Modulation of Nucleation and Growth Kinetics of Perovskite Nanocrystals Enables Efficient and Spectrally Stable Pure-Red Light-Emitting Diodes.

Perovskite light-emitting diodes (PeLEDs) based on CsPb(Br/I)3 nanocrystals (NCs) usually suffer from severe spectral instability under operating voltage due to the poor-quality PeNCs. Herein, zeolite was utilized to prepare high-quality CsPb(Br/I)3 NCs via promoting the homogeneous nucleation and growth and suppressing the Ostwald ripening of PeNCs. In addition, the decomposed zeolite interacted strongly with PeNCs through Pb-O bonds and hydrogen bonds, which inhibited the formation of defects and suppressed halide ion migration, leading to an improved photoluminescence quantum yield (PLQY) and enhanced stability of PeNCs. Moreover, the strong binding affinity of decomposed zeolite to PeNCs contributed to the formation of homogeneous perovskite films with high PLQY. As a result, pure-red PeLEDs with Commission International de I'Eclairage (CIE) coordinates of (0.705, 0.291) were fabricated, approaching the Rec. 2020 red primary color. The devices achieved a peak external quantum efficiency of 23.0% and outstanding spectral stability.

Deep Cracking of Bulky Hydrocarbons into Light Products via Tandem Catalysis over Uniform Interconnected ZSM-5@AlSBA-15 Composites.

Deep cracking of bulky hydrocarbons on zeolite-containing catalysts into light products with high activity, desired selectivity, and long-term stability is demanded but challenging. Herein, the efficient deep cracking of 1,3,5-triisopropylbenzene (TIPB) on intimate ZSM-5@AlSBA-15 composites via tandem catalysis is demonstrated. The rapid aerosol-confined assembly enables the synthesis of the composites composed of a continuous AlSBA-15 matrix decorated with isolated ZSM-5 nanoparticles. The two components at various ZSM-5/AlSBA-15 mass ratios are uniformly mixed with chemically bonded pore walls, interconnected pores, and eliminated external surfaces of nanosized ZSM-5. The typical composite with a ZSM-5/AlSBA-15 mass ratio of 0.25 shows superior performance in TIPB cracking with outstanding activity (≈100% conversion) and deep cracking selectivity (mass of propylene + benzene > 60%) maintained for a long time (> 6 h) under a high TIPB flux (2 mL h-1), far better (several to tens of times higher) than the single-component and physically mixed catalysts and superior to literature results. The high performance is attributed to the cooperative tandem catalytic process, that is, selective and timely pre-cracking of TIPB to isopropylbenzene (IPB) in AlSBA-15 and subsequently timely diffusion and deep cracking of IPB in nanosized ZSM-5.

Molecular Accessibility and Diffusion of Resorufin in Zeolite Crystals.

We have used confocal laser scanning microscopy on the small, fluorescent resorufin dye molecule to visualize molecular accessibility and diffusion in the hierarchical, anisotropic pore structure of large (~10 µm-sized) zeolite-ß crystals. The resorufin dye is widely used in life and materials science, but only in its deprotonated form because the protonated molecule is barely fluorescent in aqueous solution. In this work, we show that protonated resorufin is in fact strongly fluorescent when confined within zeolite micropores, thus enabling fluorescence microimaging experiments. We find that J-aggregation guest-guest interactions lead to a decrease in the measured fluorescence intensity that can be prevented by using non-fluorescent spacer molecules. We characterized the pore space by introducing resorufin from the outside solution and following its diffusion into zeolite-ß crystals. The eventual homogeneous distribution of resorufin molecules throughout the zeolite indicates a fully accessible pore network. This enables the quantification of the diffusion coefficient in the straight pores of zeolite-ß without the need for complex analysis, and we found a value of 3×10-15  m2  s-1 . Furthermore, we saw that diffusion through the straight pores of zeolite-ß is impeded when crossing the boundaries between zeolite subunits.

Double Four Ring Units-Containing Zeolites: Synthesis, Structural Modification and Catalytic Applications.

