TEM investigation of formation mechanism of monocrystal-thick b-oriented pure silica zeolite MFI film

The first direct transmission electron microscopic (TEM) observation has been carried out on the continuous monocrystal-thick b-oriented pure silica zeolite MFI films produced by in situ crystallization. The self-supporting film samples for TEM study were fabricated by dissolving the steel substrate with acid. This TEM study is free of those artifacts that are typically associated with TEM sample preparations, and allows us to investigate the "true" structure and texture of a very large area of the film and at the same time to focus at will on each individual zeolite crystal in the film. Abundant TEM information including crystallographic orientation relationships among crystals in the film (both out-of-plane and in-plane), grain boundaries, and each crystal grain was obtained. This TEM investigation provides direct unambiguous new evidence to support the homogeneous nucleation mechanism, by which the films form through homogeneous nucleation and crystal growth in the bulk to form equal-sized disk-shape crystals, followed by self-assembly of these crystals onto the substrate to produce a two-dimensional close-packed structure. The last stage of the film formation involves simultaneous space-limited growth and rotation of the individual crystals to realize the in-plane crystallographic control within the film.     

Evidences for zeolite nucleation at the solid-liquid interface of gel cavities

The entire sequence of crystallization events, starting with formation of the initial organic-cation-free gel, proceeding through the zeolite nucleation stage, and finishing with complete transformation into LTA-type zeolite crystals, has been monitored by means of high-resolution transmission electron microscopy. Formation and development of voids, containing highly hydrated material transformed later into negative crystals, has been discovered in the solid part of the system. The evolution of these areas has been found to be an integral and noteworthy part of the chemical transformation of the gel that preceded the nucleation in the system. These void structures and, in particular, their solid-liquid interfaces have been identified as the specific locations where the formation of protozeolite nuclei took place. Further development of the system followed the classical for zeolite-yielding systems of crystallization that could be described by the autocatalytic model.     

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.     

The Mosaic Structure of Zeolite Crystals

Zeolites are widely used in many commercial processes, mostly as catalysts or adsorbents. Understanding their intimate structure at the nanoscale is the key to control their properties and design the best materials for their ever increasing uses. Herein, we report a new and controllable fluoride treatment for the non‐discriminate extraction of zeolite framework cations. This sheds new light on the sub‐structure of commercially relevant zeolite crystals: they are segmented along defect zones exposing numerous nanometer‐sized crystalline domains, separated by low‐angle boundaries, in what were apparent single‐crystals. The concentration, morphology, and distribution of such domains analyzed by electron tomography indicate that this is a common phenomenon in zeolites, independent of their structure and chemical composition. This is a milestone to better understand their growth mechanism and rationally design superior catalysts and adsorbents.     

Factors that control zeolite L crystal size

Time-series hydrothermal syntheses from two organic-cation-free gels with different compositions were employed to study the factors that control the final size of zeolite L crystals. The first gel had a starting K/Al ratio of 10, whereas in the second one it was three times lower. The relatively simple chemical composition of the starting gels and the combination of complementary characterization methods allowed us to track down the different stages of transformation of the initial amorphous gels into zeolite crystals and the factors that control the nucleation and growth processes. The role of the starting mixture components in the formation of the primary amorphous particles was explored. It was found that the profoundly different reaction kinetics in the two systems are caused by the difference in diffusion rates, which in turn are controlled by the extent of the polymerization reactions at room temperature during mixing of the starting components prior to hydrothermal treatment. As a consequence, nucleation is fast and ubiquitous in the first system with higher water content and K/Al ratio, whereas it is slow and sporadic in the second system with lower water content and K/Al ratio. Ultimately, these differences in the kinetics lead to the formation of two distinctly different patterns of crystal-size distribution, with a large number of small nanocrystals in the first sample and fewer large crystals in the second sample. The new findings put zeolite crystal growth on a rational basis that would enable the control of zeolite crystal size in similar organic-template-free systems.     

Dissolution Behavior and Varied Mesoporosity of Zeolites by NH4F Etching

The mesopores formation in zeolite crystals has long been considered to occur through the stochastic hydrolysis and removal of framework atoms. Here, we investigate the NH₄F etching of representative small, medium, and large pore zeolites and show that the zeolite dissolution behavior, therefore the mesopore formation probability, is dominated by zeolite architecture at both nano- and sub-nano scales. At the nano-scale, the hidden mosaics of zeolite structure predetermine the spatio-temporal dissolution of the framework, hence the size, shape, location, and orientation of the mesopores. At the sub-nano scale, the intrinsic micropore size and connectivity jointly determine the diffusivity of reactant and dissolved products. As a result, the dissolution propensity varies from removing small framework fragments to consuming nanodomains and up to full digestion of the outmost part of zeolite crystals. The new knowledge will lead to new understanding of zeolite dissolution behavior and new adapted strategies for tailoring hierarchical zeolites.     

Products of Quasi-Involutions in Unitary Groups

Given a regular ^–-hermitian form on an n-dimensional vector space V over a commutative field K of characteristic 2 ( ). Call an element of the unitary group a quasi-involution if is a product of commuting quasi-symmetries (a quasi-symmetry is a unitary transformation with a regular (n–1)-dimensional fixed space). In the special case of an orthogonal group every quasi-involution is an involution. Result: every unitary element is a product of five quasi-involutions. If K is algebraically closed then three quasi-involutions suffice.     

Downstream targets of methyl CpG binding protein 2 and their abnormal expression in the frontal cortex of the human Rett syndrome brain

Background  

The Rett Syndrome (RTT) brain displays regional histopathology and volumetric reduction, with frontal cortex showing such abnormalities, whereas the occipital cortex is relatively less affected.