Influence of functional silanes on hydrophobicity of MCM-41 synthesized from rice husk

Mesoporous molecular sieve MCM-41 was synthesized from rice husk and rice husk ash, called RH-MCM-41 and RHA-MCM-41. The sol–gel mixtures were prepared with molar composition of 1.0 SiO₂: 1.1 NaOH: 0.13 CTAB: 0.12 H₂O. After calcination, the polarity of MCM-41 still remained on its surface due to the existence of some silanol groups. In this study, both RH-MCM-41 and RHA-MCM-41 were silylated with two different functional silanes trimethylchlorosilane (TMCS) and phenyldimethylchlorosilane (PDMS) in order to reduce the surface polarity. The efficiency of silylation was determined based on the amount of moisture adsorbed using thermogravimetric analysis (TGA). The structure of silylating agents and silica templates were found to be important parameters affecting the hydrophobic property of the MCM-41 surface. The post-grafting silylation with aliphatic silane can decrease the surface polarity better than that with aromatic silane, probably due to less sterric hindrance effect. Thus, the surface hydrophobicity of MCM-41 can be improved by the silylation of small molecular silane on RH-MCM-41.     

Room temperature synthesis of Si-MCM-41 using polymeric version of ethyl silicate as a source of silica

Synthesis of mesoporous MCM-41 materials at room temperature using less expensive polymeric version of ethyl silicate (40 wt% SiO₂) as a source of silica was established. The influence of crucial synthesis parameters such as molar ratios of H₂O/NH₄OH, NH₄OH/SiO₂ and CTMABr/SiO₂ in gel on the quality of the phase formed was investigated. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and low temperature N₂ adsorption-desorption isotherms have been employed to characterize the products. The magnitude of orderness, textural properties and thermal stability of the Si-MCM-41 samples prepared under identical judiciously pre-controlled synthesis conditions using ethyl silicate and conventional tetraethyl orthosilicate (TEOS) were assessed. Even though, ethyl silicate has proved to be suitable source for the preparation of MCM-41 at room temperature, there exists an optimum value of H₂O/NH₄OH for different NH₄OH/SiO₂ molar ratios in the gel. Changes in the morphology were observed when NH₄OH/SiO₂, H₂O/NH₄OH molar ratios in the gels were changed.     

Synthesis and characterization of CuO containing mesoporous silica spheres

A new series of mesoporous silica spheres containing nanodispersed copper oxides were synthesized in H₂O/EtOH/ammonia solution at room temperature. The mesoporous structures were characterised using X-ray powder diffraction and N₂ adsorption-desorption techniques. Scanning electron micrograph and transmission electron micrograph revealed that the MCM-41 particles have spherical morphologies. The DTA curve of pure MCM-41 exhibited a sharp single exothermic peak between 290°C and 340°C, while a broad peak with several shoulders in the temperature range between 180°C and 380°C was observed for Cu-MCM-41, indicating the possible complexation of Cu²⁺ with surfactants adhering to the inner surfaces of the mesopores. Electron paramagnetic resonance spectra of uncalcined samples revealed that Cu²⁺ ions are in an octahedral or distorted octahedral coordination with nitrogen ligands of the surfactant while in the calcined samples they are coordinated with oxygen of the MCM-41 framework. The redox properties of samples were examined by a temperature-programmed reduction and N₂O passivation method. The results indicate that CuO with increasing particle size could be formed in the mesoporous materials with increasing Cu contents, and this decreased the reducibility of the resulting CuO.     

