Preparation of MAZ-Type Zeolite with High Silica.

The Si/Al molar ratio of MAZ aluminosilicate zeolite prepared by the direct hydrothermal method is generally less than five, thus giving rise to poor thermal and hydrothermal stability for this low-silica zeolite. With the purpose of enhancing the Si/Al molar ratio of MAZ zeolite, post-synthesized methods including acetic acid treatment and steaming treatment, as well as interzeolite transformation from FAU zeolite, were employed to prepare MAZ zeolite with high silica. It was found that steaming treatment was more effective in increasing the Si/Al molar ratio in comparison with acetic acid treatment, affording a maximum Si/Al molar ratio of 16.9 along with a preserved crystallinity of approximately 75%. Additionally, high-silica MAZ zeolite with a Si/Al molar ratio of up to 7.3 was also capable of being directly hydrothermally synthesized using interzeolite transformation from FAU zeolite.

Interzeolite Transformation from FAU-to-EDI Type of Zeolite.

This study reports for the first time the transformation of the pre-made FAU type of zeolite to the EDI type of zeolite. The concentration of the KOH solution controls this interzeolite transformation, which unusually occurs at both room temperature and under hydrothermal conditions. The transformation involves the amorphization and partial dissolution of the parent FAU phase, followed by the crystallization of EDI zeolite. At room temperature, the transformation (11-35 days) provides access to well-shaped nano-sized crystals and hollow hierarchical particles while the hydrothermal synthesis results in faster crystallization (6-27 h). These findings reveal an example of an interzeolite transformation to a potassium zeolite that lacks common composite building units with the parent zeolite phase. Finally, this work also demonstrates the first room-temperature synthesis of EDI zeolite from a gel precursor.

Accelerated Synthesis of Nanolayered MWW Zeolite by Interzeolite Transformation.

Hierarchical zeolites can offer substantial benefits over bulk zeolites in catalysis. A drawback towards practical implementation is their lengthy synthesis, often requiring complex organic templates. This work describes an accelerated synthesis of nanolayered MWW zeolite based on the combination of interzeolite transformation (IZT) with a dual-templating strategy. FAU zeolite, hexamethyleneimine (HMI), and cetyltrimethylammonium bromide (CTAB) were respectively employed as Al source and primary zeolite, structure directing agent, and exfoliating agent. This approach allowed to reduce the synthesis of nanolayered MWW to 48 h, which is a considerable advance over the state of the art. Tracking structural, textural, morphological, and chemical properties during crystallization showed that 4-membered-ring (4MR) units derived from the FAU precursor are involved in the faster formation of MWW in comparison to a synthesis procedure from amorphous precursor. CTAB restricts the growth of the zeolite in the c-direction, resulting in nanolayered MWW. Moreover, we show that this approach can speed up the synthesis of nanolayered FER. The merits of nanolayered MWW zeolites are demonstrated in terms of improved catalytic performance in the Diels-Alder cycloaddition of 2,5-dimethylfuran and ethylene to p-xylene compared to bulk reference MWW sample.

Ultrasonic-pretreated hydrothermal synthesis of less dense zeolite CHA from the transformation of zeolite T.

Because of containing the same double 6-ring (D6R) building unit, the pure zeolite CHA with lower framework density (FDSi = 15.1 T/1000 Å3) has been transformed from zeolite T with higher framework density (FDSi = 16.1 T/1000 Å3) through ultrasonic-pretreated hydrothermal synthesis in MOH (KOH and NaOH) solution without adding organic template or seed crystals. Ultrasonic pretreatment facilitates the transformation rate and generates high-quality zeolite CHA. The ultrasound condition should be precisely controlled because that CHA phase is metastable, which is inclined to transform to other more stable phase. The ultrasonic conditions at 313 K and 333 K have been investigated in detail. In KOH solution, the ultrasonic treatment at 313 K can effectively restrain the generation of MER phase, however, it is hard to avoid the existence of MER phase when ultrasound temperature is 333 K. In NaOH solution, the samples with ultrasonic treatment of 313 K show the small particles size of about 1 µm, and the GIS framework topology starts to grow with the ultrasonic treatment of 333 K. The products prepared with the appropriate ultrasonic pretreatment represents smaller particles size, larger mesopore volume and higher CO2 adsorption capacity than the sample without the ultrasonic pretreatment. The structural evolution of interzeolite transformation has been explored by XRD, FT-IR and SEM observations. With the assistance of ultrasound, the parent zeolite T can quickly decompose into intermediate phase and then regenerate into CHA phase.

