Synthesis and characterization of surface-modified and organic-functionalized MCM-41 type ordered mesoporous materials

A new and efficient method for the preparation of MCM-41 type ordered mesoporous phases using phosphate as promoter under reflux conditions is reported. The various mesoporous materials studied were: silica (Si-MCM-41), alumino-silicate (Al-MCM-41), and titanium-silicate (Ti-MCM-41). Our concept of promoter-assisted synthesis of zeolites and related microporous materials was found to be applicable in the synthesis of ordered mesoporous materials as well. The addition of small catalytic quantity of phosphate ions (PO ₄ ³⁻ ), used as promoters, significantly reduced the synthesis time (by a factor of 3–4) of all these mesoporous materials. The synthesis of new MCM-41 type organic-inorganic composite materials with unique properties is also reported.     

H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript> supported on mesoporous MCM-41 and Al–MCM-41 materials: preparation and characterisation

MCM-41 and Al–MCM-41 has been synthesized using cetyl-trimethylammonium bromide (CTAB) surfactant as template and adding the silica precursor to aqueous solutions containing CTAB. The obtained solids were calcined at 600 °C for 4 h. HPW heteropolyacid supported on the mesoporous were prepared using the incipient wetness method. The characterization of materials was performed by X-ray diffraction, Transmission Electron Microscopy, N₂ adsorption, ²⁹Si Cross Polarization–Magic Angle Spinning and ²⁷Al MAS NMR. Results showed that the hexagonal structure is obtained in both cases. The Aluminium species are located inside an extra-framework. The impregnation reduces the surface area of the mesoporous materials especially of the Al–MCM-41 suggesting a participation of aluminium during the impregnation. HPW is well dispersed in the mesoporous materials and is located inside the pores interacting with the silanol group of the pores wall. ²⁷Al MAS NMR measurements have showed that the impregnation causes the removal of the non-framework aluminium.     

ZnO nanoparticles supported on mesoporous MCM-41 and SBA-15: a comparative physicochemical and photocatalytic study

A simple solvothermal impregnation method was used to prepare ZnO nanoparticles supported on MCM-41 and SBA-15. X-ray powder diffraction, N₂ adsorption–desorption, Electron Probe Micro Analysis (EPMA), and UV–vis spectroscopy were used to characterize the prepared materials. The influence of the ZnO loading of different supports on the structural characteristics and the photocatalytic activity toward degradation of methylene blue in water under ultraviolet irradiation were investigated. Wide angle X-ray diffraction and UV–vis Diffuse Reflectance confirmed the existence of ZnO phase. A much smaller influence of impregnation with ethanolic zinc salt solution on the porosity was observed for SBA-15 compared with MCM-41. Finally, the adsorption and photocatalytic activity of the ZnO/mesoporous materials depend on porous characteristics of the support materials.     

Preparation and characterization of epoxy composites filled with functionalized nano-sized MCM-41 particles

Mono-dispersed nano-sized MCM-41 (M (with template)) particles were synthesized by sol–gel reaction. The effect of interface modification on the properties of epoxy composites was investigated. Modifications were carried out either by substituting silanol groups on the surface or in the mesopore channels into amine (M-NH₂), calcinating mixture template in the mesopore channels (M(without template)), or recalcinating them at higher temperature to remove silanol groups (–OH) in the mesopore channels or on the surface (CM). Transmission electron micrograph results showed that the dispersing of MCM-41 nanoparticles was not influenced by the modification, while –NH₂ group indeed modified the mesopore channels or the surface of MCM-41 particle by using IR, XRD, and N₂ adsorption–desorption. In addition, tensile tests suggested that M-NH₂ nanoparticles could simultaneously provide epoxy matrix with strengthening and toughening effects. However, due to the different interfacial structures between the fillers and the matrix, the mechanical properties of the composites filled by M-NH₂ were much better than those of composites filled by MCM-41 (without template), MCM-41 (with mixture template), and CM.     