Bimetallic iron and cobalt incorporated MFI/MCM-41 composite and its catalytic properties

The MFI/MCM-41 composite material with bimetallic Fe and Co incorporation was prepared using templating method via a two-step hydrothermal crystallization procedure. The obtained products were characterized by a series of techniques including powder X-ray diffraction, N₂ sorption, transmission electron microscopy, scanning electron microscope, H₂ temperature programmed reduction, thermal analyses, and X-ray absorption fine structure spectroscopy of the Fe and Co K-edge. The catalytic properties of the products were investigated by residual oil hydrocracking reactions. Characterization results showed that the FeCo-MFI/MCM-41 composite simultaneously possessed two kinds of stable meso- and micro-porous structures. Iron and cobalt ions were incorporated into the silicon framework, which was confirmed by H₂ temperature programmed reduction and X-ray absorption fine structure spectroscopy. This composite presented excellent activities in hydrocracking of residual oil, which was superior to the pure materials of silicate-1/MCM-41.     

Cerium incorporating into MCM-41 mesoporous materials for CO oxidation

Ceria doped MCM-41 materials were synthesized by surfactant-assisted hydrothermal and wet impregnation methods. All the obtained Ce-MCM-41 materials were characterized by N₂ physical adsorption, X-ray diffraction (XRD), diffuse reflectance UV–visible spectroscopy (DRUV–vis), infrared spectroscopy (IR), solid-state cross-polarization magic angle spinning nuclear magnetic resonance spectroscopy (CP/MAS-NMR), and transmission electron microscopy (TEM). The catalytic properties were evaluated in CO oxidation under atmospheric pressure and various temperatures. The results showed that in the materials synthesized by hydrothermal method, most of Ce ions were well incorporated in the tetrahedral coordinated sites into the framework of the MCM-41 as Si/Ce molar ratio is 30 and 50. High cerium content may lead to mesostructure partial collapsing and ceria particles segregation. For CO oxidation, the catalytic activity of Ce-MCM-41 synthesized by hydrothermal method was significantly greater than that of the materials prepared by impregnation route. Over the Ce-MCM-41 materials prepared via hydrothermal technique, 100% CO conversion was achieved at 504, 514 and 528 K, respectively, as the Si/Ce molar ratio decreased from 50 to 30 and 10. For the first time, we found an interesting correlation of Q₃ species relative area in the ²⁹Si CP/MAS-NMR spectra of the Ce-MCM-41materials with the reaction rates of CO oxidation, which indicates that both surface hydroxyls and tetrahedral-coordinated Ce⁴⁺ ions in the MCM-41 take important roles in the CO oxidation.     

Comparative study on the structural and catalytic properties of mesoporous hexagonal silica anchored with H3PW12O40: Green synthesis of benzoic acid from benzaldehyde

Mesoporous silica anchored with 25 wt.% 12-tungstophosphoric acid (H₃PW₁₂O₄₀, HPW) were comparatively characterized on their structures and catalytic activities for benzaldehyde oxidation with H₂O₂. The results revealed that the mesoporous materials retained the typical hexagonal mesopores for the supports of HPW. It was found that HPW exhibited higher dispersion within MCM-41 than those within SBA-15 and other mesoporous molecular sieves. Moreover, the as-prepared materials were found to be the efficient catalysts for the green synthesis of benzoic acid. In particular, HPW/MCM-41 exhibited the best catalytic properties due to its suitable textural and structural characteristics.     

Amine-impregnated MCM-41 in post-combustion CO2 capture: Synthesis,characterization, isotherm modelling

