MCM-41 Type Mesoporous Materials Research Articles

HCHO Catalytic Oxidation Performance over Cerium Containing MCM-41 Type Mesoporous Materials Supported Ag Catalysts

Understanding the effects of cerium in the formaldehyde (HCHO) catalytic oxidation performance over Ag/MCM-41 catalysts, cerium modified MCM-41 mesoporous materials (Ce-MCM-41) with different ratios were synthesized by one-step hydrothermal method. The activity test results showed that Ag/Ce-MCM-41 with the ratio of Si:Ce = 1:1 catalysts could reach complete HCHO oxidation above 130 °C. These Ag/Ce-MCM-41 catalysts with different Si:Ce ratios were characterized by IR, SXRD, XRD, TEM, UV–Vis, Raman, XPS and H2-TPR. The results show that the interactions between Ag and Ce, between Ce and SiO2 in our Ag/Ce-MCM-41 are enhanced due to adding Ce to MCM-41. The presence of Ce-SiO2 interaction dramatically enhances the reducibility of surface-capping oxygen of CeO2, promotes the bulk oxygen migration to the surface and creates oxygen vacancies in the bulk region of CeO2 and the presence of more oxygen vacancies can facilitate the anchoring and dispersing of Ag particles, which lastly improves the interaction between Ag and Ce. In addition, the amount of formed oxygen vacancy is the highest when the Si:Ce = 1:1. The activation of surface oxygen is closely related to oxygen vacancy, O2 may be transformed into the highly active O2−. The high active O2− in surface adsorbed oxygen promotes the activation of oxygen molecules and enhanced the catalytic oxidation of HCHO.

Eco-friendly synthesis of nanostructured mesoporous materials from natural source rice husk silica for environmental applications.

Nanostructured mesoporous materials of MCM-41 type were synthesized using a natural, non-toxic, and cheap source of silica from rice husk. Then, this pure silica was modified with several Fe loadings by a wet impregnation method. The chemical and physic properties of MCM-41 solids obtained were similar to those of MCM-41 synthesized from commercial silica by conventional method. Thus, all catalysts exhibited good structural regularity preserving the mesoporosity after the metal incorporation. The performance of the Fe/MCM-RHA composites as photo-Fenton heterogeneous catalysts was evaluated for photocatalytic degradation of different endocrine-disrupting chemicals (EDCs), such as herbicides (atrazine), and compounds derived from the plastic industry (bisphenol A) and the pharmaceutical industry (acetaminophen). The major photo-catalytic efficiency obtained (Fe/MCM-RHA(2.5)) is consistent with the highest presence of iron species, which are finely dispersed and stabilized on the silica structure, the isolated Fe3+ ions being the accessible and active sites for the reaction. Finally, a cheaper solid arising from the valorization of residual biomass and with excellent photocatalytic performance for the degradation of EDCs (above 99%, 75%, and 60% for BPA, ATZ, and ACE respectively, in a reaction time of 240 min) was obtained.

Influence of Aluminum Addition in the Framework of MCM-41 Mesoporous Molecular Sieve Synthesized by Non-Hydrothermal Method in an Alkali-Free System

Purely siliceous MCM-41 and Al-containing MCM-41 (Al-MCM-41) mesoporous materials were synthesized by non-hydrothermal method in alkali-free ions medium at room temperature and short reaction times. Under these synthesis conditions, it was also investigated the influence of Al incorporation in the crystal structure of MCM-41. The solids were characterized by ICP-OES, AAS, N2 adsorption at 77 K, XRD, TEM, NH3-TPD, 27Al and 29Si-MAS-NMR, FT-IR and TGA. The resulting mesoporous materials showed a well-defined hexagonally ordered pore geometry maintaining a uniform and unimodal pore size distribution with high specific surface areas (1000-1400 m2g-1). The Al+3 ions were introduced successfully in the structure of the purely siliceous MCM-41 expanding the unit cell parameter and forming four-coordinated Al species, and in a less extent, forming six-coordinated Al species. In addition, the surface acidity of the MCM-41 increased with Al loading. Contrary, the presence of Al in the MCM-41 mesoporous structure resulted in a decrease of the crystallinity and specific surface area possibly due to the presence of Al species in highly distorted tetrahedral structures and Al extra-framework or amorphous alumina occluded in the pores. The MCM-41 type mesoporous materials obtained in this work show similar characteristics of those synthesized by conventional hydrothermal methods.

