kinetic parameters of surfactant remotion occluded in the pores of the AlMCM-41 nanostructured materials

A series of AlMCM-41 molecular sieves was synthesized starting from a hydrogel with the following molar composition: 1CTMABr:4.58SiO₂:(0.437 + X)Na₂O:XAl₂O₃:200H₂O. Tetramethylammonium silicate (TMAS) was used as silicon source and cethyltrimethylammonium bromide (CTMABr) was used as structure template. The obtained materials were characterized by nitrogen adsorption, XRD, FT-IR and TG/DTG. Model-free kinetic algorithms were applied in order to determinate conversion, isoconversion and apparent activation energy to decomposition of CTMA+ species from the AlMCM-41 materials with different silicon/aluminium (Si/Al) ratios of 20, 40, 60 and 80.     

杂原子介孔Ce-MCM-41分子筛的制备及其吸附脱除甲硫醚性能

以十六烷基三甲基溴化铵为模板剂,正硅酸乙酯(TEOS)为硅源,硝酸铈为铈源,采用水热法合成了杂原子介孔分子筛Ce-MCM-41。XRD和FT-IR表征结果表明,当加入的Ce/Si物质的量比小于0.04时合成了规整有序的介孔结构,并将Ce原子引入到MCM-41骨架中。N₂吸附-脱附测试获得MCM-41和Ce-MCM-41(Ce/Si物质的量比为0.04)的平均孔径分别为2.82和2.46 nm,孔容分别为0.762 1和 0.689 4 m³/g,BET比表面积分别为986.42和756.8 m²/g。NH₃-TPD表征结果表明,Ce-MCM-41的酸性要明显强于MCM-41,但两种分子筛的酸性均较弱。利用合成的MCM-41和Ce-MCM-41吸附脱除甲硫醚浓度为58 μg(甲硫醚)/g的甲硫醚/氮气混合气中的甲硫醚。甲硫醚分子尺寸的模拟结果为0.464 8 nm,可以很容易地进入分子筛的介孔孔道中。由于Ce-MCM-41分子筛具有较多的酸量,其硫吸附容量7.52 mg(S)/g明显高于MCM-41的4.57 mg(S)/g。MCM-41和Ce-MCM-41都具有较好的再生性能,再生3次后硫吸附容量仍可恢复到初始容量的80%,分别为3.52和 5.86 mg(S)/g。     

Removal of complexed mercury by dithiocarbamate grafted on mesoporous silica

Mesoporous silica (MCM-41) with d ₍₁₀₀₎ interplanar distance of 38 Å was prepared by a room temperature process through low surfactant templation technique. The surface of MCM-41 was functionalized with dithiocarbamate (dtc) ligand, named as MCM-41-dtc and this was characterized by X-ray diffraction, BET surface area, particle size analysis, ²⁹Si MAS NMR spectra and sulphur analysis. The sorption of mercury from 0.1M HCl solution by MCM-41-dtc was studied as a function of pH, [Hg²⁺], time and temperature. The sorption data obtained at various initial concentrations of mercury were fitted into Langmuir adsorption model. Mercury speciation in solution and the sorption capacity measurements indicated possible formation of a 1 : 1 square planar complex in the solid phase. A very rapid sorption of mercury was observed in the initial stages of equilibration, which can be attributed to the large surface area, wide porosity and fine particle size of MCM-41-dtc, facilitating facile accessibility of mercury into the inner pores of the sorbent. The enthalpy change accompanied by the sorption of mercury was found to decrease from 83.7 to 6.2 kJ/mol, when the initial concentration of mercury was increased from 5^.10^-4M to 1.5^.10^-3M.     

Preparation of MnCo/MCM-41 catalysts with high performance for chlorobenzene combustion