In this study, a composite mesoporous silica material MCM-41 (Mobil composite matter) is impregnated with monoethanolamine (MEA) as primary linear amine, benzylamine (BZA) as primary cyclic amine and N-(2-aminoethyl) ethanolamine (AEEA) as secondary diamine and the effects of amine loading, amine type, CO₂ partial pressure and adsorption temperatures on the CO₂ adsorption are investigated. The CO₂ adsorption performances of MCM-41 and amine impregnated MCM-41 samples are studied up to 1 bar of CO₂ partial pressure and the temperature range of 25–60 °C. The amine loadings (% impregnation) are optimized for maximum CO₂ uptake. The materials are characterised using N₂ adsorption/desorption isotherm, Fourier Transform Infrared (FT-IR) Spectroscopy, Thermogravimetric (TGA) and Elemental (CHNS) analysis. The materials have shown good structural and thermal stability. The MCM-41-40%AEEA, MCM-41-40%BZA and MCM-41-50%MEA samples are exhibited the CO₂ adsorption capacity of 2.34 mmol/g (102.98 mg/g), 0.908 mmol/g (39.96 mg/g) and 1.47 mmol/g (64.69 mg/g) respectively. The CO₂ uptake of MCM-41-40%AEEA is 3.5 times higher than that of in MCM-41 (0.68 mmol/g) and it is also the highest reported value as di-amine impregnated MCM-41. The results indicated that the adsorption capacities of the materials (MCM-41 and MCM-41-40%AEEA) are decreased with an increase of adsorption temperature in the range of 25–60 °C. The Freundlich, Langmuir, Sips and Toth isotherm models are used to correlate and predict experimental CO₂ adsorption data. The Sips and Toth isotherm models are found to be better fitted with the experimental data. The isosteric heat of adsorption of MCM-41 and MCM-41-40%AEEA samples are also calculated from Van’t Hoff plot using iSorbHP-win instrumental analysis software in the experimental temperature range.     

Compatibilizing effect of mesoporous fillers on the mechanical properties and morphology of polypropylene and polystyrene blend

Polypropylene(PP)/Polystyrene(PS) (PP/PS = 80/20) blend with different types of fillers were prepared by using melt method. Four different types of fillers, namely mesoporous MCM-41 (without template), nano-SiO₂, Polymethylmethacrylate (PMMA)/MCM-41 and PMMA/SiO₂ were considered. For PMMA/MCM-41 filler, the synthesis of the filler consisting of entrapped strand of PMMA within the pores of mesoporous MCM-41 (without template) was described. The mechanical properties of the blend determined as the nano-fillers contents and the different types of blend were found to vary with the different interface between fillers and the matrix. SEM revealed a good interaction between the matrix phases and PMMA/MCM-41 or MCM-41 (without template). The decreased T_g of PS implied that the good adhesion between PP and PS blend was obtained by adding PMMA/MCM-41 nano-filler.     

Template-directed synthesis of mesoporous silicas containing phosphonic acid derivatives in the surface layer

A template-directed process, using 1-dodecylamine as a template, is developed for the synthesis of mesoporous silicas containing the phosphonic acid derivatives ≡Si(CH₂)₂P(O)(OC₂H₅)₂ and ≡Si(CH₂)₃P(O)(CH₃)(ONa) in the surface layer. The porous materials obtained by removing the template with boiling methanol have specific surfaces of 854 and 505 m²/g, accessible pore volumes of 0.42 and 0.37 cm³/g, and pore diameters of 2.2 and 2.5 nm, respectively. As shown by scanning electron microscopy and x-ray diffraction, the mesoporous silicas are nonuniform in particle shape and size, and their structure is less ordered than that of classic mesoporous silicas, such as MCM-41. IR and ¹³C, ³¹P, and ²⁹Si CP/MAS NMR spectroscopy data indicate that, in the surface layer of the mesoporous silica prepared with the use of ≡Si(CH₂)₂P(O)(OC₂H₅)₂, the functional groups are present in the form of T ² and T ³ structural units. In addition, the surface layer contains alkoxy groups and water, which participates in hydrogen bonding.     

