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.     

Self-identification algorithm for zeolite-based thermal capacity gas sensor

Microsystem Technologies - We demonstrate a new operation mode of thermal gas sensor based on thermal capacity extraction with identification algorithm. The system is a silicon microstructure...     

Nanosized zeolite films for vapor-sensing applications

Colloidal zeolites LTA and BEA sized below 100 nm were synthesized as building blocks for the controlled growth of thin microporous films on piezoelectric sensor devices (quartz crystal microbalance, QCM). The zeolite films were prepared on pre-seeded gold substrates on QCM devices. Initially, a layer of colloidal particles was deposited on the support through chemical bonding with a silane coupling agent, followed by hydrothermal growth. BEA- and LTA-type zeolite films with thicknesses of 250 and 450 nm, respectively, were prepared by optimizing the synthesis conditions. The application of these zeolite films in microsensors for water and organic compounds is presented. The importance of the zeolite structure type with respect to the sensitivity towards different organic and water vapors at various concentrations is discussed. Both zeolites are thermally stable and show reproducible responses during long-term experiments. Based on these results, it was concluded that both zeolite films could be used effectively as humidity sensor materials for water vapor sensing purposes. High sensitivity, good reversibility and long life were demonstrated for this type of zeolite film at low water concentrations. In comparison to LTA, the BEA films show a higher sorption capacity towards water vapor and no rejection of pentane, hexane and cyclohexane, due to the larger pore size of the BEA structure.     

Transformation of amorphous silica colloids to nanosized MEL zeolite

Si-MEL molecular sieve is prepared from aged colloidal precursor solutions under hydrothermal treatment (HT) at 90 °C. In situ dynamic light scattering (DLS) investigations of the precursor solutions and the crystalline Si-MEL sols are performed with the original concentrations. Sub-colloidal particles with a mean radius of about 1 nm and colloidal aggregates with a radius of 10 nm are detected in the precursor colloidal solutions after 5 h aging at room temperature. Consumption of the sub-colloidal particles with time and an increase of the colloidal fraction of 10 nm particles after 48 h aging is observed. After heating of the aged precursor solution at 90 °C for 30 h, three particle populations of 1, 10, and 100 nm radius are formed. Complete transformation from amorphous to crystalline colloidal particles is observed after 68 h extended HT of the aged precursor solution. The mean hydrodynamic radius of the crystalline Si-MEL particles is about 100 nm based on the DLS measurements. The size of the MEL crystals was also confirmed with SEM. Additional time-dependent ²⁹Si NMR measurements of the aged precursor colloidal solutions prior to further crystal growth show that the amount of Q⁰ species (δ=−71.2) decreases, while signals of high intensity in the range between δ=−88.6 and −98.9 indicating the formation of Q³₆ and Q³₈ silicon species appear. IR data reveal that with aging of the precursor colloidal solutions at room temperature, an increased ordering of the silica species similar to those found in the final MEL product is observed.     

Mechanism of zeolite A nanocrystal growth from colloids at room temperature

The formation and growth of crystal nuclei of zeolite A from clear solutions at room temperature were studied with low-dose, high-resolution transmission electron microscopy in field emission mode and with in situ dynamic light scattering. Single zeolite A crystals nucleated in amorphous gel particles of 40 to 80 nanometers within 3 days at room temperature. The resulting nanoscale single crystals (10 to 30 nanometers) were embedded in the amorphous gel particles. The gel particles were consumed during further crystal growth at room temperature, forming a colloidal suspension of zeolite A nanocrystals of 40 to 80 nanometers. On heating this suspension at 80 degrees C, solution-mediated transport resulted in additional substantial crystal growth.     

Fluid catalytic cracking technology: current status and recent discoveries on catalyst contamination

The fluid catalytic cracking (FCC) technology is one of the pillars of the modern petroleum industry which converts the crude oil fractions into many commodity fuels and platform chemicals, such as gasoline. Although the FCC field is quite mature, the research scope is still enormous due to changing FCC feedstock, gradual shifts in market demands and evolved unit operations. In this review, we have described the current status of FCC technology, such as variation in the present day feedstocks and catalysts, and particularly, great attention is paid to the effects of various contaminants of the FCC catalysts of which the latter part has not been sufficiently documented and analyzed in the literature yet. Deposition of various contaminants on cracking catalyst during FCC process, including metals, sulfur, nitrogen and coke originated from feedstocks or generated during FCC reaction constitutes a source of concern to the petroleum refiners from both economic and technological perspectives. It causes not only undesirable effects on the catalysts themselves, but also reduction in catalytic activity and changes in product distribution of the FCC reactions, translating into economic losses. The metal contaminants (vanadium (V), nickel (Ni), iron (Fe) and sodium (Na)) have the most adverse effects that can seriously influence the catalyst structure and performance. Although nitrogen and sulfur are considered less harmful compared to the metal contaminants, it is shown that pore blockage by the coking effect of sulfur and acid sites neutralization by nitrogen are serious problems too. Most recent studies on the deactivation of FCC catalysts at single particle level have provided an in-depth understanding of the deactivation mechanisms. This work will provide the readers with a comprehensive understanding of the current status, related problems and most recent progress made in the FCC technology, and also will deepen insights into the catalyst deactivation mechanisms caused by contaminants and the possible technical approaches to controlling catalyst deactivation problems.     