MCM-41 was synthesized by a soft template technique. The specific surface area and pore volume of the MCM-41 were 805.9 m²/g and 0.795 cm³/g, respectively. MCM-41-supported manganese and cobalt oxide catalysts were prepared by an impregnation method. The energy dispersive X-ray spectroscopy clearly confirmed the existence of Mn, Co, and O, which indicated the successful loading of the active components on the surface of MCM-41. The structure and function of the catalysts were changed by modulating the molar ratio of manganese to cobalt. The 10%MnCo(6:1)/MCM-41 (Mn/Co molar ratio is 6:1) catalyst displayed the best catalytic activity according to the activity evaluation experiments, and chlorobenzene (1000 ppm) was totally decomposed at 270 °C. The high activity correlated with a high dispersion of the oxides and was attributed to the exposure of more active sites, which was demonstrated by X-ray diffraction and high-resolution transmission electron microscopy. The strong interactions between MnO₂, Co₃O₄, MnCoO_x, and MCM-41 indicated that cobalt promoted the redox cycles of the manganese system. The bimetal-oxide-based catalyst showed better catalytic activity than that of the single metal oxide catalysts, which was further confirmed by H₂ temperature-programmed reduction. Chlorobenzene temperature-programmed desorption results showed that 10%MnCo(6:1)/MCM-41 had higher adsorption strength for chlorobenzene than that of single metal catalysts. And stronger adsorption was beneficial for combustion of chlorobenzene. Furthermore, 10%MnCo(6:1)/MCM-41 was not deactivated during a continuous reaction for 1000 h at 260 °C and displayed good resistance to water and benzene, which indicated that the catalyst could be used in a wide range of applications.     

Increasing the efficiency of silicon and aluminum extraction from Volclay by a water iteration treatment for the synthesis of MCM-41 nanomaterials

This work aims to reduce the prices of a wide range of nanomaterials which are unreachable in the industry by using natural sources as silicon and aluminum precursors. In a previous work, silicon and aluminum have been extracted from Volclay after applying the alkaline fusion process at 550 °C, and a water treatment of this fused clay by adopting a weight ratio (1:4, fusion mass:H₂O) to synthesize Al-MCM-41 nanomaterials. In this study, the weight ratio of fusion mass:H₂O was increased to 1:8 to synthesize a highly structurally ordered MCM-41 under the same reaction conditions. The Al-MCM-41 nanomaterials are investigated by inductively coupled plasma optical emission spectrometry (ICP–OES), powder X-ray diffraction (XRD), N₂ adsorption–desorption measurements and scanning electron microscopy (ESEM). As a result, the increase in the weight ratio fusion mass:H₂O generates more silica and aluminum, which allows the formation of well-ordered MCM-41 nanomaterials with high pore volume (0.70 cm³/g), high surface area (1044 m²/g), and uniform mesoporous diameter (3.67 nm); as a consequence, the increase in the weight ratio fusion mass:H₂O leads to an increase in the mass of Al-MCM-41 (9.3 g for 1:8 compared to 5 g for 1:4), whereas the yield of production of mesoporous materials increases to 86%.     

Surfactant effects on the physical properties of mesoporous silica and silicates

Mesostructured silicas and silicates have been synthesized using hydrogels with molar composition: M:26.0SiO₂:5.2(C₂H₅)₄NOH:7.5[CH₃(CH₂)₁₅N(CH₃)₃]₂O:790H₂O, where M=0, Zr(OC₃H₇)₄ or Ti(OC₄H₉)₄. In all preparations, colloidal silica (Ludox) was used as the source of silica. The hydrothermal transformation at 110°C of these gels produced solids with the hexagonal structure typical of MCM-41 type materials. The effects of chain length and surfactant terminal alkyl groups on the properties of mesoporous materials containing Ti or Zr, have been investigated by using different surfactants such as cetyl trimethyl ammonium bromide and chloride, cetyl dimethyl ethyl ammonium bromide, and myristyl trimethyl ammonium bromide. When the surfactant's carbonyl chain decreased to 14 from 16 carbon atoms, a reduction in unit cell dimension and average pore diameter was observed in the mesoporous silicas, titaniumsilicates and zirconiumsilicates under study. Replacement of methyl groups with ethyl groups on the surfactant hydrophobic head, had no measurable effects on crystals' properties. However, a surfactant with a bulky aromatic head group, such as cetyl pyridinium chloride, inhibited crystallization. In general, the use of bromide in place of chloride salts yielded more ordered MCM-41 type crystals. The high thermal stability (to 800°C), surface area (1000–1500 m²/g), pore volume (0.90–1.20 cm³/g) and uniform mesoporosity (with pore diameter in the 2.9 nm–3.6 nm range), of these metalsilicates could be of particular interest in the preparation of catalysts requiring siliceous metal supports.     

