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Abstract: A two-step route comprising treatment in sodium aluminate followed by acid washing was developed to introduce secondary mesoporosity in ZSM-5 zeolites with different Si/Al ratios. The parent and treated zeolites were characterized by ICP-OES (solids and filtrates), XRD, TGA, TEM, gas adsorption (N2 at 77K and Ar at 87K), FTIR, and NH3-TPD. The contact of the zeolite with NaAlO2 solutions induced mild leaching of framework silicon, viz. desilication. However, the porosity of the resulting samples was mostly blocked by NaAlO2-derived deposits and Si-containing debris. A subsequent acid washing with HCl or oxalic acid removed the blocking species, largely regaining the native microporosity and further uncovering the extensive intracrystalline mesoporosity generated in the first step. In order to maximize the micro- and mesoporosity in the final zeolites, the conditions of the NaAlO2 and acid treatments were varied with respect to concentration, temperature, and time. The efficiency of the two-step treatment was remarkable for zeolites with Si/Al=25 and 40. The mesopore surface area of the hierarchical ZSM-5 was 3–4 times higher than in the parent zeolites, while other intrinsic properties like crystallinity and acidity were largely preserved. The physico-chemical properties of hierarchical ZSM-5 obtained by the two-step route and by conventional desilication in NaOH were compared. Both desilication variants led to equivalent mesopore surface areas, although the two-step route presented a higher solid yield and produced smaller mesopores due to the much lower amount of silicon leached compared to the treatment in sodium hydroxide. Mechanistic and kinetic aspects of silicon dissolution and porosity development in ZSM-5 were discussed on the basis of alkaline treatments in mixtures of NaOH and NaAlO2. [Copyright &y& Elsevier]

Abstract: The combination of dealumination and desilication of ZSM-5 zeolites has been investigated in order to decouple mesoporosity creation and modification of acidity. Individually, desilication by treatment in alkaline medium leads to a spectacular mesoporosity development, without distinct modification of the acidic properties, while dealumination by steam treatment mainly impacts on the acidity of the ZSM-5 zeolite. It is shown that application of the alkaline treatment first followed by steam treatment results in MFI zeolites with independently tailored pore architecture and acidic properties, with proven hydrothermal stability under severe conditions. The independent modification of porous and acidic properties cannot be accomplished if the alkaline treatment is performed after the steam treatment, since the presence of extra-framework Al species inhibit Si extraction and related mesopore formation. A promising outlook of the successive alkaline-steam treatment is expected in catalytic applications of microporous materials. [Copyright &y& Elsevier]

Physical gas adsorption is extensively used in the characterization of micro- and mesoporous materials and is often considered as a straightforward-to-interpret technique. However, physical phenomena like the tensile strength effect, adsorbate phase transitions, and monolayer formation in combined micro- and mesoporous materials frequently lead to extra contributions in the adsorption isotherm. Models for pore size determination mostly do not account for this, and assignment to real pores leads to improper analysis of adsorption data. In this review, common pitfalls and limitations in the analysis of pore size distributions derived from adsorption isotherms of micro- and mesoporous materials are identified and discussed based on new results and examples reported in the recent literature. [Copyright &y& Elsevier]

The predominantly insulating nature of zeolites, as many classes of porous catalysts, can severely impair heat transfer and hence their performance in industrial processes. Strategies developed to engineer the thermophysical properties of technical zeolites for fixed-bed applications comprise the use of conductive secondary phases as structured catalyst supports or as inert diluents. However, the impact of integrating conductive additives into composite zeolite bodies (pellets, extrudates, or granules) has not been widely explored. Here, using a transient hot-plate technique to decouple the distinct contributions of porosity, sample hydration, and temperature, we quantify the impact of metallic (copper), ceramic (silicon carbide, aluminum nitride, boron nitride), and carbonaceous (graphite, carbon nanotubes) phases on the thermal conductivity of shaped zeolites at the body and packed-bed scales. The decisive role of particle morphology, dominating over the intrinsic conductivity of an additive, is corroborated through the three-dimensional reconstruction of data acquired by focused ion beam-scanning electron microscopy and X-ray microtomography coupled with in-situ thermographic studies. In particular, the order-of-magnitude improvement evidenced on application of graphite sheets stems from the extended paths of low thermal resistance created in the millimeter-sized catalyst ensemble. Through the identification of structure-property relations, our approach provides new insights into the rational design of composite porous materials with enhanced heat-transfer properties. [ABSTRACT FROM AUTHOR]