In zeolite frameworks, double four-ring (d4r) configurations are among the most frequent composite building units. The composition variations in d4r units greatly influence the energy and structural modifiability of the zeolitic framework. The introduction of germanium, with a larger ionic radius than silicon or aluminum, not only reduces the energy constraints of d4r in the nucleation and crystal growth of zeolites, but also opens a new window for constructing novel crystalline structures, especially with large or extra-large pores and channels. Ge-enriched d4r units endow germanosilicates with structure diversity readily for post treatments. Promising catalytic materials have been gradually developed and increasingly studied by direct synthesis or post-synthetic isomorphous substitution for Ge. This review focuses on the recent progress in the synthesis, modification, and catalytic application of d4r-containing zeolites, including germanosilicates, aluminosilicates, and silicates.

Acidity of Isomorphic Substituted Zeolites with B, Al and Ga Revisited.

Isomorphic substitution of zeolites with B, Al and Ga is a widely used approach in catalysis. The experimentally reported trend of their acidities decreases in the order: Al>Ga>B. However, a consistent explanation is still lacking in the literature. To bring more understanding of this trend, density functional theory computations were conducted on several model systems. First, the acidity of small clusters with two (2T) and five (5T) tetrahedral sites was analyzed. These systems were then projected onto three large void structures: H-[A]-BEA (52T), H-[A]-FAU (84T) and H-[A]-MOR (112T) with A=B, Al, Ga. Our electron density and Interacting Quantum Atom analyses show that the acidity of Al zeolites originates from the much stronger O-Al bond, which is dominated by the electrostatic attraction. The bridging hydroxyl therefore donates more charge density to the metal, the proton becomes more positive and consequently more acidic. Ga zeolites are more acidic than B zeolites due to the greater covalent nature on the O-Ga bond. The resulting acidity, as seen by ammonia, depends on both the acidic oxygen and the charge distribution of the surrounding oxygens exerted by the substituents.

IrSn Bimetallic Clusters Confined in MFI Zeolites for CO Selective Catalytic Reduction of NOx in the Presence of Excess O2.

We developed a simple strategy for preparing IrSn bimetallic clusters encapsulated in pure silicon zeolites via a one-pot hydrothermal synthesis by using diethylamine as a stabilizing agent. A series of investigations verified that metal species have been confined successfully in the inner of MFI zeolites. IrSn bimetallic cluster catalysts were efficient for the CO selective catalytic reduction of NOx in the presence of excess O2. Furthermore, the 13CO temperature-programmed surface reaction results demonstrated that NO2 and N2O could form when most of the CO was transformed into CO2 and that Sn modification could passivate CO oxidation on the IrSn bimetallic clusters, leading to more reductants that could be used for NOx reduction at high temperatures. Furthermore, SO2 can also influence the NOx conversion by inhibiting the oxidation of CO. This study provides a new strategy for preparing efficient environmental catalysts with a high dispersion of metal species.

Production of light olefins and monocyclic aromatic hydrocarbons from the pyrolysis of waste plastic straws over high-silica zeolite-based catalysts.

Owing to the ever-increasing generation of plastic waste, the need to develop environmentally friendly disposal methods has increased. This study explored the potential of waste plastic straw to generate valuable light olefins and monocyclic aromatic hydrocarbons (MAHs) via catalytic pyrolysis using high-silica zeolite-based catalysts. HZSM-5 (SiO2/Al2O3:200) exhibited superior performance, yielding more light olefins (49.8 wt%) and a higher MAH content than Hbeta (300). This was attributed to the increased acidity and proper shape selectivity. HZSM-5 displayed better coking resistance (0.7 wt%) than Hbeta (4.4 wt%) by impeding secondary reactions, limiting coke precursor formation. The use of HZSM-5 (80) resulted in higher MAHs and lower light olefins than HZSM-5 (200) because of its higher acidity. Incorporation of Co into HZSM-5 (200) marginally lowered light olefin yield (to 44.0 wt%) while notably enhancing MAH production and boosting propene selectivity within the olefin composition. These observations are attributed to the well-balanced coexistence of Lewis and Brønsted acid sites, which stimulated the carbonium ion mechanism and induced H-transfer, cyclization, Diels-alder, and dehydrogenation reactions. The catalytic pyrolysis of plastic straw over high-silica and metal-loaded HZSM-5 catalysts has been suggested as an efficient and sustainable method for transforming plastic waste materials into valuable light olefins and MAHs.

