OSDA-Free Seeded Cu-Containing ZSM-5 Applied for NH3-SCR-DeNOx.

A series of ZSM-5 zeolite materials were synthesized from organic structure-directing agent (OSDA)-free seeded systems, including nanosized silicalite-1 (12 wt % water suspension or in powder form) or nanosized ZSM-5 (powder form of ZSM-5 prepared at 100 or 170 °C). The physicochemical characterization revealed aggregated species in the samples based on silicalite-1. Contrarily, the catalysts based on ZSM-5 seeds revealed isolated copper species, and thus, higher NO conversion during the selective catalytic reduction of NOx with NH3 (NH3-SCR-DeNOx) was observed. Furthermore, a comparison of the Cu-containing ZSM-5 catalysts, conventionally prepared in the presence of OSDAs and prepared with an environmentally more benign approach (without OSDAs), revealed their comparable activity in NH3-SCR-DeNOx.

The Durable Chitosan Functionalization of Cellulosic Fabrics.

In this work, the durability of chitosan functionalization of cellulosic textile substrates, cotton and cotton/polyester blended fabrics, was studied. Chitosan is a naturally occurring biopolymer that can be produced inexpensively. It should be dissolved in an acidic solution to activate its antimicrobial and other properties, i.e., good biocompatibility, bioabsorbability, wound healing, hemostatic, anti-infective, antibacterial, non-toxic, and adsorptive properties. The application of chitosan to textile products has been researched to achieve antimicrobial properties, but the durability, after several maintenance cycles, has not. Chitosan functionalization was carried out using maleic acid (MA) and 1,2,3,4-butanetetracarboxylic acid (BTCA) as crosslinking and chitosan-activating agents and sodium hypophosphite monohydrate as a catalyst. To determine durability, the fabrics were subjected to 10 maintenance cycles according to ISO 6330:2012 using Reference detergent 3 and drying according to Procedure F. The properties were monitored after the 3rd and 10th cycles. The crosslinking ability of chitosan with cellulosic fabrics was monitored by Fourier infrared spectrometry using the ATR technique (FTIR-ATR). Changes in mechanical properties, whiteness and yellowing, and antimicrobial properties were determined using standard methods. Compared to maleic acid, BTCA proved to be a better crosslinking agent for chitosan.

Defect Sites in Zeolites: Origin and Healing.

This paper deals with the synthesis conditions-defect formation relationship in zeolites. Silicalite-1 (MFI-type) is used as a model material. Samples synthesized from a system with high basicity (at 100 °C), a system with moderate basicity (at 150 °C), and a fluoride-containing system in neutral medium (at 170 °C) are compared. Well-crystallized materials with sizes ≈0.1, 1-10, and 30-40 µm are obtained. The samples are analyzed by complementary methods providing information on the short- and long-range order in the zeolite framework. A strong correlation between the number of point defects in the zeolite framework and preparation conditions is established. Silicalite-1 synthesized under mild synthesis conditions from a highly basic system exhibits a larger number of framework defects and thus low hydrophobicity. Further, the calcined samples are subjected to aluminum and silicon incorporation by postsynthesis treatment. The Al/Si incorporation in the zeolite framework and its impact on the physicochemical properties is studied by XRD, TEM/SEM, solid-state NMR, FTIR, and thermogravimetric analyses. The defects healing as a function of the number of point defects in the initial material and zeolite crystal size is evaluated. The results of this study will serve for fine-tuning zeolite properties by in situ and postsynthesis methods.

Time-resolved dissolution elucidates the mechanism of zeolite MFI crystallization.

Zeolite crystal growth mechanisms are not fully elucidated owing to their complexity wherein the formation of a particular zeolite can occur by more than one crystallization pathway. Here, we have conducted time-resolved dissolution experiments of MFI-type zeolite crystals in ammonium fluoride medium where detailed structural analysis allowed us to extrapolate and elucidate the possible mechanism of nucleation and crystal growth. A combination of electron and scanning probe microscopy shows that dissolution initiates preferentially at lattice defects and progressively removes defect zones to reveal a mosaic structure of crystalline domains within each zeolite crystal. This mosaic architecture evolves during the growth process, reflecting the changing conditions of zeolite formation that can be retroactively assessed during zeolite crystal dissolution. Moreover, a more general implication of this study is the establishment that dissolution can be used successfully as an ex situ technique to uncover details about crystal growth features inaccessible by other methods.

Tuning Zeolite Properties for a Highly Efficient Synthesis of Propylene from Methanol.

A series of nanosized ZSM-5 samples was synthesized at 170, 150, 120, and 100 °C. Experimental data show that the decrease of crystallization temperature leads to significant changes in zeolite properties. Crystals synthesized at 100 °C exhibit many framework defects with lower acid-site density, strength, and a larger external surface area. The selectivity to light olefins and the propylene-to-ethylene ratio increases as the crystallization temperature decreases. A propylene-to-ethylene ratio of above 6 with the highest selectivity to propylene of 53 % was obtained over ZSM-5 catalyst prepared at 100 °C. The stability of the nanosized zeolite in methanol to olefins (MTO) was also improved compared to the industrial sample with a similar Si/Al ratio. This catalytic performance is a result of the decrease in the acid-site density, strength, and the crystals' size, providing a shorter diffusion path and larger external surface area. The presence of structural defects and a different external surface in the crystals has been shown to play an important role in the MTO catalyst performance.

3D Study of the Morphology and Dynamics of Zeolite Nucleation.

The principle aspects and constraints of the dynamics and kinetics of zeolite nucleation in hydrogel systems are analyzed on the basis of a model Na-rich aluminosilicate system. A detailed time-series EMT-type zeolite crystallization study in the model hydrogel system was performed to elucidate the topological and temporal aspects of zeolite nucleation. A comprehensive set of analytical tools and methods was employed to analyze the gel evolution and complement the primary methods of transmission electron microscopy (TEM) and nuclear magnetic resonance (NMR) spectroscopy. TEM tomography reveals that the initial gel particles exhibit a core-shell structure. Zeolite nucleation is topologically limited to this shell structure and the kinetics of nucleation is controlled by the shell integrity. The induction period extends to the moment when the shell is consumed and the bulk solution can react with the core of the gel particles. These new findings, in particular the importance of the gel particle shell in zeolite nucleation, can be used to control the growth process and properties of zeolites formed in hydrogels.

Relation of the aged gels microstructure on the zeolite a particulate properties.

The microstructure of the starting hydrogel has extremely important role in the synthesis of the microporous materials. Due to the fact that very limited number of experimental methods (techniques) can be used for gel analysis, there are still a lot of missing informations about the processes on molecular level, which occur before and during the nuclei formation. In this paper, various methods were used in characterization of pretreated (aged) hydrogel before the process of its hydrothermal transformation to zeolite A. Results show the changes in chemical composition and in microstructure of the solid phase (FTIR, PALS, BET, DTG), indicating that the structure of the ordered phase (potential nuclei) within gel matrix (completely amorphous according to PXRD patterns) is rather of different structural units typical for FAU and SOD (or their mixture) than the final product (LTA) only!