Functionalization of mesoporous MCM-41 for the delivery of curcumin as an anti-inflammatory therapy

In this study, mesoporous silica nanoparticles (MSNs) composed of MCM-41 were synthesized and modified with amine groups (i.e., NH₂) to form NH_2/MCM-41, which was loaded with curcumin (CUR) to form CUR@NH₂/MCM-41 to create an efficient carriers in drug delivery systems (DDSs). The three samples (i.e., pure MCM-41, NH₂/MCM-41, and CUR@NH₂/MCM-41) were characterized using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transition electron microscopy (TEM), and a thermogravimetric analyzer (TGA). The study investigated the effect of the carrier dose, CUR concentration, pH, and contact time on the drug loading efficiency (DLE%) by adsorption. The best DLE% for MCM-41 and NH₂/MCM-41 was found to be 15.78 and 80%, respectively. This data demonstrated that the Langmuir isotherm had a greater correlation coefficient (R²) of 0.9840 for MCM-41 and 0.9666 for NH₂/MCM-41 than the Freundlich and Temkin isotherm models. A pseudo-second-order kinetic model seems to fit well with R² = 0.9741 for MCM-41 and R² = 0.9977 for NH₂/MCM-41. A phosphate buffer solution (PBS) with a pH of 7.4 was utilized to study CUR release behavior. As a result, the full release after 72 h was found to have a maximum of 74.1% and 29.95% for pure MCM-41 and NH₂/MCM-41, respectively. The first-order, Weibull, Hixson-Crowell, Korsmeyer-Peppas, and Higuchi kinetic release models were applied to releasing CUR from CUR@MCM-41 and CUR@NH₂/MCM-41. The Weibull kinetic model fit well, with R² = 0.944 and 0.96912 for pure MCM-41 and NH₂/MCM-41, respectively.     

Crystalline phase formation in metakaolinite geopolymers activated with NaOH and sodium silicate

The effect of the NaOH content and the presence of sodium silicate activators on the formation of crystalline phases from metakaolinite-based geopolymers were studied by X-ray powder diffraction (XRD), Rietveld quantitative XRD, solid-state MAS NMR and SEM in samples synthesized with varying NaOH contents and different curing times at 40 °C. Geopolymers activated with NaOH alone with Si/Na ratios of 4/4 or less formed the crystalline zeolite Na–A (Na₉₆Al₉₆Si₉₆O₃₈₄·216H₂O), but at ratios >4/4 nanosized crystals of another zeolite (Na₆[AlSiO₄]₆·4H₂O) were formed. The Si/Na ratio of 4/4 produces a product of greatest crystallinity. The addition of sodium silicate in addition to NaOH significantly reduces crystallite formation. The network units of all the materials containing NaOH and sodium silicate are essentially the same, namely, tetrahedral [SiO₄] units coordinated through four bridging oxygens to four aluminium atoms [denoted as Q⁴ Si(4Al) units]. A templating function of the various silicate units of the sodium silicate molecules is suggested to occur in geopolymerization, which differs from the reaction route operating when NaOH alone is used as the activator. This templating function is responsible for the suppression of crystallization and the increase in strength of the geopolymers activated with sodium silicate.     

Study on thermodynamics and oxidation mechanism of ethylene glycol in the preparation of nanometer nickel powders

Nanometer nickel powders have been prepared using the polyol method with NaOH, Ni(NO₃)₂·6H₂O, ethylene glycol (EG), and polyvinylpyrrolidone (PVP) as raw materials. The thermodynamics of the reaction system was studied, and the E–pH diagram of Ni–EG–H₂O was plotted. The oxidation products of EG were predicted from the E–pH diagram, and CO₃²⁻ in alkaline solutions was identified as the product through the IR spectrum and CaCO₃ sediment. Field-emission scanning electron micrograph (FE-SEM) showed that spherical nanometer nickel powders were obtained.     

