Search results for "ZEOLITE"
showing 10 items of 203 documents
Butene Isomerization and Double-Bond Migration on the H-ZSM-5 Outer Surface: A Density Functional Theory Study
2011
Isomerization of trans-but-2-ene to cis-but-2-ene and double bond migration of trans-but-2-ene to but-1-ene have been investigated by means of density functional theory calculations on a suitable model of H-ZSM-5 surface. The study has been afforded on outer surface sites by considering the hydroxyl group of either a SiO2(OH)2 or a AlO2H(OH)2 moiety. On these outer surface sites, one alkoxide species occurs as a stable intermediate both along the isomerization and double bond migration pathways. The latter process could also occur via a single-step mechanism, which involves a six-center transition state. The energy barriers of the outer surface processes above do not take any advantage by t…
Heterocyclic rearrangements in constrained media. A zeolite-directed photorearrangement of 1,2,4-oxadiazoles
2005
[reaction: see text] The first intrazeolite-photoinduced rearrangement of a five-membered heterocycle is reported. A completely different behavior compared to solution irradiations has been observed. The zeolite's role in directing the photoreaction of 3-phenyl-1,2,4-oxadiazoles toward the formation of the corresponding 1,3,4-oxadiazoles in a ring contraction-ringexpansion route is discussed.
Photooxidations of Alkenes in Fluorinated Constrained Media: Fluoro-organically Modified NaY as Improved Reactors for Singlet Oxygen “Ene” Reactions
2007
Creating a stationary fluorinated environment inside the zeolite cavity can increase the reactivity observed for intrazeolite photooxidation of alkenes. Exchanging the zeolite with fluorinated organic cations is a much more effective strategy than simply using a fluorinated solvent for slurry irradiations. Use of cations containing C-F bonds is also more efficient than use of deuterated cations for creation of a singlet oxygen friendly environment where the quenching processes are slowed down. Doping the zeolite with fluoro-organic cation 4 resulted in an increase in the singlet oxygen lifetime to 12 micros.
A new experimental protocol for intrazeolite photooxidations. The first product-based estimate of an upper limit for the intrazeolite singlet oxygen …
2002
The intrazeolite photooxidations of several alkenes have been examined in hexane and in perfluorohexane slurries. The ability of perfluorohexane to increase the affinity of alkenes for the interior of the zeolite was documented. The nearly identical reaction rates in the two slurry solvents are attributed to a leveling of the singlet oxygen lifetime by the zeolite framework. A consideration of the rates of the various intrazeolite processes was used to estimate an upper limit for the intrazeolite lifetime of singlet oxygen.
A Novel Zeolite-Induced Population of a Planar Viologen Conformation. New Viologen Charge Transfer Complexes and Alkene/Viologen/Zeolite Arrays
2004
A rare example of a novel zeolite-induced conformational change and a mechanism for this process are suggested in order to rationalize an unexpected spontaneous intrazeolite reduction observed during preparation of a new viologen (MQ2+)-doped zeolite (NaY). In addition, the formations of six new alkene/viologen/ zeolite charge transfer (CT) arrays using NaMQY and the previously reported NaMVY are also reported. The binding constants between MQ2+ and MV2+ and 2,3-dimethyl-2-butene (TME) were determined using the Benesi-Hildebrand approach, and the stabilities of these CT complexes are compared to their intrazeolite analogue.
On the Mechanism of Xylene Isomerization and its Limitations as Reaction Test for Solid Acid Catalysts
1993
The kinetics of the gas-phase isomerization of m-xylene, over a series of ultraestable Y zeolites, has been studied in a fixed-bed flow reactor under initial conditions. Using deuterated p-xylene as reactant it has been seen that more than 20% of the m- and o-xylene obtained, are formed via a bimolecular mechanism. The relative proportion of uni- to bimolecular mechanism depends on the zeolite composition. The relation between the turnover number, calculated from the kinetic rate constant for the unimolecular mechanism, and the framework Al content of the zeolite, was coincident with the topological zeolite model. Besides, the values of the adsorption constants indicate that dealumination h…
Determination of the Pore Topology of Zeolite IM-5 by Means of Catalytic Test Reactions and Hydrocarbon Adsorption Measurements
2000
Abstract The pore topology of a recently synthesized zeolite IM-5 has been determined by means of catalytic test reactions, i.e., n -decane hydroisomerization–cracking, m -xylene isomerization–disproportionation, n -hexadecane isodewaxing, and adsorption–microcalorimetry of molecules with different sizes and shapes ( n -hexane, toluene, m -xylene, and 1,3,5 trimethylbenzene). It has been found that the channel network consists of a system of unidirectional 10 MR with lobes or side pockets, or crossing 10 membered ring pores with a pore diameter somewhat smaller than those in ZSM-5. This structure offers interesting shape selectivity features for catalytic reactions.
Quantum-chemistry calculations of surface complex and orbital control in para/ortho toluene alkylation catalyzed by big pore zeolites
1994
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…
Synthesis of hyacinth, vanilla, and blossom orange fragrances: the benefit of using zeolites and delaminated zeolites as catalysts
2004
The synthesis of phenylacetaldehyde glycerol acetals, 2-benzyl-4-hydroxymethyl-1,3-dioxolane (1), 2-benzyl-5-hydroxy-1,3-dioxane (2), and vanillin propylene glycol acetal (2-(4-hydroxy-3-methoxyphenyl)-4-methyl-1,3-dioxolane) (3) which are flavoring compounds with hyacinth and vanilla scent fragrances, have been carried out successfully by acetalization of phenylacetaldehyde and vanillin with glycerol and propylene glycol, respectively, using toluene as solvent and zeolite catalysts whose adsorption properties have been optimized. However, in the case of a larger size acetal such as 2-acetonaphthone propylene glycol acetal (4) with blossom orange scent, geometrical constraints make the diff…
Steam-activated FeMFI zeolites. Evolution of iron species and activity in direct N2O decomposition
2003
Abstract In this paper the effect of the composition and steaming conditions of FeMFI catalysts on activity in direct N2O decomposition is investigated. MFI zeolites with different framework compositions (FeAlSi, FeGaSi, and FeSi) and without iron ( 100 mbar H2O in N2) favor the extraction of framework iron, enabling the application of lower activation temperatures. The optimum temperature during steam activation is that at which extraction of framework iron is complete without extensive clustering of extra-framework iron species into oxide particles, as was demonstrated by transmission electron microscopy and electrochemical characterization of the samples. Additional experiments show…