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.

Low temperature heat capacity and thermal stability of nanocrystalline nickel

The heat capacity (C-p) of nanocrystalline nickel (nc-Ni, 40 mn crystallite size) has been measured over the temperature range of 78-370 K with a high-resolution automated adiabatic calorimeter. The measured results are compared with the C-p values of the corresponding coarse-grained crystal, and an enhancement of heat capacity of the nanocrystalline nickel was observed to be 2-4% in the temperature range between 100 and 370 K. The thermal stability of the nanocrystalline nickel sample was determined by a differential scanning calorimeter and a thermogravimetric system. The melting point of nc-Ni is the same as that of the corresponding coarse-grained crystalline nickel and the sample is stable at temperature lower than 500 K. (C) 2002 Elsevier Science B.V. 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.

Collisional quantum interference effect on rotational energy transfer in an atom-diatom system

The theoretical model of collisional quantum interference (CQI) in intramolecular rotational energy transfer is described in an atom-diatom system, based on the first Born approximation of time-dependent perturbation theory and considering a long-range interaction potential. The relation between differential and integral interference angles is obtained. For the CO A(1)Pi (v = 0)/e(3)Sigma (-)(v = 1)-He collision system, the calculated integral interference angles are consistent with the experimental values. The physical significance of interference angle and the essential factors it depends on as well as the influence of the short-range interaction on CQI are discussed. (C) 2001 Elsevier Science B.V. All rights reserved.