Structure elucidation of alkaline earth impregnated MCM-41 type mesoporous materials obtained by direct synthesis: An experimental and theoretical study

In this work, MCM-41 were synthesized hydrothermally and functionalized with calcium and strontium salts by direct method, using the Si/M=50 molar ratio, in order to elucidate the way as the alkaline earth is incorporated on MCM-41 molecular sieve. The materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, nitrogen adsorption–desorption and theoretical calculations by DFT method. Experimental results and computer simulations showed that the alkaline earths were incorporated on MCM-41 through a complex structure, which negatively influences on basic sites formation.

NiMo/MCM-41 Catalysts for the Hydrotreatment of Polychlorinated Biphenyls

MCM-41 type mesoporous materials of pure silicon and aluminosilicates (with Si/Al atomic ratios of 20 and 40) were prepared by a facile synthesis method and used to support NiMo catalysts. Characterization by XRD showed typical patterns of this type of mesoporous solids with a partial collapse of the structure on increasing Al content. In addition, signals attributed to the formation of MoO3, NiO and Al2(MoO4)3 in the transition-metal containing catalysts were observed. The 29Si-NMR-MAS spectra showed that local arrangement of the Si–O–Si bonds was regular, independently of the solid being pure or modified with Al, while the 27Al-MAS-NMR spectra of the aluminosilicates showed both structural and non-reticular species. The N2 adsorption–desorption curves showed type IV isotherms, with considerable diminution in the BET areas once the metals were incorporated. The catalytic results in thiophene hydrodesulfurization (HDS) and polychlorinated biphenyl hydrodechlorination (HDCl) revealed a considerable catalytic activity for all prepared catalysts as compared with a commercial NiMo/Al2O3 one, being highest in the case of the NiMo/Al-MCM-41(40) one for HDS, and for NiMo/Al-MCM-41(20) in HDCl. The excellent properties for HDCl can be attributed to good dispersion of Ni and Mo active phases and to the bifunctional character of the catalysts, namely, to the participation of both coordinatively unsaturated sites of the NiMoS active phase and Bronsted acid sites of the support.

Adsorption of 2-methylbenzoic acid onto MCM-41 mesoporous material: kinetics and equilibrium studies

Ordered mesoporous molecular sieves are widely studied as alternative materials in areas where sorptive and catalytic applications are required. MCM-41 type mesoporous material was tested as sorbent of 2-methylbenzoic acid (MBA), an aromatic carboxylic acid selected as model molecule for adsorption studies on mesoporous silicas. Adsorption kinetic studies of MBA on MCM-41 type materials were carried out using ethanol solutions at different MBA concentrations. Experimental results followed Langmuir isotherm model showing large adsorption capacity (3.5 g/g). Two kinetic models, the pseudo first- and second-order, were selected to describe the adsorption process and to determine the best model fitting with the experimental data. Kinetic parameters for each kinetic equation were calculated and discussed. It was shown that the MBA adsorption process onto MCM-41 material could be described by the pseudo-second-order equation and that the MCM-41 performs as a suitable adsorbent material.

Steam-assisted crystallization of TPA+-exchanged MCM-41 type mesoporous materials with thick pore walls

Hierarchical MCM-41/MFI composites were synthesized through ion-exchange of as-made MCM-41 type mesoporous materials with tetrapropylammonium bromide and subsequent steam-assisted recrystallization. The obtained samples were characterized by powder X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis, FT-IR, 1H–13C CP/MAS and nitrogen adsorption–desorption. The XRD patterns show that the MCM-41/MFI composite possesses both ordered MCM-41 phase and zeolite MFI phase. SEM and TEM images indicate that the recrystallized materials retained the mesoporous characteristics and the morphology of as-made mesoporous materials without the formation of bulky zeolite, quite different from the mechanical mixture of MCM-41 and MFI structured zeolite. Among others, lower recrystallization temperature and the introduction of the titanium to the parent materials are beneficial to preserve the mesoporous structure during the recrystallization process.

