Enhancement on the hydrothermal stability of ZSM-5 zeolites by the cooperation effect of exchanged lanthanum and phosphoric species

It was explored by density functional calculations that exchanged La or P species exert great influence on the local Al sites as well as on the adjacent exchanged species. In partially exchanged La- or P/H-ZSM-5 zeolite, some of the Al sites will fall off from the zeolite framework even more easily than in H-form ZSM-5, consistent with our XRF experiments. However, when exchanged by both La and P species, Al at either of the two exchanged sites shows better stability compared to H-from. zeolite. La and P species will interact strongly with each other, as evidenced by the charge donation process and the shortening of P-O-1 bond length. It was just the cooperation of La and P species that enabled RSCC catalysts worked normally under severe conditions. (C) 2004 Elsevier B.V. All rights reserved.

Hydrothermal stability and catalytic activity of aluminum-containing mesoporous ethane-silicas

Aluminum was incorporated into the mesoporous framework of ethane-silica by one-pot condensation of Al(OiPr)(3) with 1,2-bis(trimethoxysilyl)ethane using octadecyltrimethylammonium chloride as surfactant. Powder X-ray diffraction patterns, nitrogen sorption analysis, and TEM results reveal the formation of an ordered mesoporous material with uniform porosity. Al-27 MAS NMR confirms the incorporation of aluminum in the framework. The synthesized materials exhibit extremely high hydrothermal stability in boiling water (no obvious change of mesostructure and textural properties was observed even after refluxing in water for 100 h), which could be mainly contributed to the ethane-bridged mesoporous framework. The aluminum-containing mesoporous ethane-silicas are efficient catalysts for the alkylation of 2,4-di-tert-butylphenol by cinnamyl alcohol to yield a flavan.

Solid-state MAS NMR studies on the hydrothermal stability of the zeolite catalysts for residual oil selective catalytic cracking

By using the solid-state MAS NMR technique, the hydrothermal stabilities (under 100% steam at 1073 K) of HZSM-5 zeolites modified by lanthanum and phosphorus have been studied. They are excellent zeolite catalysts for residual oil selective catalytic cracking (RSCC) processes. It was indicated that the introduction of phosphorus to the zeolite via impregnation with orthophosphoric acid led to dealumination as well as formation of different Al species, which were well distinguished by Al-27 3Q MAS NMR. Meanwhile, the hydrothermal stabilities of the zeolites (P/HZSM-5, La-P/HZSM-5) were enhanced even after the samples were treated under severe conditions for a prolonged time. It was found that the Si-O-Al bonds were broken under hydrothermal conditions, while at the same time the phosphorous compounds would occupy the silicon sites to form (SiO)(x)Al(OP)(4 - x) species. With increasing time, more silicon sites around the tetrahedral coordinated Al in the lattice can be replaced till the aluminum is completely expelled from the framework. The existence of lanthanum can partially restrict the breaking of the Si-O-Al bonds and the replacement of the silicon sites by phosphorus, thus preventing dealumination under hydrothermal conditions. This was also proved by P-31 MAS NMR spectra. (C) 2004 Elsevier Inc. All rights reserved.

On configuration of exchanged La3+ on ZSM-5: A theoretical approach to the improvement in hydrothermal stability of La-modified ZSM-5 zeolite

Density functional calculations have been employed to investigate the locating and binding of lanthanum cation, i.e., La(OH)(2)(+), on HZSM-5 zeolite. Through geometry optimization, it was determined that lanthanum ions are favorably accommodated in the two 6-T rings of the straight channels (Clusters 1 and 2, see Sec. III A for details). Cluster 1 was found to exist in prior to Cluster 2 due to the preference of Al substitution in the T11 site (Cluster 1) rather than in the T8 site (Cluster 2). Geometry-optimization of Cluster 1 containing another two lanthanide ions Nd3+ and Yb3+ was also carried out and it was found that a monotonic decrease in Ln-O bond length will take place as the atomic number increases, conforming well to the rule of lanthanide contraction. Some of the optimized parameters are comparable to the corresponding experimental values in Y zeolite, which confirms that the optimized configurations are acceptable. The average frequencies of hydroxyls attached to La3+ or Yb3+ in Cluster 1 fall at 3609.16 and 3579.76 cm(-1), respectively, with the gap of these two frequencies close to that in the sodalite cage of Y zeolite. Compared to H-form zeolite, the charges on both Al and O atoms in Ln-ZSM-5 zeolite show an obvious increase, which will undoubtedly lead to a stronger mutual interaction and hence enhance the stability of the [AlO4](-) anion. Moreover, the Ln(OH)(2)(+) seem to have thickened the zeolite framework, which can effectively retard the process of dealumination. Through the evaluation of the possibility for dimer formation, it turned out that when the exchange degree arrived to approximately 0.28, lanthanum monomers began to aggregate into dimers, and were completely converted into dimers when the exchange degree approached 0.60. (C) 2003 American Institute of Physics.