Highlights: [•] Mechanochemical treatment, a versatile tool for zeolite synthesis and modification. [•] Scalable, efficient, and mechanistically-distinct to solvent-intensive routes. [•] Structural transformations classified according to the energy required. [•] Catalytic properties enhanced by mechanochemical activation. [•] Rationalization will facilitate the scale up of future zeolite technologies. [ABSTRACT FROM AUTHOR]

Abstract: The improvement of molecular transport properties of hierarchical H-ZSM-5 obtained by desilication was evidenced by studying the desorption of o-xylene and isooctane by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). This technique enabled monitoring simultaneously bands associated with the molecular probes and the zeolite, using powdered sample masses as low as 1mg. Two H-ZSM-5 samples with markedly different crystal sizes were investigated. The first sample was commercial and consisted of small crystallites (ca. 250nm). The second sample were laboratory-made large crystals with coffin-like shape (ca. 17×4×4μm3). The hierarchical derivatives of the small and large zeolite crystals displayed 250 and 120m2 g−1 of mesopore surface area, respectively, in contrast to the 62 and 5m2 g−1 of the parent counterparts. The data based on o-xylene desorption were partly disguised by site-desorption limitations. Desorption experiments using isooctane evidenced a 4-fold reduction in the characteristic diffusion path length on both mesoporous small and large zeolites with respect to their purely microporous analogues. These results confirm the substantial potential for improvement of commercial nanocrystalline zeolites in diffusion-limited reactions upon the introduction of intra-crystalline mesoporosity by post-synthesis modification. [Copyright &y& Elsevier]

Abstract: We introduce a novel ‘spray deposition’ method as a continuous, reproducible, versatile, simple, and scalable method for the preparation of highly-dispersed, uniformly-sized, and sintering-resistant supported metal nanoparticles on porous supports. Instant drying of aqueous aerosol droplets containing the metal precursor (e.g. palladium nitrate) and the support (e.g. ferrierite zeolite) in a commercial bench-scale spray drier proves the key for maximizing the metal dispersion. In contrast, the much lower rates of solvent removal characteristic of dry and wet impregnation methods using classical drying or even freeze drying led to broad particle size distributions. The spray-dried Pd/ferrierite catalyst exhibited high alkene selectivity in the gas-phase hydrogenation of propyne. These results demonstrate that spray drying is not only a highly suited unit operation to prepare catalyst supports but also functional catalysts in one step. The method offers attractive opportunities for large-scale catalyst manufacture and as well as for preparation of well-defined systems for academic studies. [Copyright &y& Elsevier]

Abstract: Zeolite beta crystals (Si/Al=35) synthesized in fluoride medium were treated in aqueous 0.2M NaOH solution for mesopore formation by selective extraction of framework silicon. A 16 parallel-batch reactor was used to study the influence of the treatment time and temperature on the physico-chemical properties of the zeolites, which were characterized by ICP-OES, XRD, N2 adsorption at 77K, SEM, TEM, DRIFTS, and in situ ATR-IR. Alkaline treatment of H-beta within the optimal window of Si/Al ratios identified for other zeolite families leads to extensive silicon extraction at mild treatment conditions. This originates substantial mesoporosity and presumably improved transport, but negatively impacts on the microporous and acidic properties of the resulting sample. Consequently, the alkaline-treated beta zeolites show lower catalytic activity in the acid-catalyzed liquid-phase benzene alkylation than the purely microporous parent material. The relatively low stability of framework aluminum in BEA, compared to MFI and MOR, is detrimental for the controlled mesopore formation by Si dissolution, since aluminum cannot optimally exert its pore-directing role. [Copyright &y& Elsevier]