Preparation and characterization of ruthenium films via an electroless deposition route

A metallic Ru film was prepared by an electroless deposition method, followed by hydrogen reduction treatment. The electroless deposition formulation produced a solid film on a Cu-coated Si substrate at 40 °C preactivated by PdCl₂ solution. Chemicals including K₂RuCl₅·xH₂O, NaNO₂, NaOH, and NaClO were mixed in a proper ratio that enabled heterogeneous nucleation and film growth. Results from X-ray photoelectron spectroscopy (XPS) on the as-deposited films confirmed the presence of RuO_x and Ru, while X-ray diffraction (XRD) pattern suggested an amorphous nature. Planar images from a scanning electron microscope revealed a rather smooth surface at thickness less than 250 nm. Above that formation of surface crack and partial detachment from the substrate were observed. After hydrogen reduction at 200 °C for 2 h, we obtained a metallic Ru film, as confirmed by XPS and XRD. In addition, the surface roughness was increased due to the formation of pinholes that was caused by the volume contraction associated with RuO_x reduction to Ru.     

SiC-dopped MCM-41 materials with enhanced thermal and hydrothermal stabilities

SiC-dopped MCM-41 mesoporous materials were synthesized by the in situ hydrothermal synthesis, in which a small amount of SiC was added in the precursor solvent of molecular sieve before the hydrothermal treatment. The materials were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, N₂ physical adsorption and thermogravimetric analysis, respectively. The results show that the thermal and hydrothermal stabilities of MCM-41 materials can be improved obviously by incorporating a small amount of SiC. The structure collapse temperature of SiC-dopped MCM-41 materials is 100 °C higher than that of pure MCM-41 according to the differential scanning calorimetry analysis. Hydrothermal treatment experiments also show that the pure MCM-41 will losses it's ordered mesoporous structure in boiling water for 24 h while the SiC-dopped MCM-41 materials still keep partial porous structure.     

Influence of pH on the sorption behaviour of uranyl ions in mesoporous MCM-41 and MCM-48 molecular sieves

The sorption of uranyl ions in mesoporous MCM-41 and MCM-48 was accomplished with the help of a direct-template-exchange route, and the progress was monitored as a function of pH of the precursor uranyl nitrate solution. Under identical conditions of synthesis, around one and a half times larger amount of uranium was found to be sorbed in MCM-48 (∼12.5 wt.%) as compared to MCM-41 (∼9.5 wt.%). Further, the powder X-ray diffraction (XRD) data revealed that the expansion of unit cell parameters and broadening of reflections of the uranium containing samples depended on the pH of the precursor uranyl solution. Likewise, the Fourier transform infrared spectroscopy (FT-IR) studies showed a progressive decrease in the frequency of the axial OUO asymmetric stretching vibrational band, ν_a(UO) of the anchored uranyl groups with the increase of pH of the exchanging uranyl solution. The presence of two bands at ∼920 and 879 cm⁻¹ for uranyl exchanged samples prepared at pH > 5 indicated the presence of trinuclear (UO₂)₃⁺₅(OH) species. The occlusion of uranium thus depends upon the pore structure of the host material and the nature and dimension of the hydrolysis species formed at a particular pH of uranyl solution. Furthermore, the template-exchange of hexavalent uranium in MCM-41 and MCM-48 not only results in the formation of bulky hydrolysis species in the mesovoids, but also substitutes (isomorphously) in the silicate matrix resulting in the formation of UMCM-41 and UMCM-48.     

In situ preparation of self-bonded zeolite MCM-22 bodies by vapor-phase transport method

Self-bonded bodies of zeolite MCM-22 were prepared by vapor-phase transport method. The resultant materials were characterized by means of X-ray diffraction, scanning electron microscope, mercury porosimetry, and nitrogen porosimetry. Self-bonded MCM-22 bodies were in situ prepared at pH 10.0 with the molar composition of 0.05Na₂O:SiO₂:0.033Al₂O₃. It was found that the bodies, prepared by aluminosilicate gel, had been transformed into zeolite MCM-22. The MCM-22 bodies of which the mechanical resistance was 126 N/cm avoided binder accession. By adding auxiliary chemical–PEG20000 to the aluminosilicate gel, the pore size distributions of MCM-22 bodies could be adjusted. The average pore radius of MCM-22 bodies reached in the 149.41–653.64 nm range when AC/SiO₂ ratio was 1.5 × 10⁻⁴–9.0 × 10⁻⁴.     