Sorption-Enhanced Reforming of Ethanol over Ni- and Co-Incorporated MCM-41 Type Catalysts

Ni- and Co-incorporated MCM-41 type mesoporous materials with Ni/Si and Co/Si molar ratios of 0.12 were synthesized, characterized, and tested in both steam reforming of ethanol (SRE) and sorption-enhanced steam reforming of ethanol (SESRE) reactions. Characterization results showed that Co and Ni were successfully incorporated and well-dispersed in the mesoporous MCM-41 support. Ni- and Co-incorporated MCM-41 catalysts had surface area values of 449.0 and 303.6 m2/g, respectively. They also had narrow pore size distributions, with average pore diameters of 2.2 and 1.98 nm, respectively. SESRE results obtained with these catalysts showed that in situ capture of CO2 during ethanol reforming reaction significantly enhanced hydrogen yield in the temperature range of 500–600 °C. The catalytic performance of Ni-incorporated MCM-41 was much better than the Co-incorporated MCM-41, in hydrogen production by ethanol reforming. The highest hydrogen yield value obtained over the Ni-incorporated MCM-41 catalyst was achieved at 600 °C as 5.6 in SESRE reaction. This was ∼94% of the maximum possible hydrogen yield value of 6.0.

The BET equation, the inflection points of N 2 adsorption isotherms and the estimation of specific surface area of porous solids

The N 2-adsorption isotherms of porous solids are received in the form V = f( P/ P o). If such data are depicted in the form V(1 − P/ P o) = f( P/ P o) or V(1 − P/ P o)/( P/ P o) = f( V(1 − P/ P o)), they show an identical inversion point (I-point, Inversion or Inflection point), which corresponds exactly to the monolayer volume V m . As a result the value of specific surface area S is determined with unique precision via the trivial relationship S (m 2 g −1) = 4.356 V m (cm 3 g −1) without any use of the classic BET treatment. The derivates dV/ d[( P/ P o)] vs. ( P/ P o) and d( V[1 − ( P/ P o)])/ d[( P/ P o)] vs. ( P/ P o) exhibit maxima exactly at the same pressure ( P/ P o), while the second order derivative d 2 V/ d[( P/ P o)] 2 vs. ( P/ P o) exhibits a minimum exactly at the same pressure ( P/ P o) with the I-point. As a consequence the specific surface area of solids can be determined just from experimental raw ( P/ P o), V data without any use, neither of linear BET treatment nor the Inversion or Inflection type graphs. For some MCM-41 type mesoporous materials, the I-plots show not one but two Inversion points/I-points. The first inversion/inflection point at lower ( P/ P o) values, “ I LP-point ”, corresponds to the completion of the adsorption procedure on the bare surface and the formation of monolayer and is useful for the determination of specific surface area S. The second inversion/inflection point at higher ( P/ P o) values, “ I HP-point ”, corresponds to the completion of the pore filling via condensation and may be useful for the determination of mesopore volume.

Application of ToF-SIMS to the study of surfactant removal from AuNbMCM-41 and AuMCM-41 materials

Abstract This work is focused on the application of time-of-flight secondary ion mass spectrometry (ToF-SIMS) in investigation of the surfactant removal process from AuNbMCM-41 and AuMCM-41 catalysts (MCM-41 “Mobil Composition of Matter”, ordered mesoporous materials discovered by Mobil R&D Corporation). The samples investigated were prepared by co-precipitation in the presence of a cationic surfactant (cetyltrimethylammonium chloride—CH3(CH2)15N(Cl)(CH3)3) and the incipient wetness impregnation methods. The results obtained showed that the time-of-flight secondary ion mass spectrometry appears to be a very useful tool for the investigation of the residual organic template on the surface of ordered mesoporous materials of MCM-41 type. It was demonstrated that the calcination of AuNbMCM-41 and AuMCM-41 catalysts at 550 °C caused a complete removal of the surfactant from the surface of the material investigated. Moreover, it was shown that the use of bismuth liquid metal ion gun in ToF-SIMS experiments permitted obtaining higher emission intensity (more than one order of magnitude when compared to the Ga+ primary ion source) of secondary ions originating from the surfactant molecules and may facilitate an interpretation of the results obtained.

A new functionalized mesoporous matrix supported Pd(ii)-Schiff base complex: an efficient catalyst for the Suzuki–Miyaura coupling reaction

A new Pd(II) bounded 2D-hexagonally ordered functionalized MCM-41 type material (IV) has been synthesized. Functionalization was carried out by the anchoring of 3-aminopropyltriethoxysilane in the MCM-41 type mesoporous material, followed by grafting with 2,6-diacetylpyridine (DAP) to give a N3-type Schiff base chelating attachment for the Pd(II) species. Fourier transform infrared (FTIR), powder X-ray diffraction (PXRD) and high resolution transmission electron microscopy (HRTEM) studies have been used to characterize the material. Material IV behaves as a highly active catalyst towards Suzuki-Miyaura cross-coupling reaction for the synthesis of biaryl organics. In addition, IV acts as a true heterogeneous catalyst in coupling reaction. It was found that this catalyst is highly efficient and recyclable towards Suzuki-Miyaura reaction with high turn over frequencies. X-Ray photoelectron spectroscopic (XPS) analysis was employed to understand the oxidation state of the palladium atom in the catalyst (IV) and its loading in the material.