Cooperative formation of porous silica and peptides on the prebiotic Earth.

Modern technology has perfected the synthesis of catalysts such as zeolites and mesoporous silicas using organic structure directing agents (SDA) and their industrial use to catalyze a large variety of organic reactions within their pores. We suggest that early in prebiotic evolution, synergistic interplay arose between organic species in aqueous solution and silica formed from rocks by dynamic dissolution-recrystallization. The natural organics, for example, amino acids, small peptides, and fatty acids, acted as SDA for assembly of functional porous silica structures that induced further polymerization of amino acids and peptides, as well as other organic reactions. Positive feedback between synthesis and catalysis in the silica-organic system may have accelerated the early stages of abiotic evolution by increasing the formation of polymerized species.

Effect of zeolites on the reduction of the ecotoxicity of carbamazepine in the environment.

In this study, the impact of calcination of zeolites on the ecotoxicity of carbamazepine solutions in two matrices, water and synthetic sewage, was assessed. Two types of zeolites were tested: natural zeolite, in the form of a zeolite rock consisting mainly of clinoptilolite, and a synthetic zeolite type 5 A. Additionally, zeolites were calcined at a temperature of 200 °C. The kinetics of carbamazepine adsorption in aqueous solutions and in synthetic sewage matrix was determined. Higher adsorption capacity was obtained for carbamazepine aqueous solutions as well as zeolites after the calcination process. Considering type of zeolite, the highest and fastest uptake of carbamazepine was observed for natural zeolite after calcination. In the case of ecotoxicity, carbamazepine solutions before adsorption was the most toxic towards Raphidocelis subcapitata, next Aliivibrio fischeri and Daphnia magna, regardless to the matrix type. The differentiation in toxicity regarding the type of matrix was observed, in the case of algae and bacteria, higher toxicity was demonstrated by carbamazepine solutions in the water matrix, while in the case of crustaceans-the sewage matrix. After the adsorption process, the toxicity of carbamazepine solutions on zeolites decreased by 34.5-60.9 % for R. subcapitata, 33-39 % for A. fischeri and 55-60 % for D. magna, thus confirming the effectiveness of the proposed method of carbamazepine immobilization.

Soil quality increases with long-term chabazite-zeolite tuff amendments in arable and perennial cropping systems.

The application of natural zeolites to improve soil quality and functioning has become highly popular, but we still miss information about the long-term effects on the soil due to its application. This study assesses the soil quality index (SQI) of three distinct agricultural soil systems 6-10 years after a single application of natural chabazite zeolite as a soil amendment. These soils exhibit different management practices: intensive arable (cereals), intensive perennial (pear) and organic perennial (olive). In the arable system, a zeolite application dosage of 5, 10 and 15 kg m-2 was tested and compared to unamended soil. In the two perennial systems, an application of 5 kg m-2 was tested against untreated reference sols. A set of 25 soil physical, chemical and biological parameters linked to soil health and quality were analysed at each experimental site. The dataset was investigated through Principal Component Analysis (PCA) to calculate the soil quality index (SQI) using linear scoring. In the arable-cereal field, the SQI doubled (0.3 to ca. 0.6 for all amendments) in chabazite-amended plots; a dose effect was not recognizable. In both perennial fields, the SQI was significantly higher in the chabazite-amended plots (5 kg m-2) with similar increases as compared to the arable-cereal field. At each site, the indicators selected by the PCA were different, indicating that chabazite addition impacted soil quality differently in each cropping system. Overall, the results highlighted a significant increase in soil quality with chabazite amendment, which confirms its potential for increasing soil health in the long-term.

Zeolite Properties, Methods of Synthesis, and Selected Applications.

Zeolites, a group of minerals with unique properties, have been known for more than 250 years. However, it was the development of methods for hydrothermal synthesis of zeolites and their large-scale industrial applications (oil processing, agriculture, production of detergents and building materials, water treatment processes, etc.) that made them one of the most important materials of the 20th century, with great practical and research significance. The orderly, homogeneous crystalline and porous structure of zeolites, their susceptibility to various modifications, and their useful physicochemical properties contribute to the continuous expansion of their practical applications in both large-volume processes (ion exchange, adsorption, separation of mixture components, catalysis) and specialized ones (sensors). The following review of the knowledge available in the literature on zeolites aims to present the most important information on the properties, synthesis methods, and selected applications of this group of aluminosilicates. Special attention is given to the use of zeolites in agriculture and environmental protection.