Phase Transformation of MCM-41 in the Mother Liquid at Moderate Temperature

A new crystalline phase (via amorphous intermediate), NCUZ-1, was obtained when MCM-41 (Si/Al=9) was under prolonged heating in the mother liquid (which contains NaAlO₂, [N(CH₃)₄]₂SiO₃, SiO₂, and surfactant C₁₆H₃₃N(CH₃)₃OH(aq) at 105°C for more than two weeks. The largest d spacing of NCUZ-1 calculated from X-ray diffraction data is approx. 6 Å, indicating that the long-range order of the mesopores in MCM-41 was not present in NCUZ-1. Nitrogen absorption studies showed that NCUZ-1 contains both mesopores and micropores. The volume ratio of the mesopore to micropore is approx. 10 to 1 and the BET surface area is 400 m²/g. The TEM micrograph of NCUZ-1 revealed a homogenous phase with distorted mesopores. The ¹³C NMR spectrum of NCUZ-1 before calcination is similar to that of uncalcined MCM-41, indicating that the organic templates in both phases have a similar structure. In the phase transformation process, the counteranion (OH⁻) of the surfactant template played an important role. It increased the solubility of the aluminosilicate wall; the breaking and reforming the Si–O and Al–O bonds make the phase transformation possible, although the process is very slow. When C₁₆H₃₃N(CH₃)₃Cl, instead of C₁₆H₃₃N(CH₃)₃OH, was used as a template, no NCUZ-1 phase was obtained under the same reaction conditions. TEM micrograph, nitrogen absorption isothermal, and ¹³C NMR spectra of NCUZ-1 suggested that the mesopores were present in the NCUZ-1 phase, although there is no long-range order of these mesopores.     

Progress in Pore-Size Control of Mesoporous MCM-41 Molecular Sieve Using Surfactant Having Different Alkyl Chain Lengths and Various Organic Auxiliary Chemicals

Pore-size control of mesoporous silica MCM-41 molecular sieve is described on the basis of the use of surfactant having different alkyl chain lengths and various organic auxiliary chemicals during the hydrothermal synthesis process. The BJH pore diameter of MCM-41 can be tuned from 1.6 to 4.2 nm using single or mixture of two surfactant(s) with alkyl chain lengths varied from C₈ to C₂₂. By the addition of different organic auxiliary chemicals: 1,3,5-trimethylbenzene, isopropylbenzene or tridecane into the synthesis medium, the BJH pore size of MCM-41 can be tailored up to 12.0 nm.     

The Synthesis and Application of the Mesoporous Molecular Sieves MCM-41 — A Review

We report a “delayed neutralization” process for the preparation of highly-ordered aluminosilicate MCM-41 molecular sieves with high thermal and hydrothermal stability, and sharp pore size distribution. However, the structural order and pore size are dependent on the carbon chain length. In the mixture surfactant systems, the pore size of the MCM-41 materials could be fine-tuned. The pore size can be extended from 2.5 to 4.5 nm by adding a suitable amount of hydrocarbons. The tubular morphology of the MCM-41 material of 0.3 to 10 micrometers diameter, where the wall consists of coaxial cylindrical pores of nanometers MCM-41, can be obtained by careful control of the surfactant-water content and the rate of condensation of silica. An optimum condition for automatic synthesis of the hierarchical TWT structure has been accomplished. The addition of 1-alkanols as cosurfactant would not only improve the order of the MCM-41 hexagonal structure but also promote the formation of micrometer-sized hierarchical materials, for example: tubules-within-tubule and uniform-sized hollow spheres of diameter 5.0 ± 1.0 μm. However, the inside of the micron spheres has intricate structures possessing various topological genus ranks. The MCM-41 is a good supporter for Molybdenum oxide catalysts. The rate of deactivation in the catalytic reaction of ethyl-benzene dehydrogenation to styrene increases in the order: M_T < M_P < SiO₂. The physically mixed samples have higher catalytic activity than impregnated ones.     