Kinetics of water adsorption in microporous aluminophosphate layers for regenerative heat exchangers

The performance of thick aluminophosphate molecular sieve layers for heat exchanger applications is evaluated. The aluminophosphate AlPO-18 (AEI structure type code) molecular sieve sorbent is coated on aluminium supports prior the sorption measurements. Two AlPO-18 samples with different morphological appearance, i.e. nano-sized crystals with monomodal size distribution and micron-sized crystals of varying sizes, are used to prepare layers with thickness in the range of 80–750 μm. As a binder component, polyvinyl alcohol (PVOH) was utilized in order to prepare mechanically stable layers, which are mechanically stable over numerous measuring cycles. The sorption measurements are conducted under canonical conditions at 40 °C. The AlPO-18 layers showed decreased mass flows with increasing the thickness. Additionally, the layers comprising nanosized crystals showed higher equilibrium loadings and faster kinetics compared to films based on micron-sized crystals. Following the kinetic studies of pressure, temperature and heat flow, it can be concluded that the heat transport is the rate limiting mechanism for thick aluminophosphate layers. Importantly, the diffusion limitation plays a role only for relatively thin microporous aluminophosphate layers (<200 μm). Below this thickness complete heat transfer is achieved within 2 min which allows fast heat exchanger cycles. Thus, the application of microporous aluminophosphate layers for heat transformation and storage applications is considered possible.     

Variation of the Si/Al ratio in nanosized zeolite Beta crystals

Zeolite Beta nanocrystals were prepared from basic aluminosilicate precursor solutions upon hydrothermal treatment at 100 °C. The Si/Al ratio of the initial system was systematically changed from 25 to infinity in order to study the limits in the framework composition of BEA-type crystallites synthesized from clear basic solutions. Furthermore, the effect of the Si/Al ratio on the precursor species, ultimate crystal size, morphology and yield was investigated. The results revealed that the crystallization kinetics of nanosized Beta are dependent on the amount of Al in the precursor solutions, that is, the nucleation and growth processes are faster in Al-rich systems. The crystallization process of zeolite Beta with Si/Al ratios in the initial solutions of 14, 23 and 32 was accomplished within 72 h, whereas longer crystallization times, 140 and 264 h, were necessary to obtain crystalline products with Si/Al ratios of 42 and infinity, respectively. The intermediates and final products were investigated by complementary techniques such as XRD, HRTEM, DLS, IR, NMR spectroscopy and chemical analysis. Low temperature (77 K) CO adsorption infrared spectroscopy was used to study the Brønsted acidity of zeolite Beta samples with different Si/Al ratios. The properties of Beta nanocrystals important for the design of catalysts and selective separation materials are provided based on the results obtained from the detailed characterization.     

Detection of CO<Subscript>2</Subscript> and O<Subscript>2</Subscript> by iron loaded LTL zeolite films

Detection of oxygen and carbon dioxide is important in the field of chemical and biosensors for atmosphere and biosystem monitoring and fermentation processes. The present study reports on the preparation of zeolite films doped with iron nanoparticles for detection of CO₂ and O₂ in gas phase. Pure nanosized LTL type zeolite with monomodal particle size distribution loaded with iron (Fe-LTL) was prepared under hydrothermal condition from colloidal precursor suspensions. The zeolite was loaded with iron to different levels by ion exchange. The Fe-LTL suspensions were used for preparation of thin films on silicon wafers via spin coating method. The reduction of the iron in the zeolite films was carried out under H₂ flow (50% H₂ in Ar) at 300 °C. The presence of iron nanoparticles is proved by in situ ultra-violet-visible spectroscopy. The properties of the films including surface roughness, thickness, porosity, and mechanical stability were studied. In addition, the loading and distribution of iron in the zeolite films were investigated. The Fe-LTL zeolite films were used to detect O₂ and CO₂ in a concentration dependent mode, followed by IR spectroscopy. The changes in the IR bands at 855 and 642 cm^–1 (Fe?O?H and Fe?O bending vibrations) and at 2363 and 2333 cm^–1 (CO₂ asymmetric stretching) corresponding to the presence of O₂ and CO₂, respectively, were evaluated. The response to O₂ and CO₂ was instant, which was attributed to great accessibility of the iron in the nanosized zeolite crystals. The saturation of the Fe-LTL films with CO₂ and O₂ at each concentration was reached within less than a minute. The Fe-LTL films detected both oxygen and carbon dioxide in contrast, to the pure LTL zeolite film.

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Zeolite Beta nanosized assemblies

Nanosized zeolite Beta assemblies are prepared by a steam assisted conversion (SAC) method from micron-sized porous amorphous silica grains soaked in clear solutions containing the alumina source and organic template. The zeolite Beta assemblies are built of closely packed uniform nanocrystals (100 nm) and retain the size and morphological features of the primary silica grains. The crystallinity and the phase purity depend strongly on the temperature and time of SAC treatment as well as on the initial aluminum content. For comparison, colloidal zeolite Beta samples with similar Si/Al ratio were prepared by a hydrothermal treatment (HT). The Raman and NMR spectroscopic data reveal that the method of preparation (SAC or HT) does not affect the local structure of Al-rich samples, while for high-silica samples the degree of disorder is higher in the ones obtained via the SAC approach. The adsorption/desorption isotherms of zeolite Beta assemblies and colloidal Beta powders indicate the presence of both micro- and mesoporosity. The catalytic behavior of the zeolite Beta assemblies and colloidal Beta powders in pentane hydroisomerization reaction is studied.