Chabazite Synthesis and Its Exchange with Ti, Zn, Cu, Ag and Au for Efficient Photocatalytic Degradation of Methylene Blue Dye.

A chabazite-type zeolite was prepared by the hydrothermal method. Before ion exchange, the chabazite was activated with ammonium chloride (NH4Cl). The ion exchange process was carried out at a controlled temperature and constant stirring to obtain ion-exchanged chabazites of Ti4+ chabazite (TiCHA), Zn2+ chabazite (ZnCHA), Cu2+ chabazite (CuCHA), Ag+ chabazite (AgCHA) and Au3+ chabazite (AuCHA). Modified chabazite samples were characterized by X-ray diffraction (XRD), scanning electron microscope equipped with energy-dispersive spectroscopy (SEM-EDS), transmission electron microscopy (TEM), Fourier transform infrared (FTIR), N2 adsorption methods and UV-visible diffuse reflectance spectroscopy (DRS). XRD results revealed that the chabazite structure did not undergo any modification during the exchange treatments. The photocatalytic activity of chabazite samples was evaluated by the degradation of methylene blue (MB) in the presence of H2O2 under ultraviolet (UV) light illumination. The photodegradation results showed a higher degradation efficiency of modified chabazites, compared to the synthesized chabazite. CuCHA showed an efficiency of 98.92% in MB degradation, with a constant of k = 0.0266 min-1 following a first-order kinetic mechanism. Then, it was demonstrated that the modified chabazites could be used for the photodegradation of dyes.

Polymorph Selection in Zeolite Synthesis Occurs after Nucleation.

Zeolites are porous crystals with extensive polymorphism. The hydrothermal synthesis of zeolites is a multistage process involving amorphous precursors that evolve continuously in solubility and local order toward those of the crystal. These results pose several questions: Why does a first-order transition appear as a continuous transformation? At which stage is the polymorph selected? How large are the barriers and critical sizes for zeolite nucleation? Here we address these questions using nucleation theory with experimental data. We find that the nucleation barriers and critical zeolite nuclei are extremely small at temperatures of hydrothermal synthesis, resulting in spinodal-like crystallization that produces a mosaic of tiny zeolitic crystallites that compete to grow inside each glassy precursor nanoparticle. The subnanometer size of the critical nuclei reveals that the selection between zeolite polymorphs occurs after the nucleation stage, during the growth and coarsening of the crystals around the excluded volume of the structure-directing agents.

Rational design and fabrication of a novel acid-resistant UZM-5 zeolite membrane for pervaporation dehydration processes.

Novel thin UZM-5 zeolite membranes with pure UFI phase were successfully fabricated using a charge density mismatch-assisted tertiary growth approach. Taking full advantage of the suitable Si/Al ratio and pore size, the obtained novel zeolite membranes revealed an outstanding acid-resistant capacity and provided great potential for acetic acid pervaporation dehydration applications.

Sustainable Route for Synthesizing Aluminosilicate EU-1 Zeolite.

Developing sustainable routes for the synthesis of zeolites is still a vital and challenging task in zeolite scientific community. One of the typical examples is sustainable synthesis of aluminosilicate EU-1 zeolite, which is not very efficient and environmental-unfriendly under hydrothermal condition due to the use of a large amount of water as solvent. Herein, we report a sustainable synthesis route for aluminosilicate EU-1 zeolite without the use of solvent for the first time. The physicochemical properties of the obtained EU-1 zeolite are characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry-differential thermal analysis (TG-DTA), N2 sorption, inductively coupled plasma (ICP) analysis, and solid nuclear magnetic resonance (NMR), which show the product has high crystallinity, uniform morphology, large BET surface area, and four-coordinated aluminum species. Moreover, the impact of synthesis conditions is investigated in detail. The sustainable synthesis of aluminosilicate EU-1 zeolite under solvent-free.

Hierarchically Structured Zeolites: From Design to Application.