Comparative Evaluation of Boron Sorption Dynamics on Zeolites in Irrigation Waters: An Isothermal Modeling Approach.

Efficient boron removal from irrigation waters is crucial for sustainable agriculture, as elevated levels of boron can be toxic to many plants, limiting growth and crop productivity. In this context, the present study investigated the sorption equilibrium of boron using zeolites in two types of aqueous matrices: a synthetic solution containing only boron and natural irrigation waters. Through the application of various isothermal sorption models (Langmuir, Freundlich, Sips, Toth, Jovanovic, Temkin, Dubinin-Radushkevich, and Redlich-Peterson), the efficacy of zeolite for boron removal under controlled and real conditions was evaluated. The results indicated a notable difference in sorption behavior between the two matrices, reflecting the complexity and heterogeneity of interactions in the boron-zeolite system. In the synthetic solution, the Freundlich model provided the best fit (R2 = 0.9917), suggesting heterogeneous and multilayer sorption, while the Sips model showed high efficacy in describing the sorption in both matrices, evidencing its capability to capture the complex nature of the interaction between boron and zeolite under different environmental conditions. However, in natural irrigation waters, the Jovanovic model demonstrated the most accurate fit (R2 = 0.999), highlighting the importance of physical interactions in boron sorption. These findings underscore the significant influence of the water matrix on the efficacy of zeolite as a boron removal agent, emphasizing the need to consider the specific composition of irrigation water in the design of removal treatments. Additionally, the results stress the importance of selecting the appropriate isothermal model to predict boron sorption behavior, which is crucial for developing effective and sustainable treatment strategies. This study provides a basis for optimizing boron removal in various agricultural and industrial applications, contributing to the design of more efficient and specific water treatment processes.

Zirconium Phosphate-Pillared Zeolite MCM-36 for Green Production of γ-Valerolactone from Levulinic Acid via Catalytic Transfer Hydrogenation.

γ-valerolactone (GVL), derived from biomass, is a crucial platform compound for biofuel synthesis and various industrial applications. Current methods for synthesizing GVL involve expensive catalysts and high-pressure hydrogen, prompting the search for greener alternatives. This study focuses on a novel zirconium phosphate (ZrP)-pillared zeolite MCM-36 derivative catalyst for converting levulinic acid (LA) to GVL using alcohol as a hydrogen source. The incorporation of ZrP significantly contributes to mesoporosity and greatly enhances the acidity of the catalysts. Additionally, we employed 31P MAS NMR to comprehensively investigate the influence of phosphorus species on both the acidity and the catalytic conversion of LA to GVL. By adjusting the Zr-to-P ratios, we synthesized catalysts with enhanced acidity, achieving high conversion of LA and selectivity for GVL. The catalyst exhibited high recyclability, showing only minor deactivation over the course of five cycles. Furthermore, the catalyst was successfully applied to the one-pot conversion of furfural to GVL, showcasing its versatility in biomass conversion. This study highlights the potential of the MCM-ZrP1 catalyst for sustainable biomass conversion and offers insights for future research in renewable energy technologies.

Catalyst Accessibility and Acidity in the Hydrocracking of HDPE: A Comparative Study of H-USY, H-ZSM-5, and MCM-41 Modified with Ga and Al.