On the hydrothermal stability of MCM-41. Evidence of capillary tension-induced effects

MCM-41's limited hydrothermal stability has been often related to the hydrolysis of Si-O-Si bonds due to the low degree of condensation, its thin walls or a combination of them. In this work, evidence for an additional factor is provided; a physical effect that occurs during the drying of the hydrothermally treated calcined material due to the intense capillary stress exerted in water. Depending on both physical (i.e. mechanical) and chemical (i.e. hydrolysis) resistances, the structure undergoes differently. Three MCM-41 samples with different degree of condensation were investigated. The most remarkable results are found with un-aged TEOS based material, which gets fully disordered and shrunk for all applied hydrothermal temperatures in water. Comparison between water and a low-surface-tension-solvent drying revealed that capillarity is responsible for the loss of ordering (and shrinkage) at moderate hydrothermal temperatures. The material's structure is hexagonal and shrinkage-free under the low-surface-tension-solvent route. At a high hydrothermal temperature, hydrolysis is extensive and responsible for the loss of ordering. The other remarkable finding regards the aged MCM-41 mesostructure that maintains the hexagonal features at all applied temperatures in water, and it is more stable against capillarity at high temperature. The Na-metasilicate based material is mechanically very stable and gets disordered at high temperature due to hydrolysis.

The stability of nanosized HZSM-5 zeolite: a high-resolution solid-state NMR study

The thermal and hydrothermal stabilities of HZSM-5 zeolites with crystal sizes less than 100 nm have been studied by multinuclear solid-state NMR, combined with BET and XRD. As evidenced by Al-27 and Si-29 MAS as well as their corresponding cross-polarization/MAS NMR investigations, the thermal stability of nanosized HZSM-5 is not so good as that of microsized HZSM-5. This is due to two processes concerning dealumination and desilicification involved in the calcination of nanosized HZSM-5, while only the dealumination process is conducted in microsized HZSM-5 under the similar calcination process. The hydrothermal stability of nanosized HZSM-5 is, contrary to what was expected, not so bad as that of the microsized HZSM-5 in the course of steam treatment. The actual resistance of the hydrothermal stability to the crystal size of HZSM-5 can be ascribed to an active reconstruction of zeolitic framework through an effective filling of amorphous Si species into nanosized HZSM-5 during hydrothermal treatment. (C) 2001 Published by Elsevier Science B.V.

Protocol optimization for the mild detemplation of mesoporous silica nanoparticles resulting in enhanced texture and colloidal stability

Porosity development of mesostructured colloidal silica nanoparticles is related to the removal of the organic templates and co-templates which is often carried out by calcination at high temperatures, 500-600 °C. In this study a mild detemplation method based on the oxidative Fenton chemistry has been investigated. The Fenton reaction involves the generation of OH radicals following a redox Fe3+/Fe2+ cycle that is used as catalyst and H2O2 as oxidant source. Improved material properties are anticipated since the Fenton chemistry comprises milder conditions than calcination. However, the general application of this methodology is not straightforward due to limitations in the hydrothermal stability of the particular system under study. The objective of this work is three-fold: 1) reducing the residual Fe in the resulting solid as this can be detrimental for the application of the material, 2) shortening the reaction time by optimizing the reaction temperature to minimize possible particle agglomeration, and finally 3) investigating the structural and textural properties of the resulting material in comparison to the calcined counterparts. It appears that the Fenton detemplation can be optimized by shortening the reaction time significantly at low Fe concentration. The milder conditions of detemplation give rise to enhanced properties in terms of surface area, pore volume, structural preservation, low Fe residue and high degree of surface hydroxylation; the colloidal particles are stable during storage. A relative particle size increase, expressed as 0.11%·h-1, has been determined.

Stable ordered mesoporous silica materials templated by high-temperature stable surfactant micelle in alkaline media

Ordered hexagonal mesoporous silica material (JLU-30) has been successfully synthesized in alkaline media at high temperature (> 160 degreesC, using cationic (1,3-dimethyl-2-imidazolidin-2-ylidene)hexadecylmethyl-ammonium bromide (DIHAB) as a template, and characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-desorption isotherms, differential thermal analysis (DTA), and thermogravimetric analysis (TG), as well as Al-27 and Si-29 nuclear magnetic resonance (NMR) spectroscopy. Mesoporous JLU-30 shows much higher hydrothermal stability than MCM-41. Si-29 NMR spectra indicate that the pore walls of JLU-30 samples synthesized at high temperature (160 degreesC) are fully condensed, giving a Q(4)/Q(3) ratio as high as 6.2. In contrast, MCM-41 synthesized at relatively low temperature (100 degreesC) shows the Q(4)/Q(3) + Q(2) ratio at 1.1. Such unique structural feature might be responsible for the observed highly hydrothermal stability of the mesoporous silica materials (JLU-30).

