Atomistic modeling of zeolitic materials

A review with 166 refs. on modeling the structure and properties of the bare zeolitic framework. The topics include modeling methods and interat. potential developmen

Lattice mechanical study of the structure of dodecasil-3C

A recently developed partial charge potential model for SiO2 polymorphs, derived from quantum chem. calcns., was applied to the calcn. of the lattice energy-minimized structure and phys. properties of the low-d. SiO2 crystal Dodecasil-3C. Calcns. were performed using Ewald summations and without symmetry constraints. Results are compared with calcns. using the shell model of Sanders et al. (1983). Best agreement between exptl. and theor. predicted elastic consts. is achieved assuming a triclinic structure. To establish lattice stability, the vibrational frequency spectrum was calcd. For structures with imaginary frequencies, the corresponding at. displacements are used to deform the quasi-stationary geometry. On lattice energy minimization, the deformed structure transforms to a stable energy min. The large anisotropic temp. factors obsd. exptl. are mainly due to static disorder in at. position

Positron emission profiling : a study of hydrocarbon diffusivity in MFI zeolites

Zeolites are of prime importance to the petrochemical industry as catalysts for hydrocarbon conversion. In their molecule-sized micropores, hydrocarbon diffusion plays a pivotal role in the final catalytic performance. Here, we present the results of Positron Emission Profiling experiments with labeled hydrocarbons in zeolites with the MFI morphology. Single-component self-diffusion coefficients of hexanes in silicalite-1 and its acidic counterpart H-ZSM-5 are determined. For the first time, self-diffusion co efficients of n-pentane and n-hexane in mixtures are studied. This shows that Positron Emission Profiling is a powerful technique for in situ investigations of the adsorptive and diffusive properties of hydrocarbons in zeolites. The diffusion of hydrocarbons in medium-pore zeolites is determined by a complex interplay of factors such as the loading, the temperature, the preference for certain pore locations, the interactions with other hydrocarbon molecules of the same type or of other types and the presence of acid protons. In the diffusion of mixtures, pore blockage by one of the components might occur, thus strongly decreasing the diffusivity of the faster diffusing hydrocarbon

Interatomic potentials for zeolites. Derivation of an ab-initio shell model potential

A new method has been developed for deriving parameters for the shell model of silica polymorphs. All parameters for the shell model are derived in a self-consistent way from ab-initio potential energy surfaces, polarizabilities, and dipole moments of small clusters. This yields an ab-initio partial-charge-shell model potentia

Influence of aging and dilution on the crystallization of silicate-1

The correlation between the formation of colloidal aggregates and the crystallization of silicalite-l from a clear solution has been investigated with in situ combined small-angle X-ray scattering and wide-angle X-ray scattering, and in situ ultra- small-angle X-ray scattering using synchrotron radiation. Increasing the aging time at room temperature of the synthesis mixture prior to heating to the reaction temperature reduced the induction period and increased the crystal growth rate without affecting the formation of colloidal aggregates. Dilution of the synthesis mixtures did not influence the nucleation and crystal growth rate, and did not affect the formation of colloidal aggregate

A Quasi-Elastic Neutron Scattering Study of the Ammonium Ions in CsNH4-Y Zeolite

Quasi-elastic neutron scattering was used to study the reorientation mechanism for ammonium ions in Cs-exchanged zeolite Y. This sample contains ammonium ions preferentially located in the sodalite cages at site 1'. These ions reorient with 120 or 180 Deg jumps around fixed axes through the N atom. This corresponds to a bonding geometry in which the ammonium ion interacts via 3 or 2 H atoms with the lattice O atoms. Addnl., a reorientation around a fixed axis through 2 H atoms of the ammonium ion may occur. The ammonium ion then jumps between 2 equil. positions: one position involves a 2-fold bonding geometry and the other a 3-fold bonding geometry. At 300 K the effective time interval between 2 jumps is t = 1.2 +- 0.5 ps. Compared to zeolite Rho, the ammonium ions in the Cs-exchanged zeolite Y show a more restricted reorientational behavior, resulting in a larger elastic incoherent structure factor. [on SciFinder (R)

Hydrodesulfurization activity of zeolite-supported nickel and cobalt sulfide catalysts

Various zeolite (NaY or CaY) supported metal sulfide (Ni or Co) catalysts were prepared (impregnation or ion exchange) and characterized by means of thiophene HDS, Xe-129 NMR and TPS. Especially the acidic zeolites showed a very high initial activity. The observed activity differences are discussed in terms of sulfidation, dispersion, position of the metalsulfide relative to the zeolite pore system and acidity, the latter two being the most important. It is concluded that small Ni and Co sulfide clusters are very efficient thiophene desulfurization catalyst

13C and 23Na Solid-state NMR study on zeolite Y loaded with Mo(CO)6

The Na-23 MAS and double rotation (DOR) NMR spectra of dehydrated zeolite NaY loaded with two molecules of Mo(CO)(6) per supercage show three components distinguished by the corresponding quadrupole coupling constants (QCC). Sodium cations in the hexagonal prisms (SI sites) are characterized by a narrow Gaussian line with a QCC value close to zero. A second component with quadrupole coupling constants between 4.4 and 4.8 MHz is assigned to Na+ cations located in the sodalite cages, and the third component with QCC ranging between 2.2 and 2.8 MHz is due to sodium cations in the supercages interacting with Mo(CO)(6). These sites are characterized by structural and/or dynamical disorder as observed by typical line shape properties. Adsorption of Mo(CO)(6) in Y zeolites, where all Na+ cations in the supercages of NaY have been exchanged with NH4+ Or H+, causes the sodium cations in the sodalite cages to migrate into the supercages in order to interact with the adsorbent. For the NH4+-exchanged sample, the anisotropic chemical shift parameters for C-13 in Mo(CO)(6) have been analyzed at ambient temperature. From the results a fast anisotropic local reorientation of Mo(CO)(6) follows. The rotation is about a 3-fold axis of the octahedral complex. The octahedron is slightly elongated along the rotation axis by about 4 degrees when it is located close to the sodium cation

Modeling of structure and vibrational spectra of aluminophosphate AlPO4 5 and its silica analog SSZ 24

In this study, the structural and vibrational properties of the AlPO4 structure AlPO4-5 and the silica structure SSZ-24 are compared. Lattice energy calcns. are done using existing potential parameter sets suitable for silicas and AlPO4's. For the computation of vibrational spectra of silica systems, force consts. derived by Etchepare et al. are used. For AlPO4 spectra simulations, a new force field is presented that is based on a fit on vibrational frequencies of a-berlinite, the AlPO4 analog of a-quartz. Lattice energy calcns. result in a symmetry of AlPO4-5 and SSZ-24 that is lower than derived exptl. A shift of layers is obsd. for both structures when a potential with partial charges is used. These results are indicative for an underestn. of the charges used in the partial charge model. The influence of structure on spectra is shown to be rather weak. The main differences between the spectra of AlPO4-5 and SSZ-24 are due to the interat. force const