Plastic pollution is a critical environmental issue due to the widespread use of plastic materials and their long degradation time. Hydrocracking (HDC) offers a promising solution to manage plastic waste by converting it into valuable products, namely chemicals or fuels. This work aims to investigates the effect of catalyst accessibility and acidity on the HDC reaction of high density polyethylene (HDPE). Therefore, a variety of materials with significant differences in both textural and acidic properties were tested as catalysts. These include H-USY and H-ZSM.5 zeolites with various Si/Al molar ratios (H-USY: Si/Al = 2.9, 15, 30 and 40; H-ZSM-5: Si/Al = 11.5, 40, 500) and mesostructured MCM-41 materials modified with Ga and Al, also with different Si/metal ratios (Si/Al = 16 and 30; Si/Ga = 63 and 82). Thermogravimetric analysis under hydrogen atmosphere was used as a preliminary screening tool to evaluate the potential of the various catalysts for this application in terms of energy requirements. In addition, batch autoclave reactor experiments (T = 300 °C, PH2 = 20 bar, t = 60 min) were conducted to obtain further information on conversion, product yields and product distribution for the most promising systems. The results show that the catalytic performance in HDPE hydrocracking is determined by a balance between the acidity of the catalyst and its structural accessibility. Accordingly, for catalyst series where the structural and textural properties do not vary with the Si/Al ratio, there is a clear correlation of the HDPE degradation temperature and of the HDPE conversion with the Si/metal ratio (which relates to the acidic properties). In contrast, for catalyst series where the structural and textural properties vary with the Si/Al ratio, no consistent trend is observed and the catalytic performance is determined by a balance between the acidic and textural properties. The product distribution was also found to be influenced by the physical and chemical properties of the catalyst. Catalysts with strong acidity and smaller pores were observed to favor the formation of lighter hydrocarbons. In addition to the textural and acidic properties of the catalyst, the role of coke formation should not be neglected to ensure a comprehensive analysis of the catalytic performance.

Rice Husk as Raw Material in Synthesis of NaA (LTA) Zeolite.

The present work deals with the hydrothermal synthesis of a Na-A (LTA) zeolite using rice husk as a starting material. The focus was on defining the most favorable conditions for the synthesis of zeolite Na-A from rice husk in order to economize on both energy (i.e., synthesis temperatures) and reaction time and to enlarge the field of the pure and isolated synthesized phase. Four sets of experiments were carried out at environmental pressure temperatures varying from 40 °C to 85 °C with a SiO2/Al2O3 ratio from 1.75 to 3.5. Optimal conditions for crystallization of the Na-A zeolite from rice husk were reached at 60 °C with a SiO2/Al2O3 ratio of 1.75. Sixty degrees Celsius represents the minimum known temperature used for the synthesis of NaA zeolite from rice husk. The products of synthesis were characterized by X-ray diffraction, scanning electron microscopy, infrared and Raman spectroscopy. The purity of the synthesized zeolite is verified here for the first time through quantitative phase analysis using the combined Rietveld and reference intensity ratio methods.

Strength of London Dispersion Forces in Organic Structure Directing Agent-Zeolite Assemblies.

Herein, we study the London dispersion forces between organic structure directing agents (OSDAs)-here tetraalkyl-ammonium or -phosphonium molecules-and silica zeolite frameworks (FWs). We demonstrate that the interaction energy for these dispersion forces is correlated to the number of H atoms in OSDAs, irrespective of the structures of OSDAs or FWs, and of variations in charges and thermal motions. All calculations considered-DFT-D3 and BOMD undertaken by us, and molecular mechanics from an accessible database-led to the same trend. The mean energy of these dispersion forces is ca. -2 kcal.mol-1 per H for efficient H-O contacts.

Hierarchical Zeolites Prepared Using a Surfactant-Mediated Strategy: ZSM-5 vs. Y as Catalysts for Friedel-Crafts Acylation Reaction.

Hierarchical ZSM5 and Y zeolites were prepared through a surfactant-mediated strategy with NH4OH changing the duration of the treatment and the amount of CTAB surfactant and taking as reference multiples of the critical micellar concentration (CMC). The materials were characterized using powder X-ray diffraction, N2 adsorption isotherms at -196 °C, and SEM and TEM microscopy. The catalytic performance was evaluated in Friedel-Crafts acylation of furan with acetic anhydride at 80 °C. The alkaline surfactant-mediated treatment had different effects on the two zeolites. For ZSM5, the CTAB molecular aggregates can hardly diffuse inside the medium-size pores, leading mainly to intercrystalline mesoporosity and increased external surface area, with no positive catalytic impact. On the other hand, for large-pore Y zeolite, the CTAB molecular aggregates can easily diffuse and promote the rearrangement of crystal units around micelles, causing the enlargement of the pores, i.e., intracrystalline porosity. The optimized Y-based sample, treated for 12 h with a CTAB amount 32 times the CMC, shows an increase in product yield and rate constant that was not observed when a higher amount of surfactant was added. The reuse of spent catalysts upon thermal treatment at 400 °C shows a regeneration efficiency around 90%, showing good potentialities for the modified catalysts.