Application of ToF-SIMS to the study of surfactant removal from AuNbMCM-41 and AuMCM-41 materials

This work is focused on the application of time-of-flight secondary ion mass spectrometry (ToF-SIMS) in investigation of the surfactant removal process from AuNbMCM-41 and AuMCM-41 catalysts (MCM-41 “ Mobil Composition of Matter”, ordered mesoporous materials discovered by Mobil R&D Corporation). The samples investigated were prepared by co-precipitation in the presence of a cationic surfactant (cetyltrimethylammonium chloride—CH 3(CH 2) 15N(Cl)(CH 3) 3) and the incipient wetness impregnation methods. The results obtained showed that the time-of-flight secondary ion mass spectrometry appears to be a very useful tool for the investigation of the residual organic template on the surface of ordered mesoporous materials of MCM-41 type. It was demonstrated that the calcination of AuNbMCM-41 and AuMCM-41 catalysts at 550 °C caused a complete removal of the surfactant from the surface of the material investigated. Moreover, it was shown that the use of bismuth liquid metal ion gun in ToF-SIMS experiments permitted obtaining higher emission intensity (more than one order of magnitude when compared to the Ga + primary ion source) of secondary ions originating from the surfactant molecules and may facilitate an interpretation of the results obtained.

Hybrid functionalised mesoporous silica–polymer composites for enhanced analyte monitoring using optical sensors

We report herein a new optical sensor for the colorimetric monitoring of aqueous amines designed by anchoring a suitable reactand on a hybrid material that was further incorporated on a polymeric matrix. An azo chromophore containing a trifluoroacetophenone moiety was used as signalling reporter. In this system colour modulation is a consequence of the reversible reaction of the amine with the trifluoroacetyl group that results in the formation of a hemiaminal. Based on this approach but at the same time trying to enhance selectivity the chromoreactand was anchored in a first step onto suitable mesoporous nanoscopic hydrophobic pockets. As a mesoporous system we selected a UVM-7 solid (a MCM41-type material) containing a homogeneous distribution of pores of about 3 nm and a specific surface area of over 1000 m2/g. This material was chemically modified to yield a trifluoroacetylazobenzene indicator dye within the pores, resulting in the hybrid material S3. It was found that whereas the analogous trifluoroacetylazobenzene dye in solution gives an unspecific response, the hybrid material S3 shows enhanced features in terms of selectivity, only reacting with the not-too-large but lipophilic enough aminesn-octylamine and n-decylamine. The material S3 reacts with neither small hydrophilic amines (due to the hydrophobicity of the inner pores in S3) nor very large aliphatic amines (due to the size of the pore). In the second part of this work a composite material (P–S3) was prepared by mixing hydrophilic polyurethane polymer and S3. The X-ray diffraction patterns of P–S3 displays the characteristic intense peak of the MCM-41 type mesoporous material and TEM images show a homogeneous dispersion of the nanometric mesoporous particles into the polymeric matrix. The measurements were carried out in a flow-through module connected to an optical fibre via a Y-probe at pH 9.5 (borax buffer). The P–S3 composite retains the favourable features in terms of selectivity shown by S3 and only displays a clear change in colour for n-octylamine or n-decylamine, but no response to the remaining linear primary amines. The response time of the sensor P–S3 to solutions of these amines was in the range of a few seconds, the regeneration time was between 5 to 10 min and the detection limit was 6 × 10−4 mol L−1. The sensor response was reproducible and reversible.