Hierarchical zeolites combine the intrinsic catalytic properties of microporous zeolites and the enhanced access and transport of the additional meso- and/or macroporous system. These materials are the most desirable catalysts and sorbents for industry and become a highly evolving field of important current interests. In addition to the enhanced mass transfer leading to high activity, selectivity, and cycle time, another essential merit of the hierarchical structure in zeolite materials is that it can significantly improve the utilization effectiveness of zeolite materials resulting in the minimum energy, time, and raw materials consumption. Substantial progress has been made in the synthesis, characterization, and application of hierarchical zeolites. Herein, we provide an overview of recent achievements in the field, highlighting the significant progress in the past decade on the development of novel and remarkable strategies to create an additional pore system in zeolites. The most innovative synthesis approaches are reviewed according to the principle, versatility, effectiveness, and degree of reality while establishing a firm link between the preparation route and the resultant hierarchical pore quality in zeolites. Zeolites with different hierarchically porous structures, i.e., micro-mesoporous structure, micro-macroporous structure, and micro-meso-macroporous structure, are then analyzed in detail with concrete examples to illustrate their benefits and their fabrications. The significantly improved performances in catalytic, environmental, and biological applications resulting from enhanced mass transport properties are discussed through a series of representative cases. In the concluding part, we envision the emergence of "material-properties-by-quantitative and real rational design" based on the "generalized Murray's Law" that enables the predictable and controlled productions of bioinspired hierarchically structured zeolites. This Review is expected to attract important interests from catalysis, separation, environment, advanced materials, and chemical engineering fields as well as biomedicine for artificial organ and drug delivery systems.

Advances in the Synthesis of Ferrierite Zeolite.

As one of the most important porous materials, zeolites with intricate micropores have been widely employed as catalysts for decades due to their large pore volume, high surface area, and good thermal and hydrothermal stabilities. Among them, ferrierite (FER) zeolite with a two-dimensional micropore structure is an excellent heterogeneous catalyst for isomerization, carbonylation, cracking, and so on. In the past years, considering the important industrial application of FER zeolite, great efforts have been made to improve the synthesis of FER zeolite and thus decrease the synthesis cost and enhance catalytic performance. In this review, we briefly summarize the advances in the synthesis of FER zeolite including the development of synthesis routes, the use of organic templates, organotemplate-free synthesis, the strategies of morphology control, and the creation of intra-crystalline mesopores. Furthermore, the synthesis of hetero-atomic FER zeolites such as Fe-FER and Ti-FER has been discussed.

Synthesis of FAU-Type Zeolite Membranes with Antimicrobial Activity.

In this study, a layer of a pure and dense phase of FAU-type zeolite was synthesized directly on the surface of α-Al2O3 plane macroporous support. Before hydrothermal synthesis, a step of cleaning of the support by an anionic detergent was performed, a roughness surface is created, allowing the anchoring of the zeolite nuclei and then their growth, favoring in this sense the formation of a homogeneous zeolite layer. The obtained membranes were fully characterized using X-ray diffraction analysis (XRD), nitrogen sorption, scanning electron microscopy (SEM), and mercury porosimetry. After 24 h of thermal treatment at 75 °C, a homogeneous zeolite layer composed of bipyramidal crystals of FAU-type zeolite is obtained with a thickness of about 2.5 µm. No obvious defects or cracks can be observed. It was found that the increase in heating temperature could lead to the appearance of an impurity phase, GIS-type zeolite. Then the ideal zeolite membrane was exchanged with Ag+ or Zn2+ cations to studies their antimicrobial properties. Zeolites membranes exchanged with Ag+ showed an agar-diffusive bactericidal activity against gram negative Escherichia coli (E. coli) bacteria. Zn2+ exchanged zeolite membrane presented a bacteriostatic activity that is less diffusive in agar. As expected, non-exchanged zeolite membrane (in its Na+ form) have no effect on bacterial activity. This process is particularly interesting for the synthesis of a good quality FAU-type zeolite membranes with antimicrobial properties.

Effect of Alkali-Free Synthesis and Post-Synthetic Treatment on Acid Sites in Beta Zeolites.