Supercapacitive performance of hydrous ruthenium oxide (RuO2 · nH2O) thin films synthesized by chemical route at low temperature

In the present investigation, we report the synthesis of ruthenium oxide (RuO₂ · nH₂O) thin films by simple chemical bath deposition (CBD) method at low temperature on the stainless steel substrate. The prepared thin films are characterized for their structural and morphological properties by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT–IR) and scanning electron microscopy (SEM). The structural study revealed that the ruthenium oxide thin films are amorphous. Scanning electron microscopy study shows compact morphology with small overgrown particles on the surface of the substrate. FT–IR study confirms the formation of RuO₂ · nH₂O material. The supercapacitor behaviour of RuO₂ · nH₂O thin film was studied using cyclic voltammetry (CV) technique in 0 · 5 M H₂SO₄electrolyte. RuO₂ · nH₂O film showed maximum specific capacitance of 192 F · g^{? 1}at a scan rate of 20 mV · s^{? 1}. The charge–discharge studies of RuO₂ · nH₂O carried out at 300 μA · cm^{? 2}current density revealed the specific power of 1 · 5 kW.kg^{? 1}and specific energy of 41 · 6 Wh.kg^{? 1}with 95% coulombic efficiency.     

Apatite formation on titanium substrates by electrochemical deposition in metastable calcium phosphate solution

An apatite layer was successfully formed on titanium substrates by electrochemical deposition in a metastable calcium phosphate solution, which had 1.5 times the ion concentrations of a normal simulated body fluid, but did not contain MgCl₂·6H₂O, at 41 °C for 40 or 60 min at 13 mA. The current did not produce large effects on the crystalline size of the apatite, but the thickness of the apatite layer could be controlled by deposition conditions such as electrolyte temperature, current and deposition time. It is expected that the present electrochemical deposition will be useful to rapidly coat apatite on metallic materials.     

A simple method to ameliorate hierarchical porous structures of SiO2 xerogels through adjusting water contents

In this contribution, hierarchical micro-/meso-porous SiO₂ xerogels were successfully prepared through a Stöber methodology coupled with following drying process. The SiO₂ xerogels were consisted of nanoparticles of 20–40 nm in size with different contents of water. Fourier transform infrared spectroscopy proved that SiOC₂H₅ and SiOH groups could be formed in SiO₂ xerogels. Further analyses declared that the amount of the SiOC₂H₅ groups decreased while the concentration of SiOH was firstly increased and then suffered a decline with improving contents of water. Besides, the SiO₂ xerogels was endowed with controllable micro-/meso-porous structure. Furthermore, the formation mechanism of the micro-/meso-porous SiO₂ xerogels was tentatively put forward. As a consequence, SiO₂ xerogels with controllable hierarchical micro-/meso-porous structure could act as the smart material for huge development in catalytic fields.     

Synthesis, characterization and catalytic performance of a novel zeolite ITQ-2-like by treating MCM-22 precursor with H2O2

A novel zeolite material denoted as ITQ-2-like was synthesized by treating MCM-22 precursor with H₂O₂ and characterized by various physicochemical techniques (X-ray powder diffraction, transmission electron microscopy, thermogravimetric-differential thermal analyses, Fourier transform infrared spectroscopy and nitrogen adsorption-desorption). It was found that not only the organic template could be completely removed but also the morphology and topology structure of MCM-22 precursor was well preserved after H₂O₂ treatment. Novel zeolite material ITQ-2-like presented relatively ordered cascaded layers in a face-to-face orientation along the c-axis and exhibited different physicochemical properties in comparison with ITQ-2 and MCM-22 prepared from the same precursor. Moreover, the catalytic behaviour and pore roles of three kinds of Mo-containing catalysts of ITQ-2-like, MCM-22 and ITQ-2 were investigated in the reaction of methane aromatization.