Synthesis of Pt Nanowires Inside Aerosol Derived Spherical Mesoporous Silica Particles

Spherical mesoporous silica particles prepared by evaporation induced self assembly (EISA) were used as templates to form Pt nanowires. Transmission electron microscope (TEM) images of these aerosol-derived silica particles reveal hexagonally ordered pores coiled within each particle, with no obvious termination of the pores on the external surface. Near the particle surface the pores are seen to run parallel to the surface, consistent with the external constraint of spherical geometry. For MCM-41 type mesoporous materials, the pores are straight and accessible at either end for pore filling, but for spherical silica particles prepared by EISA, the pores are not open to the external surface. Hence it is remarkable that Pt nanowires can be formed within the closed pores inside these spherical silica particles, where conventional mechanisms of pore filling would not be expected to be operative. These results suggest that the silica walls in these mesoporous silica allow transport of volatile Pt complexes during wet reduction in H2. The permeability to gases makes these spherical silica particles especially suitable for gas phase catalytic reactions, while at the same time confining metallic particles within the silica pores.

Promoter-induced synthesis of MCM-41 type mesoporous materials including Ti- and V-MCM-41 and their catalytic properties in oxidation reactions

The addition of small amounts of certain oxyanions of group VA, VIA and VIIA (such as nitrate, phosphate, arsenate, sulfate, bromate, iodate etc.) to the synthesis gel mixture of MCM-41 type mesoporous materials reduces the synthesis time considerably. The hydrothermal syntheses of Si-MCM-41, Al-MCM-41, Ti-MCM-41 and V-MCM-41 were carried out in the presence and absence of promoters by refluxing the gel mixture at atmospheric pressure. Studies on the effect of different promoters in the synthesis of Si-MCM-41 show different degrees of enhancement in the long-range ordering process. It has been observed that the higher the charge/radius ratio ( Z/ r, Å −1) of the central cation of the promoter, the higher is the ability of the promoter to speed up the synthesis. The concept of promoter-induced synthesis of MCM-41 type mesoporous materials is applicable not only to Si-MCM-41 but also to Al-MCM-41, Ti-MCM-41 and V-MCM-41. The materials were characterized by XRD, N 2 adsorption, diffuse reflectance UV–vis spectroscopy, FTIR, solid state MAS NMR, SEM, EDX and TEM. The XRD patterns and the quite high BET surface areas with isotherms of type IV of all the samples are typical for hexagonal MCM-41 type ordered mesoporous materials. EDX analysis, solid state 27 Al and 51 V MAS NMR spectra and diffuse reflectance UV–vis spectra of the M-MCM-41 (M = Ti and V) samples confirm the incorporation of Al, Ti and V into the framework. The catalytic properties of the two Ti-MCM-41 samples and the two V-MCM-41 samples, prepared in the presence and absence of a promoter, were compared by means of the epoxidation of cyclohexene and the hydroxylation of 1-naphthol in the presence of different peroxide sources. Comparable catalytic properties indicate that the samples, prepared in the presence and absence of a promoter, are similar in nature and the metal ions are present in the framework, presumably in a tetrahedral coordination.

The catalytic activity of new chiral salen complexes immobilized on MCM-41 in the asymmetric hydrolysis of epoxides to diols

The synthesis of MCM-41 type mesoporous material has been performed by the solvent evaporation method. The chiral salen Co(III)(OAc) complexes are immobilized on a siliceous MCM-41 through the multi-step anchoring and applied as catalysts in the hydrolytic kinetic resolution of racemic epoxides to diols. The incorporation of salen complexes onto the mesoporous material is demonstrated by UV–Vis spectroscopy, and tested with the catalytic hydrolysis reaction. The chiral salen Co(III) complexes catalyze the hydrolysis of epichlorohydine, 1,2-epoxyhexane, epoxystyrene and epoxycyclohexane under very mild conditions. This reaction can proceed in acetonitrile and THF solvents.

Organozeolite materials and their properties

Attempts in developing organozeolites, namely microporous and mesoporous crystalline inorganic-organic composites with a zeolite-like three-dimensional framework and organic moieties covalently connected to the framework, are briefly reviewed. MCM-41 type mesoporous materials modified by organic functional groups have been prepared by use of organosiloxane as a part of Si sources and by post-modification of the purely inorganic materials using organosiloxane. Also, the incorporation of organic moieties into the zeolite frameworks has been tried. Recently, several novel metal organophosphonates with a three-dimensional framework, which can be regarded as organozeolites, have been prepared. Along with these new attempts, the authors' studies in preparation, structural analysis and gas adsorption properties of microporous aluminomethylphosphonates are introduced.

Direct TEM Imaging of Tubules in Calcined MCM-41 Type Mesoporous Materials

Direct TEM Imaging of Tubules in Calcined MCM-41 Type Mesoporous Materials