Characterization and optimization of mesoporous magnetic nanoparticles for immobilization and enhanced performance of porcine pancreatic lipase

In this paper, Fe₃O₄ nanoparticles coated with mesoporous silica were prepared successfully, noted as Fe₃O₄ at the mobile composition of matter No. 41 (MCM-41). Also, Fe₃O₄ at MCM-41 was grafted by both 3-aminopropyltriethoxysilane (APTS) and 3-chloropropyltriethoxysilane (CPS), noted as Fe₃O₄ at MCM-41/APTS and Fe₃O₄ at MCM-41/CPS. The compounds were characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, vibrating sample magnetometry, thermogravimetry and N₂ adsorption/desorption. Then, the enzyme, porcine pancreas lipase (PPL), was immobilized onto these modified nanoparticles by covalent attachment, physical adsorption and cross-linking, noted as Fe₃O₄ at MCM-41/CPS-PPL, Fe₃O₄ at MCM-41-PPL and Fe₃O₄ at MCM-41/APTS-PPL, respectively. The results showed that Fe₃O₄ at MCM-41/CPS was the best nanomaterial for PPL immobilization, exhibiting enhanced immobilization efficiency (maximum 96%), maximum relative activity (up to 96%), high stability and reusability (83% 56 days and 86.7% ten cycles). Additionally, it offered some other advantages, such as easy recycling and reuse, complying with the trend of green chemistry. Therefore, Fe₃O₄ at MCM-41/CPS in combination with a relevant method can be proposed for commercial applications.     

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.     

The Synthesis and Characteristics of Vanadoaluminosilicate MCM-41 Mesoporous Molecular Sieves

A series of vanadoaluminosilicate MCM-41 mesoporous molecular sieves with various compositions have been hydrothermally synthesized. Hexadecyltrimethylammonium bromide was used as a surfactant in the synthesis. The samples were characterized with nitrogen sorption, X-ray diffraction, differential thermal analysis, thermogravimetric analysis, Fourier transform-Infrared spectroscopy, UV-visible spectroscopy, scanning electron microscopy, transmission electron microscopy, and solid state NMR. The solid products had the MCM-41 structure and contained only atomically dispersed vanadium and aluminum consistent with framework vanadium and aluminum. The samples were hydrophobic and contained large amount of surfactant in the as-synthesized samples. The surfactant could be removed upon calcination at 450°C. N₂ sorption measurements and TEM demonstrate the high mesoporosity of [V, Al]-MCM-41. The incorporation of vanadium and aluminum into MCM-41 decreased the surface area to some extent. The morphologies of all the samples were the agglomerate of plates. ²⁹Si MAS NMR shows that the pore wall is amorphous. ²⁷Al MAS NMR shows that all of aluminum species were tetrahedrally coordinated even after calcination at 550°C.     

Preparation of ethylene/α-olefins copolymers using (2-RInd)2ZrCl2/MCM-41 (R:Ph,H) catalyst,microstructural study

(2-RInd)₂ZrCl₂ (R:Ph,H) catalyst was supported on MCM-41 and ethylene copolymerization behavior as well as microstructure of copolymers were studied. A steady rate–time profile behavior was observed for homo and copolymerization of ethylene using supported catalysts. It was noticed that increasing the comonomer content can result in lower physical properties. The obtained results indicated that (2-PhInd)₂ZrCl₂/MCM-41 had higher ability of comonomer incorporation than the non-substituted supported catalysts. The CCC, CCE, and ECC (C: comonomer, E: ethylene) triad sequence distribution in backbone of copolymers were negligible, that means no evidence could be detected for comonomer blocks. The polymer characterization revealed that utilizing 1-octene instead of 1-hexene as the comonomer leads to more heterogeneous distribution of chemical composition. The heterogeneity of the chemical composition distribution and the physical properties were influenced by the type of comonomer and catalyst. (2-PhInd)₂ZrCl₂/MCM-41 produced copolymers containing narrower distribution of lamellae (0.3–1 nm) than the copolymer produce using Ind₂ZrCl₂/MCM-41 (0.3–1.6 nm).     

不同结构颗粒对PMMA基复合材料性能影响

采用原位本体聚合法制备PMMA/MCM-41(with template),PMMA/SBA-15(with template),PMMA/SiO2三种复合材料.研究了介孔分子筛MCM-41,SBA-15和SiO2对PMMA复合材料拉伸强度,冲击强度,热稳定性的影响.由于合成介孔分子筛MCM-41,SBA-15时所用的模板剂CTAB和P123分布于孔口处和颗粒表面上,分别与PMMA基体产生物理缠结作用,增加了两者的相容性;且P123(EO20PO70EO20)表面有较大的PO/EO比率,与小分子量的CTAB相比有较强的疏水性,使得PMMA/SBA-15(with template)复合材料的性能要优于PMMA/MCM-41(with template).