Stable tetrahedral aluminum sites in hexagonal mesoporous aluminosilicates

A unique templating approach for the synthesis of hexagonal mesoporous aluminosilicates via self-assembly of pre-formed aluminosilcate nanoclusters with the templating micella formed by cetyltrimethylammonium bromide (CTAB) is described. The obtained materials of MAS-5 are hydrothermally stable, which is shown by X-ray diffraction (XRD) analysis. Furthermore, as characterized by NMR technique, MAS-5 has stable tetrahedral aluminum sites that is the major contributions to the acidity of aluminosilicate molecular sieve, and on non-framework aluminium species in the samples was observed.

Growth of ultrafine zeolite Y crystals on metakaolin microspheres

Ultrafine zeolite Y crystals (ca. 100-200 nm) have been successfully grown on metakaolin microspheres (< 100 mu m) for which good hydrothermal stability was observed; products were characterized by powder X-ray diffraction, scanning electronic microscopy and transmission electronic microscopy.

Structural relation properties of hydrothermally stable functionalized mesoporous organosilicas and catalysis

The surfactant assistant syntheses of sulfonic acid functionalized periodic mesoporous organosilicas with large pores are reported. A one-step condensation of tetramethoxysilane (TMOS) with 1,2-bis(trimethoxysilyi)ethane (BTME) and 3-mercaptopropyltrimethoxysilane (MPTMS) in highly acidic medium was performed in the presence of triblock copolymer Pluronic P123 and inorganic salt as additive. During the condensation process, thiol (-SH) group was in situ oxidized to sulfonic acid (-SO3H) by hydrogen peroxide (30 wt % H2O2). X-ray diffraction studies along with nitrogen and water sorption analyses reveal the formation of stable, highly hydrophobic, and well-ordered hexagonal mesoscopic structures in a wide range of -CH2CH2-concentrations in the mesoporous framework. The resultant materials were also investigated by Si-29 MAS and C-13 CP MAS NMR, thermogravimetric analyses, UV-Raman spectroscopy, and FT-IR spectroscopy. The role of the bridged organic group on the hydrothermal stability of the mesoporous materials was established, which revealed an enhancement in hydrothermal stability of the materials with incorporation of the bridged organic groups in the network. The catalytic performance of -SO3H functionalized mesoporous materials was investigated in the esterification of ethanol with acetic acid, and the results demonstrate that the ethane groups incorporated in the mesoporous framework have a positive influence on the catalytic behavior of the materials.

Catalytic performance of sheet-like Fe/ZSM-5 zeolites for the selective oxidation of benzene with nitrous oxide

Hierarchical Fe/ZSM-5 zeolites were synthesized with a diquaternary ammonium surfactant containing a hydrophobic tail and extensively characterized by XRD, Ar porosimetry, TEM, DRUV-Vis, and UV-Raman spectroscopy. Their catalytic activities in catalytic decomposition of NO and the oxidation of benzene to phenol with NO as the oxidant were also determined. The hierarchical zeolites consist of thin sheets limited in growth in the b-direction (along the straight channels of the MFI network) and exhibit similar high hydrothermal stability as a reference Fe/ZSM-5 zeolite. Spectroscopic and catalytic investigations point to subtle differences in the extent of Fe agglomeration with the sheet-like zeolites having a higher proportion of isolated Fe centers than the reference zeolite. As a consequence, these zeolites have a somewhat lower activity in catalytic NO decomposition (catalyzed by oligomeric Fe), but display higher activity in benzene oxidation (catalyzed by monomeric Fe). The sheet-like zeolites deactivate much slower than bulk Fe/ZSM-5, which is attributed to the much lower probability of secondary reactions of phenol in the short straight channels of the sheets. The deactivation rate decreases with decreasing Fe content of the Fe/ZSM-5 nanosheets. It is found that carbonaceous materials are mainly deposited in the mesopores between the nanosheets and much less so in the micropores. This contrasts the strong decrease in the micropore volume of bulk Fe/ZSM-5 due to rapid clogging of the continuous micropore network. The formation of coke deposits is limited in the nanosheet zeolites because of the short molecular trafficking distances. It is argued that at high Si/Fe content, coke deposits mainly form on the external surface of the nanosheets. © 2012 Elsevier Inc. All rights reserved.