Properties Of Zeolites Research Articles

Composites Based on Natural Zeolites and Green Materials for the Immobilization of Toxic Elements in Contaminated Soils: A Review

Soil contamination by toxic elements is a global problem, and the remediation of contaminated soils requires complex and time-consuming technology. Conventional methods of soil remediation are often inapplicable, so an intensive search is underway for innovative and environmentally friendly ways to clean up ecosystems. The use of amendments that stabilize the toxic elements in soil by reducing their mobility and bioavailability is one of the simplest and most cost-effective ways to remediate soil. This paper provides a summary of studies related to the use of composites based on natural zeolites and green materials for the immobilization of toxic elements in contaminated soils and highlights positive examples of returning land to agricultural use. The published literature on natural zeolites and their composites has shown that combinations of zeolite with biochar, chitosan and other clay minerals have beneficial synergistic effects on toxic element immobilization and soil quality. The effects of zeolite properties, different combinations, application rates, or incubation periods on toxic elements immobilization were tested in laboratory scale or field experiments, whereas the mobility of toxic elements in soil was evaluated by chemical extractions of toxic elements transferred to the plants. This review highlights the excellent potential of natural zeolites to be used as single or combined sustainable green materials to solve environmental pollution problems related to the presence of toxic elements.

Volcanic Zeolites from the Yagodninskoe Deposit (Kamchatka Krai)

This work is devoted to typification, study of the compositional features and properties of hydrothermal zeolites of the Yagodninskoe deposit (Kamchatka Krai), formed over volcanic rocks. To carry out the research, X-ray phase and X-ray fluorescence analyses, optical and scanning electron microscopy were used; the specific surface area, pore size distribution, and cation exchange capacity of zeolites were determined. As a result of the research, 4 main types of rocks found at the deposit were identified: original unaltered perlites, zeolites themselves, zeolitized tuffs, and weakly zeolitized tuff breccias. The content of zeolite group minerals reaches 70%, and are mainly represented by clinoptilolite and to a lesser extent mordenite, stilbite and heulandite. Zeolites are of the alkaline type, the cation exchange capacity of which is 205.9 mEq/100 g. It was established that the formation of zeolites occurred mainly in perlites and tuff breccias. It is noted that the zeolites of the Yagodninskoye deposit have high quality raw materials and are the promising object for further development.

Temperature-Programmed Desorption of Single Zeolite Nanoparticles.

Zeolites are essential solid acid catalysts in various chemical processes. Temperature-programmed desorption (TPD) is one of the most established techniques used to characterize the acidity of zeolites by measuring the desorption kinetics of probes from bulk samples. However, conventional TPD can hardly deliver the intrinsic acid properties of zeolites because the apparent desorption kinetics are inevitably mixed with mass transfer and thermal conduction due to the large sample amount (∼0.1 g). Herein, we developed an optical microscopy approach to measure the TPD spectra of single zeolite nanoparticles, termed oTPD, by in situ monitoring of the reduced scattering intensity of individuals as a result of the desorption of probe molecules during heating. A significantly reduced sample amount contributed to the oTPD spectrum, revealing an intrinsic desorption temperature of ∼300 °C lower than the apparent value and also a greatly narrowed peak width from ∼150 to ∼15 °C. Correlating oTPD and micro-Raman spectra of the very same individuals further uncovered a linear dependence between the acidity and the content of silicon islands. This study provided unprecedented capabilities for measuring the intrinsic acid properties and the desorption kinetics of single zeolite nanoparticles, with implications for better understanding the structure-acidity relationship and for designing better zeolite catalysts.