Catalytic activity of Co/MCM-41 and Co/SBA-15 materials in toluene oxidation

Cobalt-containing MCM-41 and SBA-15 mesoporous materials were prepared by the pH-adjusting of the impregnation solution. The modified materials were investigated by X-ray diffraction, N₂ physisorption, temperature-programmed reduction, DR UV–Vis diffuse reflectance, and FT-IR spectroscopy of adsorbed pyridine. The pH of the impregnation solution influences the surface charge of the mesoporous support and therefore determines the strength of interaction between the cobalt precursor and the mesoporous support. The formation of different cobalt oxide species in different ratios, depending on the pH of the impregnation solution, was established for both materials. The modified Co/MCM-41 and Co/SBA-15 materials were active in toluene oxidation. Their catalytic activity is predetermined by the nature, the reducibility, and the dispersion of the obtained cobalt oxide species.     

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.     

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.     

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.     

Glass–ceramic scaffolds containing silica mesophases for bone grafting and drug delivery

Glass–ceramic macroporous scaffolds were prepared using glass powders and polyethylene (PE) particles of two different sizes. The starting glass, named as Fa-GC, belongs to the system SiO₂–P₂O₅–CaO–MgO–Na₂O–K₂O–CaF₂ and was synthesized by a traditional melting-quenching route. The glass was ground and sieved to obtain powders of specific size which were mixed with PE particles and then uniaxially pressed in order to obtain crack-free green samples. The compact of powders underwent a thermal treatment to remove the organic phase and to sinter the Fa-GC powders. Fa-GC scaffolds were characterized by means of X-Ray Diffraction, morphological observations, density measurements, image analysis, mechanical tests and in vitro tests. Composite systems were then prepared combining the drug uptake-delivery properties of MCM-41 silica micro/nanospheres with the Fa-GC scaffold. The system was prepared by soaking the scaffold into the MCM-41 synthesis batch. The composite scaffolds were characterized by means of X-Ray Diffraction, morphological observations, mechanical tests and in vitro tests. Ibuprofen was used as model drug for the uptake and delivery analysis of the composite system. In comparison with the MCM-41-free scaffold, both the adsorption capacity and the drug delivery behaviour were deeply affected by the presence of MCM-41 spheres inside the scaffold.     

Effects of pH and concentration on ability of Cl<Superscript>−</Superscript> and NO<Stack><Subscript>3</Subscript><Superscript>−</Superscript></Stack> to intercalate into a hydrotalcite-like compound during its synthesis

In this study, we confirmed that the characteristics of anion intercalation into the interlayer of a hydrotalcite-like compound (HT) during synthesis are similar to those of the anion-exchange reaction of HTs as well as the reconstruction reaction of HTs from Mg-Al oxide. We demonstrated that (i) Cl⁻, which has a higher charge density than NO₃⁻, more easily reacted with Mg and Al species to form HT structure, resulting in greater intercalation of Cl⁻ into the HT interlayer; and (ii) for HTs with lower Mg: Al molar ratios, OH⁻, which has a higher charge density than Cl⁻ and NO₃⁻, was more likely to interact with Mg and Al species to form HT structure, blocking the intercalation of Cl⁻ and NO₃⁻. Furthermore, we showed that high concentrations of Cl⁻ and NO₃⁻ in solution regulated their intercalation into the HT interlayer. The high activity of Cl⁻ and NO₃⁻ in solution would facilitate the anions’ reactions with Mg and Al species to form HTs, resulting in a high degree of anion intercalation into the interlayer of HTs.     

Pt nanoparticles inside the mesopores of TiO<Subscript>2</Subscript>–MCM-48: synthesis,characterization and catalytic activity for CO oxidation

TiO₂ and Pt nanoparticles were deposited in the channels of siliceous MCM-48 via a sequential incipient wetness-impregnation method employing (NH₄)₂PtCl₄ as platinum source. The resulting composite Pt/TiO₂–MCM-48 (1 wt% Pt, ca. 3 wt% Ti) was characterized using XRD, TEM, nitrogen physisorption, hydrogen chemisorption, UV–vis spectroscopy, and XPS; its catalytic activity for CO oxidation was also explored. These data were compared with those of Pt/MCM-48 prepared via an analogous route. The results reveal that the platinum was deposited inside the intact pore system in both cases. It remains inside upon mild reduction but tends to segregate out of the pore system at higher reduction temperatures or during CO oxidation. Both composites were found to be highly active in CO oxidation, with 50% conversion at 460–475 K after activation of the unreduced catalysts in the (net oxidizing) feed. Striking differences in this activation process between Pt/MCM-48 and Pt/TiO₂–MCM-48 suggest that the precursor reduction is influenced by an interaction with the TiO₂ component in the latter.     

