0000000000393610
AUTHOR
German Sastre
Quantum-chemistry calculations of surface complex and orbital control in para/ortho toluene alkylation catalyzed by big pore zeolites
Summary By means of MNDO-PM3 semiempirical quantum-chemistry calculations, the mechanism for alkylation of toluene by methanol on two zeolite clusters with Al and Ga as T III has been studied. The process variables controlled through the hypersurface of the reaction were: the distances of methyl group to the cluster of zeolite and to the toluene molecule; and the distances of the hydrogen atom of the toluene to be transfered to the zeolite cluster and to the toluene. The energetic factor associated with the electronic interaction between the molecular orbitals (LUMO of the zeolite-methoxy and HOMO of toluene) have been calculated by a PMO analysis for two geometries: the transition state an…
Computational screening of structure directing agents for the synthesis of zeolites. A simplified model
Abstract Zeolite micropores become more energetically stable by the occlusion of organic structure directing agents (templates). This energetic stabilisation, if approximated by van der Waals zeo-template interactions, can be calculated in a fast way by using modern computing techniques incorporating big data handling algorithms for massive screening. A software suite is presented which calculates an arbitrarily large 2-D matrix (template×zeolite) giving the zeo-template van der Waals interaction energy corresponding to the minimum energy conformation assuming one template molecule in a pure silica zeolite unit cell. With the goal of simplicity, the software only needs two coordinate input …
Synthesis of a novel zeolite through a pressure-induced reconstructive phase transition process
et al.
Xylene isomerization and aromatic alkylation in zeolites NU-87, SSZ-33, β, and ZSM-5: molecular dynamics and catalytic studies
The unique pore topology of zeolite NU-87, with 10-membered ring (MR) channels intersected by perpendicular 12-MR cavities, can offer new opportunities for alkylaromatics isomerization, as well as for aromatics alkylation. The catalytic performance has been studied for meta-xylene isomerization and disproportionation, as well as toluene alkylation with methanol, ethanol, propanol, and isopropanol. Product distribution was interpreted on the basis of pore topology and compared to zeolites with 12-MR (β), 10- and 12-MR (SSZ-33), and 10-MR (ZSM-5) zeolites. The presence of cavities allows more space for the location of bulky intermediates and/or products, and also traps the molecules, allowing…
Isomerization and disproportionation of m-xylene in a zeolite with 9- and 10-membered ring pores: Molecular dynamics and catalytic studies
The unique pore topology of zeolite ITQ-13 with 9-membered ring (MR) channels intersected by perpendicular 10-MR channels and larger void space with 10-MR cross-sections was studied for meta-xylene isomerization and disproportionation. Product distribution was interpreted on the basis of pore topology and compared with zeolites with 12-MR (β), 10-MR, and intersecting 12-MR cavities (NU-87), as well as 10-MR (ZSM-5) zeolites. The presence of cavities allows more space for bulky intermediates and/or products and also provides room for molecules to drive consecutive reactions toward thermodynamic equilibrium. Channels, on the other hand, allow diffusion without trapping if their free diameters…
Identification of New Templates for the Synthesis of BEA, BEC, and ISV Zeolites Using Molecular Topology and Monte Carlo Techniques
The presence of organic structure directing agents (templates) in the synthesis of zeolites allows the synthesis to be directed, in many cases, toward structures in which there is a large stabilization between the template and the zeolite micropore due to dispersion interactions. Although other factors are also important (temperature, pH, Si/Al ratio, etc.), systems with strong zeolite-template interactions are good candidates for an application of new computational algorithms, for instance those based in molecular topology (MT), that can be used in combination with large databases of organic molecules. Computational design of new templates allows the synthesis of existing and new zeolites …
Water-Hydrophobic Zeolite Systems
Water intrusion-extrusion in hydrophobic microporous AFI, IFR, MTW and TON pure silica zeolites (zeosils) has been investigated through molecular dynamics (MD) simulations. It was found that intruded water volumes correlate with the free volume of the zeosil unit cells. Calculated adsorption isotherms allowed us to estimate the amounts of water intruded, and deviations from experiments (lower experimental with respect to calculated intrusion pressures) have been;explained in terms of connectivity defects in the synthesized materials. Water phase transitions in defectless zeosils occur in a narrow range at high pressure. On the basis of a simple model, we derived a thermodynamic equation tha…
Quantum chemistry calculations on the effect of electron confinement upon the frontier molecular orbitals of ethylene and benzene in sodalite. Implications on reactivity
Abstract Quantum chemistry calculations using HF / STO-3G, CEP-41G, and 3-21G basis sets have been carried out in order to study the effect of the electron confinement of ethylene and benzene in the microporous environment existing in a sodalite cage. The electron confinement produces an increase of 1.06 and 1.31 eV at the 3-21G level in the energy of the HOMO of ethylene and benzene, respectively, when placed in the centre of the cavity with respect to the HOMO energy in the gas phase. There is an increase in the energy of the HOMO when the molecules approach the walls of the zeolite.