Beta zeolites with Si/Al around 14 were prepared using three new alkali-free synthesis methods based on the application of amorphous aluminosilicate precursor and calcined in ammonia or air. All samples exhibit structural and textural properties of standard beta zeolite. Comprehensive study by 27Al and 29Si MAS NMR, together with FTIR adsorption of d3-acetonitrile and pyridine were used to characterize the influence of both the synthesis and calcination procedure on the framework Al atoms and related Brønsted and Lewis acid sites. While calcination in ammonia preserves all framework Al atoms, calcination in air results in 15% release of framework Al, but without restrictions of the accessibility of the beta zeolite channel system for bulky pyridine molecules. Terminal (SiO)3AlOH groups present in the hydrated zeolites were suggested as a precursor of framework Al-Lewis sites. Surprisingly, the mild dealumination of the air-calcined zeolites result in an increase of the concentration of Brønsted acid sites and a decrease of the total concentration of Lewis sites with the formation of the extra-framework ones.

Combining Soft- and Hard-Templating Approaches in MWW-Type Zeolites.

A combination of hard-templating (HT) and soft-templating (ST) approaches was studied to obtain MWW-type materials with intermediate physicochemical properties. The HT methodology involved the introduction of carbon particles as hard templates during gel synthesis to obtain a layered zeolitic precursor (LZP) with particles possessing a microspherical morphology. The LZP obtained was treated with surfactants as soft templates to expand the layers of the LZP, followed by a pillaring procedure. The materials were characterized by X-ray diffraction, transmission and scanning electron microscopy, elemental analysis and N2 adsorption. The results demonstrate that the obtained material possesses intermediate properties from both approaches, with interparticle mesopores/macropores and pore sizes between 18 and 46 Å. However, the ST procedure causes a partial disruption of some microspheres, forming small crystallite aggregates, and results in a decrease in the number of interparticle mesopores/macropores previously formed by the HT method. All synthesized solids presented catalytic activity, which was evaluated by the cracking of low-density polyethylene (LDPE) as a probe reaction.

Mineralization of pH-Sensitive Doxorubicin Prodrug in ZIF-8 to Enable Targeted Delivery to Solid Tumors.

The zeolitic imidazolate framework (ZIF-8), composed of zinc ion and dimethylimidazole, is widely used in drug delivery because of the easy fabrication process and the good biosafety. However, ZIF-8 suffers from low affinity to nonelectric-rich drugs and does not have surface functional groups. Here, to deliver doxorubicin (DOX) with ZIF-8 to specific target sites, DOX was first modified with a pH-sensitive linker containing two carboxyl groups to form the inactive prodrug CAD and subsequently seeded inside ZIF-8 by a 5 min mineralization process. CAD has high affinity to ZIF-8 because of the carboxyl groups and can anchor to the ZIF-8 surface to enable the surface modification with folic acid for tumor targeting. Moreover, the DOX release is precisely controlled by three steps of acidic pH response, with the dissociation of the FA layer, the breakdown of the ZIF-8 structure, and the cleavage of the pH-sensitive linker in prodrug. This novel "prodrug-ZIF-8" strategy has opened a new horizon in drug delivery.

Ultrasound and Near-Infrared Light Dual-Triggered Upconversion Zeolite-Based Nanocomposite for Hyperthermia-Enhanced Multimodal Melanoma Therapy via a Precise Apoptotic Mechanism.

High reactive oxygen species (ROS) generation efficiency and induction of targeted cell apoptosis are recognized as key objectives to achieve a highly efficient strategy for cancer therapy with minimum side effects of inflammatory reactions. However, it is still a challenge to realize higher therapeutic efficiency with a cell apoptosis model. Herein, we present strong upconversion luminescent biosafe cores derived from Linde Type A (LTA) zeolites and modification with targeted/therapeutic drugs for multimodal therapy, in which sonodynamic therapy (SDT) combined with photodynamic therapy (PDT) increases therapeutic efficiency especially in deep sites of tumor via producing cytoplasmic ROS and mitochondrial superoxide and photothermal therapy (PTT) enhances PDT effects via higher fluorescence resonance energy transfer (FRET) efficacy attributed to an increased temperature. Furthermore, the transcriptomic analysis reveals that cellular internalization of the nanosystem can lead to tumor ablation via cell apoptosis. We expect that the multimodal therapy based on LTA zeolite drug nanocarriers could be applied in the cancer therapeutics in the near future.