Synthesis and characterization of mesoporous Si-MCM-41 materials and their application as solid acid catalysts in some esterification reactions

Mesoporous MCM-41 has been synthesized by sol–gel method at room temperature possessing good thermal stability, high surface area as well as retention of surface area at high temperature. The MCM-41 neutral framework has been modified and put to practical use by incorporating Al³⁺ in the siliceous MCM-41 framework and supporting 12-TPA (12-tungstophosphoric acid) onto MCM-41 by process of anchoring and calcination to induce Brønsted acidity in MCM-41 to yield Al-MCM-41 and 12TPA-MCM-41, respectively. The synthesized materials have been characterized for elemental analysis by ICP-AES, XRD, SEM, TEM, EDX, FT–IR and TGA. Surface area has been determined by BET method and pore size and pore size distribution determined by BJH method. Surface acidity has been evaluated by NH₃-TPD method. The potential use of Al-MCM-41 and 12TPA-MCM-41 as solid acid catalysts has been explored and compared by studying esterification as a model reaction wherein monoesters such as ethyl acetate (EA), propyl acetate (PA), butyl acetate (BA) and benzyl acetate (BzA) have been synthesized, optimizing several parameters such as catalyst amount, reaction time, reaction temperature and mole ratio of reagents.     

On the structure and surface properties of NiO/MgO–La2O3 catalyst: Influence of the support composition and preparation method

This work addresses the effect of catalyst preparation method and the carrier compositions (MgO–La₂O₃) over the NiO-support interaction, which affect the reducibility, textural properties and the different oxygen species chemisorbed at different temperatures over MgO–La₂O₃ supported NiO catalysts. The materials were prepared by wet sequential impregnation and wet co-impregnation with different Mg molar fractions [Mg/(La+Mg)]. The samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), infrared (IR) spectroscopy, scanning electron microscopy (SEM), changes of surface potential and BET surface area measurements. The total oxidation of methane was use as model reaction. It has been found that the catalyst formulations (i.e. NiO/MgO–La₂O₃) and the preparation methods not only affect the interaction among the catalyst components, but also the texture and material morphology as a result of different degrees of particle aggregation. The wet sequential impregnation-prepared catalysts showed a stronger MgO–La₂O₃ interaction than wet co-impregnation-prepared samples. A marked tendency of NiO to react with MgO rather than La₂O₃ following a mechanism of lattice substitution is observed. Mg-free catalyst showed LaNiO₃ and NiO as major crystalline Ni-containing phases. The ternary Ni–Mg–La–O system, on the other hand, facilitates the formation of poorly reducible Ni phase, whereas the La-free catalyst (i.e. NiO/MgO) displayed the lowest content of Ni-reducible phase, owing to the formation of Ni_1−xMg_xO solid solution. Measurements of surface potential changes together with catalytic studies suggest that La-containing catalysts present oxygen vacancies, which markedly affect the chemical nature of the surface oxygen species and hence their catalytic behaviour.     

Growth of quantum-confined CdS nanoparticles inside Ti-MCM-41 as a visible light photocatalyst

CdS nanocrystallites have been successfully incorporated into the mesopores of Ti-MCM-41 by a two-step method involving ion-exchange and sulfidation. The X-ray diffraction patterns (XRD), UV-vis absorption spectra (UV-vis), photoluminescence spectra (PL), Raman spectra and N₂ adsorption-desorption isotherms were used to characterize the structure of the composite materials. It is found that most of the CdS nanocrystallites are about 2.6 nm, less than the pore diameter of Ti-MCM-41. The CdS nanocrystallites inside the mesopores of Ti-MCM-41 host show a significant blue shift in the UV-vis absorption spectrum. Under irradiation of visible light (λ > 430 nm), the composite material has greater and more stable photocatalytic activity for hydrogen evolution than bulk CdS, which can be explained by the effective charge separation between the CdS nanocrystallites and mesoporous Ti-MCM-41.     