The Influence of Mg, Na, and Li Oxides on the CO2 Sorption Properties of Natural Zeolite

This study presents a comparative analysis of the CO2 sorption properties of natural zeolites sourced from the Tayzhuzgen (Tg) and Shankanay (Sh) deposits in Kazakhstan. The Tayzhuzgen zeolite was characterized by a Si/Al ratio of 5.6, suggesting partial dealumination, and demonstrated enhanced specific surface area following mechanical activation. Modification of the Tayzhuzgen zeolite with magnesium oxide significantly improved its CO2 sorption capacity, reaching 8.46 mmol CO2/g, attributed to the formation of the CaMg(Si2O6) phase and the resulting increase in basic active sites. TPD-CO2 analysis confirmed that MgO/Tg exhibited the highest basicity of the modified samples, further validating its potential for CO2 capture applications.

Cerium-induced modification of acid-base sites in Ni-zeolite catalysts for improved dry reforming of methane

Dry reforming of methane (DRM) is a promising route to mitigate greenhouse gas emissions by converting CH4 and CO2 into valuable syngas. The present work explores the effect of Ce addition to Ni-based catalysts supported on CBV3020E (ZSM-5) for DRM. The use of Ce as a promoter to tune the acid-base properties of zeolites for DRM is addressed for the first time in detail. While Ce has traditionally been used to improve oxygen storage capacity, this work explores its novel use as a means to enhance surface basicity and promote CO2 adsorption. The samples were prepared by wet impregnation, characterized using N2-sorption, X-ray diffraction, H2-temperature-programmed reduction, temperature-programmed desorption of CO2 and ammonia, and Fourier transforms infrared spectroscopy, and tested for DRM at 800 °C and 42,000 mL/g.h GHSV. Results show that ZSM-5 zeolite can be beneficial in achieving high metal dispersion. The introduction of 2 wt% Ce to Ni5/ZSM-5 increases the concentration of strong basic sites, resulting in improved catalytic performance from 37 % CH4 conversion and 48 % CO2 conversion for Ni5/ZSM-5 to 55 % and 65 % on promoted Ni5Ce2/ZSM-5, respectively. Thus, the best results are observed on Ni5Ce2/ZSM-5 and an optimal H2/CO ratio of 0.84 is achieved in this case. Upon decreasing GHSV to 15,000 mL/g.h, CH4 and CO2 conversions jump to 83 % and 88 %, respectively on Ni5Ce2/ZSM-5. Cerium doping produces more desirable strong basic sites and enhances NiO reducibility. This promotes CO2 adsorption and drives the catalytic reaction towards syngas formation, which eventually results in increased efficiency and improved performance.

Fabrication of LTA zeolite core and UiO-66 shell structures via surface zeta potential modulation and sequential seeded growth for zeolite/polymer composite membranes

Zeolite-based polymer composites have garnered significant attention for their applications in separation, catalysis, and energy storage, owing to the unique properties of zeolites. The development of core–shell structures provides a promising strategy to enhance these properties, enabling the fine-tuning of zeolite characteristics within composite films. In this study, we present an innovative approach that leverages surface zeta potential differences to facilitate the growth of an organophilic metal–organic framework (MOF) on hydrophilic zeolite surfaces. Specifically, UiO-66 was successfully attached and grown on Linde Type A (LTA) zeolite particles, resulting in the formation of a robust core–shell structure (LTA@UiO-66). This core–shell architecture significantly minimized interfacial voids when embedded into a polyimide (PI, Matrimid® 5218) matrix, yielding composite films (LTA@UiO-66/PI) with superior mechanical integrity and enhanced gas-separation performance. The LTA@UiO-66/PI films demonstrated remarkable ideal selectivity for O2/N2 (10.7) and CO2/CH4 (47), outperforming traditional LTA/PI composites. These enhancements are attributed to the synergistic effects between the LTA core and the UiO-66 shell, which preserve the molecular sieving capability of the zeolite while ensuring strong adhesion and a void-free interface with the polymer matrix. The findings underscore the significant potential of zeolite-based core–shell structures in advancing industrial applications, particularly in the domains of sustainable gas separation and purification technologies.