Nanocrystalline BEA-CNT Composites with High Metal Dispersion Obtained via Inter-Zeolite Transformation for Antibacterial Application.

The rational design of interface materials containing carbon nanotubes (CNTs) and zeolites (zeolite-CNTs) is a promising perspective in chemical and biochemical communities because they exhibit several outstanding properties such as tunable hydrophobicity-hydrophilicity at interfaces. In this contribution, we report the fabrication of Ag-incorporated nanocrystalline BEA-carbon nanotube (CNT) composites via the one-pot inter-zeolite transformation of the micron-sized FAU-CNT composite in the presence of a Ag precursor. By varying the crystallization time, the inter-zeolite transformation mechanism was explored. Indeed, this process involves an amorphous intermediate of aluminosilicate species with a significant change of the crystal morphology in the presence of CNTs in the synthesis gel. Interestingly, the redispersion of metal particles was observed after the inter-zeolite transformation process, resulting in the high dispersion of metal nanoparticles over BEA nanocrystals. Notably, it was revealed that the Ag sites were also stabilized in the presence of CNT interfaces, leading to the availability of highly active Ag+ ions. To illustrate the beneficial aspect of designer materials, the synthesized Ag-incorporated BEA-CNT composites exhibited high antibacterial activity againstEscherichia coli due to the synergistic effect of the active Ag+ species and appropriate hydrophobic and hydrophilic properties of the hybrid material interfaces. This first example opens up perspectives of the rational design of zeolite-CNT interfaces with high metal dispersion via the inter-zeolite transformation approach for biomedical applications.

Understanding the Anion-Templated, OSDA-Free, Interzeolite Conversion Synthesis of High Silica Zeolite ZK-5.

High silica zeolite ZK-5 (framework Si/Al=4.8) has been prepared by interzeolite conversion from ultrastable zeolite Y via a co-templating route using alkali metal cations and nitrate anions but without organic structure directing agents. The mechanism, which involves zeolite framework - alkali metal cation - nitrate anion ordering, has been established by a combination of chemical and thermal analyses, Raman spectroscopy, computational modelling, and X-ray powder diffraction. Ammonium exchange gives ZK-5 with occluded ammonium nitrate and subsequent heating gives microporous zeolite ZK-5.

Interzeolite Conversion-Synthesized Sub-1 µm NaA Zeolite Membrane for C2H2/C2H4 Selective Separation.

Zeolite membranes with reduced thickness and high continuity are of paramount importance for accelerating selective gas separation for resemblant molecules, and the synthesis of such membranes remains a grand challenge. Herein, we developed an interzeolite conversion synthesis approach to grow NaA zeolite membranes on NaX. The conversion of NaX into NaA proceeded via mild hydrothermal treatment of a dilute synthesis solution, preferentially forming a continuous polycrystalline NaA layer on the surface of NaX, which was precrystallized on a porous alumina support. The thickness of the NaA zeolite membrane was successfully controlled to the submicron scale (500 nm). The synthesized NaA membrane functioned as a selective separator for C2H2 and C2H4 gases. Taking the traditionally in situ grown membrane as a reference, the interzeolite-derived membrane exhibited a 3.5-fold separation factor and ∼4.0 times C2H2 permeance. This approach provides an alternative synthesis option for zeolite membranes with advanced properties, and high efficiency in terms of superior gas selectivity and permeability is promising in precise gas separation.

Immobilization of Radioiodine via an Interzeolite Transformation to Iodosodalite.