Synthesis and characterization of Co-Fe Prussian blue nanoparticles within MCM-41

A Prussian blue analogue, K_0.84Co_1.08[Fe(CN)₆] is prepared by reaction between [Fe(CN)₆]³⁻ in aqueous solution and ion-exchanged Co²⁺ in the channels of MCM-41. Powder X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, nitrogen adsorption/desorption isotherms, diffuse reflectance UV-vis absorption spectroscopy and magnetic measurements were employed to characterize the product. The results show that the Prussian blue analogue is in nanoparticles within the channels and the hexagonal phase of MCM-41 remains intact during the reactions. A particle size effect on optical and magnetic properties of the nanoparticles was observed.     

Preparation of lanthanum-doped TiO<Subscript>2</Subscript> photocatalysts by coprecipitation

The lanthanum-doped TiO₂ (La³⁺-TiO₂) photocatalysts were prepared by coprecipitation and sol–gel methods. Rhodamine B was used as a model chemical in this work to evaluate the photocatalytic activity of the catalyst samples. The optimum catalyst samples were characterized by XRD, N₂ adsorption–desorption measurement, SEM and electron probe microanalyses to find their differences in physical and chemical properties. The experimental results showed that the La³⁺-TiO₂ catalysts prepared by coprecipitation exhibited obviously higher photocatalytic activities as compared with that prepared by the conventional sol–gel process. The optimum photocatalysts prepared by the coprecipitation and sol–gel process have similar adsorption equilibrium constants in Rhodamine B solution and particle size distribution in water medium although there are larger differences in their surface area, morphology and pore size distribution. The pores in the sol-gel prepared catalysts are in the range of mesopores (2–50 nm), whereas the pores in the coprecipitation prepared catalysts consist of bigger mesopores and macropores (>50 nm). The morphology of the primary particles and agglomerates of the La³⁺-TiO₂ catalyst powders was affected by doping processes. The inhibition effect of lanthanum doping on the phase transformation is greater in the coprecipitation process than in the sol–gel process, which could be related with the different amount of Ti–O–La bonds in the precursors. This finding could be used for preparing the anatase La³⁺-TiO₂ catalysts with more regular crystal structure through a higher heat treatment temperature. The optimum amount of lanthanum doping is ca. 1.0 wt.% and the surface atomic ratio of [O]/[Ti] is ca. 2.49 for 1.0 wt.% La³⁺-TiO₂ catalysts prepared by the two processes. The obviously higher photocatalytic activity of the La³⁺-TiO₂ samples prepared by the coprecipitation could be mainly attributed to their more regular anatase structure and more proper surface chemical state of Ti³⁺ species. The optimum preparation conditions are 1.0 wt.% doping amount of lanthanum ions, calcination temperature 800 °C and calcination time 2 h using the coprecipitation process. As compared with the sol-gel process, the coprecipitation process used relatively cheap inorganic raw materials and a simple process without organic solvents. Therefore, the coprecipitation method provides a potential alternative in realizing large scale production.     

Synthesis of Fe-Ti-MCM-48 from silatrane precursor via sol-gel process and its hydrothermal stability

A series of bimetallic Fe–Ti-MCM-48 materials was successfully synthesized via sol–gel method using cetyltrimethylammonium bromide (CTAB) as a template and silatrane, iron (III) chloride, and titanium (IV) isopropoxide as silica, iron, and titanium sources, respectively. Scanning electron microscopy (SEM) showed the truncated octahedron morphology of Fe–Ti-MCM-48.X-ray diffraction (XRD) patterns showed well-defined, order cubic mesoporous structures. X-ray fluorescence (XRF) revealed the total metal content of the final product. UV–visible absorption spectra confirmed both iron (Fe³⁺) and cerium (Ti⁴⁺) species highly dispersed in the framework, while N₂ adsorption/desorption measurements indicated a high specific surface area. As metal content increased, the mesoporous order and surface area decreased. The synthesized Fe–Ti-MCM-48 with 0.01Fe/Si and 0.01Ti/Si ratio still retained a cubic structure after hydrothermal treatment at 100 °C for 72 h.     