A phosphorylcholine-based zwitterionic copolymer coated ZIF-8 nanodrug with a long circulation time and charged conversion for enhanced chemotherapy.

In recent years, zeolitic imidazolate framework-8 (ZIF-8) has become an attractive metal organic framework (MOF) material in drug delivery for cancer chemotherapy. However, as a drug delivery system, ZIF-8 still shows some disadvantages, such as short blood circulation time and poor tumor targeting, leading to reduced drug delivery efficiency and unsatisfactory treatment. Herein, we developed a phosphorylcholine-based zwitterionic copolymer coated ZIF-8 nanodrug (DOX@ZIF-8@P(MPC-co-C7A)), and the obtained nanodrug was prepared via a charge-conversional zwitterionic copolymer coating on DOX@ZIF-8 composites. In this system, DOX was encapsulated in the framework of ZIF-8, which could reduce the drug leakage in the bloodstream. The phosphorylcholine-based zwitterionic copolymer effectively extended the blood circulation time, resulting in enhanced tumor accumulation of the nanodrug. Once the nanodrug reached the tumor site, the surface charge of the system could rapidly convert to positive, resulting in an enhanced tumor cellular uptake. Finally, in the acidic environment inside intracellular organelles, DOX will be released rapidly for chemotherapy owing to the fast disintegration of ZIF-8 frameworks. Therefore, the obtained nanodrug could effectively inhibit the growth of A549-bearing tumors (93.2% tumor inhibition rate) with negligible side effects. Overall, this work significantly improved the drug delivery efficiency of ZIF-8, which may pave the way for the biomedical applications of ZIF-8 crystals in anti-tumor drug delivery.

Synthesis of Hierarchical Zeolites with Morphology Control: Plain and Hollow Spherical Beads of Silicalite-1 Nanosheets.

Binderless pure silica zeolites (zeosils) spheres and hollow spheres with a diameter of 20 µm composed of silicalite-1 nanosheets particles were prepared by pseudomorphic transformation of spherical silica beads using different temperatures (110, 130, and 150 °C) and treatment times (1-5 days) in order to adapt the local dissolution rate of silica to the crystallization rate of silicalite-1 nanosheets allowing to preserve the initial morphology of the silica beads. Fully crystalline beads of 20 µm were obtained at 110 °C for 5 days, whereas hollow spheres similar in size were synthesized at higher temperatures. The crystallization process seems to begin at the outer surface of the amorphous silica beads and spreads with the time in the interior of the beads leading to a dissolution of the inner amorphous part of the beads to create zeosil hollow spheres for the highest treatment temperatures (130 and 150 °C). The dissolution rate of the inner amorphous part of the beads increases by increasing the hydrothermal treatment temperature from 130 to 150 °C. The silicalite-1 beads synthesized at 110 °C for 5 days showed to be promising for rapid molecular decontamination by adsorbing n-hexane in larger amount than the silicalite-1 conventional big crystals in powder forms.

Conversion of the Propane-Butane Fraction into Arenes on MFI Zeolites Modified by Zinc Oxide and Activated by Low-Temperature Plasma.

The effect of modification of MFI zeolite 1-5 wt.% ZnO activated by plasma on acid and catalytic properties in the conversion of the propane-butane fraction into arenes was investigated. The high-silica zeolites with silicate module 45 were synthesized from alkaline alumina-silica gels in the presence of an 'X-oil' organic structure-forming additive. The modification of the zeolite with zinc was carried out by impregnating the zeolite granules in the H-form with an aqueous solution of Zn(NO3)2. The obtained zeolites were characterized by X-ray phase analysis and IR spectroscopy. It is shown that the synthesized zeolites belong to the high-silica MFI zeolites. The study of microporous zeolite-containing catalysts during the conversion of C3-C4 alkanes to aromatic hydrocarbons made it possible to establish that the highest yield of aromatic hydrocarbons is observed on zeolite catalysts modified with 1 and 3% ZnO and amount to 63.7 and 64.4% at 600 °C, respectively, which is 7.7-8.4% more than on the original zeolite. The preliminary activation of microporous zeolites modified with 1-5% ZnO and plasma leads to an increase in the yield of aromatic hydrocarbons from the propane-butane fraction; the maximum yield of arenes is observed in zeolite catalysts modified with 1 and 3% ZnO and activated by plasma, amounting to 64.9 and 65.5% at 600 °C, respectively, which is 8.9-9.5% more than on the initial zeolite. The activity of the zeolite catalysts modified by ZnO and activated by plasma show good agreement with their acid properties. Activation of the zeolites modified by 1 and 3% ZnO and plasma leads to an increase in the concentration of the weak acid sites of the catalyst to 707 and 764 mmol/g in comparison with plasma-inactivated 1 and 3% ZnO/ZKE-XM catalysts at 626 and 572 mmol/g, respectively.