A Multisite Molecular Mechanism for Baeyer-Villiger Oxidations on Solid Catalysts Using Environmentally Friendly H2O2 as Oxidant
The molecular mechanism of the Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide catalyzed by the Sn-beta zeolite has been investigated by combining molecular mechanics, quantum-chemical calculations, spectroscopic, and kinetic techniques. A theoretical study of the location of Sn in zeolite beta was performed by using atomistic force-field techniques to simulate the local environment of the active site. An interatomic potential for Sn/Si zeolites, which allows the simulation of zeolites containing Sn in a tetrahedral environment, has been developed by fitting it to the experimental properties of quartz and SnO 2 (rutile). The tin active site has been modeled by means of a S…
Gas confinement in compartmentalized coordination polymers for highly selective sorption
Discrimination between different gases is an essential aspect for industrial and environmental applications involving sensing and separation. Several classes of porous materials have been used in this context, including zeolites and more recently MOFs. However, to reach high selectivities for the separation of gas mixtures is a challenging task that often requires the understanding of the specific interactions established between the porous framework and the gases. Here we propose an approach to obtain an enhanced selectivity based on the use of compartmentalized coordination polymers, named CCP-1 and CCP-2, which are crystalline materials comprising isolated discrete cavities. These compar…
The benefit of multipore zeolites: Catalytic behaviour of zeolites with intersecting channels of different sizes for alkylation reactions
Abstract The catalytic behaviour of two multipore zeolites containing channels of different sizes, SSZ-33 (10 windows × 12 MR) and ITQ-22 (8 × 10 × 12 MR pores), for alkylation of benzene with ethanol and benzene with isopropanol or propylene, has been studied and compared to that of zeolites with intersecting channels of the same size, ZSM-5 (10 × 10 MR channels) and Beta (12 × 12 MR channels), which are industrially used for the above-mentioned process. For the alkylation of benzene with ethanol in gas phase, ITQ-22 behaves like the 10 MR ZSM-5 with respect to ethylbenzene selectivity, while the behaviour of SSZ-33 is close to that of a 12 MR zeolite such as Beta. For the alkylation of be…
SOFT AND HARD ACIDITY IN ZEOLITES AND ZEOTYPES: EVALUATION AND CATALYTIC IMPLICATIONS
It has been found by Molecular Orbital calculations, that the energy of the LUMO of a zeolite cluster can be used to measure the softness–hardness acidity. It has been found that the higher the framework Si/AI ratio the softer is the acidity. When applied to the alkylation of aromatics, it has been calculated that the higher the framework Si/AI ratio of the zeolite, the more “orbital controlled” will be the reaction, and therefore a higher para to ortho ratio is expected. This has been confirmed experimentally during the alkylation of toluene and m–xylene by methanol on HY zeolites with different framework Si/AI ratio.