Shifting mechanisms in the initial stage of dye photodegradation by hollow TiO2 nanospheres

Hollow TiO₂ (HT) sphere aggregates were prepared using carbon spheres as templates. The photocatalytic activity of HT was determined by degradation of two nitrogen-containing dyes, methylene blue (MB) and methyl orange (MO). The adsorption isotherms and the photocatalytic degradation kinetics of the two dyes were studied and compared using different concentrations of dyes for the pure, isopropanol-added, and KI-added systems. Isopropanol was used as a OH^? radical scavenger, while KI was added as a valance band hole scavenger. The results showed that the reaction mechanism of the photocatalytic process of MB was first governed by OH^? radicals, and then by valence band holes, whereas holes played a major role in the whole photodegradation process of MO. The photocatalytic adsorption constant K _V has a positive correlation with the reaction constant k _ov in all systems. The photodegradation efficiencies of the dyes were discussed considering the surface characteristics of HT and the structure of the dyes with different catalyst loads (0.25–2 g L^?1) and under different pH (3–10) conditions. Compared with solid TiO₂, HT exhibited enhanced performance in photocatalytic degradation of both MB and MO.     

Manganese–Schiff base complex immobilized silica materials for electrocatalytic oxygen reduction

Curtailment of platinum catalysts loading in fuel cell is a recent central issue. As substitutes, these days several organic metal chelate compounds having featured moieties of M–N₄ or M–N₂O₂ (M = transition metal ion) are being used as cathode catalysts in fuel cells. Here, in this study, we report in detail the electrocatalytic activity of manganese–Schiff base complexes for oxygen reduction reaction in 0·05 M HClO₄ at room temperature. Actually, [Mn(salen)]⁺: [N,N′-bis(salicylaldehyde) ethylenediimino manganese(III)]⁺ and [Mn(salophen)]⁺: [N,N′-bis(salicylaldehyde)-1,2-phenylenediimino manganese(III)]⁺ were introduced into/onto the MCM-41 type silica spheres and used for the electrocatalytic reduction of oxygen. Synthesized materials were characterized by UV–Vis, FT–IR and electrochemical techniques. Significant low overpotential for oxygen reduction in 0·05 M HClO₄ on [Mn(salen)]⁺- and [Mn(salophen)]⁺-incorporated silica-modified glassy carbon electrodes was observed.     

Structure and photocatalytic activity studies of TiO2-supported over Ce-modified Al-MCM-41

Ce-Al-MCM-41, TiO₂/Al-MCM-41 and TiO₂/Ce-Al-MCM-41 materials with varying contents of Ce (by impregnation) and TiO₂ loaded (by solid-state dispersion) on Al-MCM-41 support are prepared. The Ce modified and TiO₂ loaded composite systems are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectra (DRS) and X-ray photoelectron spectroscopy (XPS) techniques. The DRS and XPS of low Ce content (0.2-0.5 wt.%) modified Al-MCM-41 samples are showing more characteristic of Ce³⁺ species wherein cerium in interaction with Al-MCM-41 and that of high Ce (0.8, 3.0 wt.%) content modified samples are showing the characteristic of both Ce⁴⁺and Ce³⁺species. A series of Ce-modified Al-MCM-41 and TiO₂ loaded composite catalysts are evaluated for photocatalytic degradation of phenol under UV irradiation. Low Ce content in Ce³⁺ state on Al-MCM-41 is showing good photoactivity in comparison with high Ce content samples and pure ceria. The composite TiO₂/Ce-Al-MCM-41 is showing enhanced degradation activity due decreased rate of electron-hole recombination on TiO₂ surface by the redox properties of cerium. The photocatalyst TiO₂/Ce-Al-MCM-41 with an optimum of 10 wt.% TiO₂ and 0.3 wt.% Ce is showing maximum phenol degradation activity. The possible mechanism of phenol degradation on the composite photocatalyst is proposed.