Dispersive solid-phase extraction of buprenorphine from biological fluids using metal-organic frameworks and its determination by ultra-performance liquid chromatography.

In this work, various types of metal-organic frameworks were synthesized, and their affinities toward buprenorphine were evaluated using dispersive solid-phase extraction. The extracted buprenorphine was determined by ultra high performance liquid chromatography-ultraviolet detection system. The highest extraction recovery was observed by employing zeolitic imidazole framework-67. Then, a facile and fast extraction method was designed for the extraction and purification of the target drug. Optimization of the extraction method was carried out by the design of experiment approach. A linearity range of 1-1000 µg/L with the limit of detection of 0.15 µg/L and relative standard deviations (50 µg/L, n = 5) of 3.4% was obtained for standard sample analysis. Under optimized experimental and instrumental conditions, the relative recoveries were in the range of 95 to 111%. Eventually, zeolitic imidazole framework-67 was successfully employed for the extraction and determination of buprenorphine in the biological fluids with satisfactory results.

[Zeolite Produced from Fly Ash by Thermal Treatment in Alkaline Solution and Its Capability to Adsorb Cs(I) and Sr(II) in Aqueous Solution].

In this study, we evaluated the efficiency of fly ash (FA) recycling technology, produced from a coal-fired power plant, with the capability to adsorb cesium ion[Cs(I)] and strontium ion [Sr(II)] from aqueous phase. Zeolite was produced from FA by hydrothermal treatment in an alkaline solution. Zeolite 12, 24, and 48 have a Garronite structure. Moreover, the specific surface area of Zeolite was greater than that of FA. Zeolite 12 demonstrated the adsorption capability of Cs(I) and Sr(II) from aqueous phase. Adsorption isotherms data fitted both the Langmuir equation (correlation coefficient: >0.895) and the Freundlich equation (correlation coefficient: >0.881). In addition, the kinetic data fitted the pseudo-second-order model when compared to the pseudo-first-order model. Cs(I) and Sr(II) were selectively adsorbed by Zeolite 12 in complex solution system. Our findings indicate that Zeolite can be produced from FA by hydrothermal treatment in an alkaline solution and shows the capability to adsorb Cs(I) and Sr(II) from aqueous phase. Therefore, Zeolite can be useful adsorbent for purification in water environments.

Organic Structure-directing Agent-free Synthesis for *BEA-type Zeolite Membrane.

Membrane separation has drawn attention as a novel-energy saving separation process. Zeolite membranes have great potential for hydrocarbon separation in petroleum and petrochemical fields because of their high thermal, chemical, and mechanical strength. A *BEA-type zeolite is an interesting membrane material because of its large pore size and wide Si/Al range. This manuscript presents a protocol for *BEA membrane preparation by a secondary growth method that does not use an organic structure-directing agent (OSDA). The preparation protocol consists of four steps: pretreatment of support, seed preparation, dip-coating, and membrane crystallization. First, the *BEA seed crystal is prepared by conventional hydrothermal synthesis using OSDA. The synthesized seed crystal is loaded on the outer surface of a 3 cm long tubular α-Al2O3 support by a dip-coating method. The loaded seed layer is prepared with the secondary growth method using a hydrothermal treatment at 393 K for 7 days without using OSDA. A *BEA membrane having very few defects is successfully obtained. The seed preparation and dip-coating steps strongly affect the membrane quality.

