Synthesis of ZSM‐5 Films and Monoliths with Bimodal Micro/Mesoscopic Structures

A route to synthesize ZSM‐5 crystals with a bimodal micro/mesoscopic pore system has been developed in this study; the successful incorporation of the mesopores within the ZSM‐5 structure was performed using tetrapropylammonium hydroxide (TPAOH)‐impregnated mesoporous materials containing carbon nanotubes in the pores, which were encapsulated in the ZSM‐5 crystals during a solid rearrangement process within the framework. Such mesoporous ZSM‐5 zeolites can be readily obtained as powders, thin films, or monoliths.     

Femtochemistry of Guest Molecules Hosted in Colloidal Zeolites

The ultrafast deprotonation of 2‐(2′‐hydroxyphenyl)benzothiazole (HBT) hosted in nanometer‐sized FAU and MFI zeolites is reported. Samples are prepared via in‐situ incorporation of HBT in the precursor colloidal solutions resulting in the formation of nanometer‐sized zeolites under hydrothermal treatment. The diameter of the zeolite particles formed in the crystalline suspensions is determined by dynamic light scattering and high‐resolution transmission microscopy to lie in the range 40–100 nm. It is shown that the HBT loading does not influence the degree of the zeolite crystallinity but does change the size and the morphology of the individual zeolite nanoparticles. Colloidal suspensions containing the crystalline nanoparticles are well suited for optical investigations since they are sufficiently transparent and clear. The photochemical properties of the HBT guest in the zeolite‐host systems are studied with femtosecond transient transmission spectroscopy. Depending on the acid–base properties either the enol or the keto tautomer of HBT is found to be hosted in the internal voids of the zeolites; upon UV excitation, the HBT‐keto tautomer is converted to the enol form in both MFI‐ and FAU‐type hosts. The HBT photoconversion takes place via an ultrafast deprotonation within 1.5 ps as detected by femtosecond transient absorption spectroscopy.     

Epoxidation of olefines with PDMS membranes containing zeolite occluded manganese diimine complexes

A new composite catalyst for selective epoxidation of olefins with tert-butyl hydroperoxide (tBHP) is reported. The catalyst contains manganese diimine complexes (cis-Mn bis-2,2′-Bipyridyl), occluded within a NaY zeolite, in turn incorporated in a polydimethylsiloxane membrane (cis-[Mn(bpy)₂]²⁺-NaY-PDMS). The three-step synthesis consists of a Mn²⁺exchange of NaY, ligand sorption to form cis-[Mn(bpy)₂]²⁺-NaY and incorporation of the latter in a PDMS membrane. The major differences between [Mn(bpy)₂]²⁺-NaY as such and occluded in PDMS are observed in the sorption and catalytic characteristics. With the membrane system, the use of a solvent becomes obsolete. Whereas optimal cyclohexene oxidation with [Mn(bpy)₂]²⁺-NaY occurs with hydrogen peroxide in acetone, tBuOOH proves to be a better oxidant for [Mn(bpy)₂]²⁺-NaY-PDMS. The reactions in batch and fed-batch reactors are discussed. A simple regeneration procedure, monitored by FT-IR spectroscopy is proposed.     

Advances in Microporous and Mesoporous Solids—Highlights of Recent Progress

This report highlights developments in the fields of microporous and mesoporous materials that were published mostly during the year 2002. Selected examples are provided to illustrate new zeolite structures, porous coordination materials, mesoporous solids with new compositions, controlled morphologies, and increased hydrothermal and thermal stabilities, as well as porous solids with tunable pore openings or other structural features that can be dynamically modified. A number of applications are discussed, including stabilization of reactive guests, separations, electronic materials, and sensors.     

Density functional theory studies of Cu-zeolite de-NOx catalysts

Summary Recent progress in the modelling of exchanged Cu sites and their interactions with small molecules, based on DFT cluster calculations, is briefly reviewed.     

Change in the decomposition mode of 1-propanamine due to the presence of cations in MFI zeolite

The adsorption and thermal analysis of 1-propanamine has been compared over MFI zeolites which contain H, Ga, and In cations. In the case of H⁺-containing materials, NH₃ and propene are simultaneously desorbed above 600 K. This behavior, is well known and characteristic of the Hofmann elimination reaction. However, a distinctly different mode of reaction is observed in the case of Ga and In containing materials. NH₃ is released below 600 K, propene and other products are released above 600 K, and a stable residue remains above 800 K. It is suggested that such behavior results from Lewis acid interactions of Ga or In cations with propanamine.On leave from the Bulgarian Academy of Sciences, Institute of Organic Chemistry.     

Zeolite based films, membranes and membrane reactors: Progress and prospects

The integration of reaction and separation in catalytic membrane reactors has received increasing attention during the past 30 years. The combination promises to deliver more compact and less capital-intensive processes with substantial savings in energy consumption. With the advent of new inorganic materials and processing techniques, there has been renewed interest in exploiting the benefits of membranes in many industrial applications. Zeolite membranes, however, have only recently been considered for catalytic membrane reactor applications. Despite the significant recent interest in these types of membranes there are relatively few reports of the application of such membranes in high-temperature catalytic membrane reactor applications. This can be attributed to a number of limitations that still need to be addressed such as the relatively high price of membrane units, the difficulty of controlling the membrane thickness, permeance, high-temperature sealing, reproducibility and the dilemma of upscaling. A number of research efforts, with some degree of success have been directed to finding solutions to the remaining challenges. This review makes a critical assessment of what has been achieved in the past few years in terms of hurdles that still stand in the way of the successful implementation of zeolite membrane reactors in industry.