Post-Synthetic Ensembling Design of Hierarchically Ordered FAU-type Zeolite Frameworks for Vacuum Gas Oil Hydrocracking.

Zeolites hold importance as catalysts and membranes across numerous industrial processes that produce most of the world's fuels and chemicals. In zeolite catalysis, the rate of molecular diffusion inside the micropore channels defines the catalyst's longevity and selectivity, thereby influencing the catalytic efficiency. Decreasing the diffusion pathlengths of zeolites to the nanoscopic level by fabricating well-organized hierarchically porous architecture can efficiently overcome their intrinsic mass-transfer limitations without losing hydrothermal stability. We report a rational post-synthetic design for synthesizing hierarchically ordered FAU-type zeolites exhibiting 2D-hexagonal (P6mm) and 3D-cubic (Ia 3 ‾ ${\bar{3}}$ d) mesopore channels. The synthesis involves methodical incision of the parent zeolite into unit-cell level zeolitic fragments by in situ generated base and bulky surfactants. The micellar ensembles formed by these surfactant-zeolite interactions are subsequently reorganized into various ordered mesophases by tuning the micellar curvature with ion-specific interactions (Hofmeister effect). Unlike conventional crystallization, which offers poor control over mesophase formation due to kinetic constraints, crystalline mesostructures can be developed under dilute, mild alkaline conditions by controlled reassembly. The prepared zeolites with nanometric diffusion pathlengths have demonstrated excellent yields of naphtha and middle-distillates in vacuum gas oil hydrocracking with decreased coke deposition.

Reference-Quality Free Energy Barriers in Catalysis from Machine Learning Thermodynamic Perturbation Theory.

For the first time, we report calculations of the free energies of activation of cracking and isomerization reactions of alkenes that combine several different electronic structure methods with molecular dynamics simulations. We demonstrate that the use of a high level of theory (here Random Phase Approximation-RPA) is necessary to bridge the gap between experimental and computed values. These transformations, catalyzed by zeolites and proceeding via cationic intermediates and transition states, are building blocks of many chemical transformations for valorization of long chain paraffins originating, e.g., from plastic waste, vegetable oils, Fischer-Tropsch waxes or crude oils. Compared with the free energy barriers computed at the PBE+D2 production level of theory via constrained ab initio molecular dynamics, the barriers computed at the RPA level by the application of Machine Learning thermodynamic Perturbation Theory (MLPT) show a significant decrease for isomerization reaction and an increase of a similar magnitude for cracking, yielding an unprecedented agreement with the results obtained by experiments and kinetic modeling.

Implanting Colloidal Nanoparticles into Single-Crystalline Zeolites for Catalytic Dehydration.

The encapsulation of functional colloidal nanoparticles (100 nm) into single-crystalline ZSM-5 zeolites, aiming to create uniform core-shell structures, is a highly sought-after yet formidable objective due to significant lattice mismatch and distinct crystallization properties. In this study, we demonstrate the fabrication of a core-shell structured single-crystal zeolite encompassing an Fe3O4 colloidal core via a novel confinement stepwise crystallization methodology. By engineering a confined nanocavity, anchoring nucleation sites, and executing stepwise crystallization, we have successfully encapsulated colloidal nanoparticles (CN) within single-crystal zeolites. These grafted sites, alongside the controlled crystallization process, compel the zeolite seed to nucleate and expand along the Fe3O4 colloidal nanoparticle surface, within a meticulously defined volume (1.5×107≤V≤1.3×108 nm3). Our strategy exhibits versatility and adaptability to an array of zeolites, including but not restricted to ZSM-5, NaA, ZSM-11, and TS-1 with polycrystalline zeolite shell. We highlight the uniformly structured magnetic-nucleus single-crystalline zeolite, which displays pronounced superparamagnetism (14 emu/g) and robust acidity (~0.83 mmol/g). This innovative material has been effectively utilized in a magnetically stabilized bed (MSB) reactor for the dehydration of ethanol, delivering an exceptional conversion rate (98 %), supreme ethylene selectivity (98 %), and superior catalytic endurance (in excess of 100 hours).