We described a technology for immobilizing radioiodine in the sod-cages by the interzeolite transformation of iodine-containing LTA (zeolite A) and FAU (zeolites X and Y) into a sodalite (SOD) structure. The immobilization of iodine in the sod-cage was confirmed using diverse characterization methods including powder XRD, elemental analysis, SEM-EDS, 127I MAS NMR, and I 3d XPS. Although both zeolites A (Na-A) and X (Na-X) were well converted into SOD structure in the presence of NaI and AgI, the iodide anions were fixed in the sod-cages only when NaI was used. The ability to adsorb methyl iodide (CH3I) was evaluated for zeolites A and X in which Na+ and/or Ag+ ions were exchanged, and Ag+ and zeolite X showed better adsorption properties than Na+ and zeolite A, respectively. However, when both CH3I adsorption ability and the successive immobilization of iodine by interzeolite transformation were considered, Na-X was determined to be the best candidate of adsorbent among the studied zeolites. More than 98% of the iodine was successfully immobilized in the sod-cage in the SOD structure by the interconversion of Na-X following CH3I adsorption, although the Na-X zeolite exhibited half the CH3I adsorption capacity of Ag-X.

Recent advances in zeolite-encapsulated metal catalysts: A suitable catalyst design for catalytic biomass conversion.

Metal clusters and nanoparticles, which have been used to tune the acidity of zeolite support, are beneficial for promoting the catalytic performance of various reaction processes, including biomass conversion. However, catalytic instabilities resulting from metal coalescence, sintering and leaching are major problems that need to be resolved. Therefore, metal encapsulation within the zeolite structure has been proposed as a feasible solution for this issue, particularly for biomass conversions that require high temperatures. In this current review, recent developments in metal confinement techniques are described along with experimental examples of biomass upgrading reactions. The present and future perspectives of zeolite-encapsulated metal catalysts in biomass conversions are also given.

Building Zeolites from Precrystallized Units: Nanoscale Architecture.

Since the early reports by Barrer in the 1940s on converting natural minerals into synthetic zeolites, the use of precrystallized zeolites as crucial inorganic directing agents to synthesize other crystalline zeolites with improved physicochemical properties has become a very important research field, allowing the design, particularly in recent years, of new industrial catalysts. This Review highlights how the presence of some crystalline fragments in the synthesis media, such as small secondary building units (SBUs) or layered substructures, not only favors the crystallization of other zeolites with similar SBUs or layers, but also permits control over important parameters affecting their catalytic activity (chemical composition, crystal size, or porosity, etc.). Recent advances in the preparation of 3D and 2D zeolites through seeding and zeolite-to-zeolite transformation processes will be discussed extensively in this Review, including their preparation in the presence or absence of organic structure-directing agents (OSDAs). The aim is to introduce general guidelines for more efficient approaches for target zeolites.

Hydrophobic Nanosized All-Silica Beta Zeolite: Efficient Synthesis and Adsorption Application.

All-silica beta zeolite, synthesized by conventional hydroxide route, usually possesses small crystal size of a few hundred nanometers but poor hydrophobicity, whereas the fluoride-mediated one exhibits to be highly hydrophobic but microsized. To obtain nanosized all-silica beta zeolite with excellent hydrophobicity, an innovative and efficient hydrothermal route via interzeolite transformation for synthesizing all-silica beta zeolite is proposed in present study. With the assistance of beta seeds and tetraethylammonium hydroxide as the structure-directing agent, siliceous beta zeolite is well-crystallized at a high solid yield via dissolution-recrystallization of all-silica ITQ-1 crystals at an extremely low water content (H2O/SiO2 molar ratio of 1). The obtained all-silica beta crystals are composed of 30-70 nm nanoparticles and highly hydrophobic just next to siliceous beta-F zeolite synthesized by environmentally unfriendly fluoride route, which is derived from relatively small amounts of internal defect sites. Thus, this beta zeolite is superior to other pure silica beta zeolites in the adsorption of large-sized volatile organic compounds (VOCs), which is mainly attributed to its high total pore volume and specific surface area as well as excellent hydrophobicity.