Exploring the Scope of Macrocyclic "Shoe-last" Templates in the Mechanochemical Synthesis of RHO Topology Zeolitic Imidazolate Frameworks (ZIFs).

The macrocyclic cavitand MeMeCH2 is used as a template for the mechanochemical synthesis of 0.2MeMeCH2@RHO-Zn16(Cl2Im)32 (0.2MeMeCH2@ZIF-71) and RHO-ZnBIm2 (ZIF-11) zeolitic imidazolate frameworks (ZIFs). It is shown that MeMeCH2 significantly accelerates the mechanochemical synthesis, providing high porosity products (BET surface areas of 1140 m2/g and 869 m2/g, respectively). Templation of RHO-topology ZIF frameworks constructed of linkers larger than benzimidazole (HBIm) was unsuccessful. It is also shown that cavitands other than MeMeCH2-namely MeHCH2, MeiBuCH2, HPhCH2, MePhCH2, BrPhCH2, BrC5CH2-can serve as effective templates for the synthesis of x(cavitand)@RHO-ZnIm2 products. The limitations on cavitand size and shape are explored in terms of their effectiveness as templates.

Mitochondria-targeting zeolitic imidazole frameworks to overcome platinum-resistant ovarian cancer.

Epithelial ovarian cancer is still the leading cause of death in gynecology due to its resistance to platinum-based first-line chemotherapeutic drugs. The utilization of mitochondria-targeted drugs has become an important direction in anti-tumor drug research and development. In this work, cisplatin (DDP)-loaded ZIF-90 with mitochondrial-targeting was synthesized at room temperature with a high drug loading (11.7 %, calculated based on Pt content). The ZIF-90@DDP showed high cellular uptake and less toxicity in both non- and DDP-resistant ovarian cancer cells with effective pH- and ATP-responsive drug release. Both mitochondria-targeting and responsive drug release could increase the drug concentration in mitochondria of drug-resistant cancer cells to reverse such resistance. Conclusively, the mitochondria-targeting ZIF-90@DDP with high drug loading could trigger responsive drug release in mitochondria of epithelial ovarian cancer cells, inhibit DPP-resistant epithelial ovarian cancer cells, and reverse drug resistance.

Taguchi L16 optimization approach for simultaneous removal of Cs+ and Sr2+ ions by a novel scavenger.

This study targeted to investigate the efficacy of a novel nano 2-naphtyl amine6:6-azulene sodium methanesulfonate di sulphonic acid-impregnated zeolite scavenger for simultaneous elimination of Cs+ and Sr2+ ions from binary aqueous systems. Fractal analysis is introduced to assign a fractal dimension and other fractal characteristics necessary for the surface characterization in terms of fractal dimension (Ds) and pre-exponential coefficient (C), which, in theory, are independent tool and sole for each surface. It is found that the Ds value of nano 2-naphtyl amine6:6-azulene sodium methanesulfonate di sulphonic acid-impregnated zeolite of type Y (NAASMS-ZY) is higher than that of nano 2-naphtyl amine6:6-azulene sodium methanesulfonate di sulphonic acid-impregnated zeolite of type X (NAASMS-ZX) and nano 2-naphtyl amine6:6-azulene sodium methanesulfonate di sulphonic acid-impregnated zeolite of type A (NAASMS-ZA) which accordingly, suggests the irregularity of NAASMS-ZY surface and thus demonstrates a large surface area. To increase the scavenge efficacy, effecting parameters on scavenge process were investigated and optimized via the use of adopting Taguchi L16 design of experiments approach. It is found that, the initial metal ions concentration is the most powerful variable, and its value of contribution percentage is up to 33% and 31% for Cs+ and Sr2+, respectively. The kinetic curves and sorption isotherms at 298, 303 and 313 K were obtained, which well fitted to hyperbolic and Langmuir equations, respectively. Thermodynamic parameters demonstrated that the scavenge process was endothermic for both the concerned ions. Our results showed that the novel synthesized NAASMS-ZY is an effective nano-scavenger for cesium and strontium decontamination.