Research on the modification technology of beta molecular sieve

The influence of temperature and time of the acid washing and hydrothermal treatment on Beta zeolite properties was examined in detail, the results revealed that acid washing at 2h and 80℃and 2h hydrothermal treatment at 650℃are the best modification operating conditions. The different SiO2/Al2O3ratio of Beta zeolite are systematically modified using optimized modification operating conditions. Beta zeolite modified from higher SiO2/Al2O3ratio of the starting Beta also has higher SiO2/Al2O3 ratio. Crystallinity of starting Beta zeolite has less effect on the modified Beta zeolite. As the SiO2/Al2O3 ratio of starting Beta increased, total acid amount of modified Beta decreased. When the SiO2/Al2O3 ratio of starting Beta is bigger, the surface area and pore volume is higher.

In situ visualisation of zeolite anisotropic framework flexibility during catalysis

Zeolites exhibit framework flexibility driving their chemical and catalytic properties. Since the zeolitic pores are extremely small, a slight strain generated in the crystal induces compelling changes in shape, connectivity, accessibility, and the framework chemical properties. These modifications affected the adsorption and desorption of reactants/products and the diffusion within the channels during reaction. Using in situ 3D Bragg coherent X-ray diffraction imaging, we unveil the dynamics of the zeolite structure during catalysis, contraction and/or expansion of its framework also known as zeolite framework flexibility. We imaged three-dimensionally a single faujasite zeolite crystal during the ethanol dehydration reaction revealing anisotropic lattice dynamics simultaneously to guest molecules formation. Understanding zeolite flexibility could permit to tune zeolites properties towards potentially higher adsorption and selectivity.

Fabrication and adsorption properties of hierarchical NaY zeolite with mesopores in the range of 2–5 nm

Adsorption is one of the most effective methods for controlling the concentration of VOCs pollution. In this work, the hierarchical NaY zeolites with size-controlled mesopores in the range of 2–5 nm are obtained via NH4HF2-etching and surfactant-templating process. By using the different cationic surfactant (CnTAB), we fabricate the surfactant-templated zeolite with controllable mesopores, and improve its adsorption capacity for toluene. In addition, the modified zeolite’s hydrophobicity is enhanced, and it maintains a high adsorption capacity in a complex humid environment.

Removal of heavy metals from aqueous solutions by adsorption on zeolites synthesized from aluminum saline slags

Three heavy metals (Cu2+, Cd2+ and Pb2+) were removed from aqueous solutions using zeolites prepared from saline slags, a very important waste generated during aluminum recycling. Zeolites were characterized by powder X-ray diffraction, thermal analysis, Fourier transform infrared spectroscopy, X-ray microfluorescence, element chemical analysis, nitrogen adsorption at −196 °C and electron microscopy. The textural and structural properties of X-type faujasite zeolite convert it in a promising adsorbent in aqueous streams. Removal of the heavy metals was evaluated in batch mode, studying the adsorbent dose, the initial concentration of the heavy metal, the selectivity of the solid in case of mixtures with various metal cations and the recyclability of the solid. The kinetic and equilibrium results were evaluated using both pseudo-first- and pseudo-second-order kinetics, and Langmuir, Freundlich and Toth equation isotherms for the equilibrium. The time needed to reach equilibrium was between 10 and 20 min. Faujasite was highly effective in removing Cu2+, Cd2+ and Pb2+ from aqueous solutions, much higher than analcime and pollucite, other two zeolites recently synthesized by us from aluminum slags, and used in this work for comparison purposes. The maximum adsorption capacity was 591 mg/g for Pb2+, 304 mg/g for Cu2+ and 279 mg/g for Cd2+.

Effect of temperature and extraframework cation type on CHA framework flexibility

The sorption properties of zeolites are controlled by several factors, i.e. Si/Al ratio of the aluminosilicate framework [AlSiO4]-, the type and position of the extraframework (EF) cations, and the applied temperature. Here we investigate the flexibility of CHA framework as a function of EF cation-content and temperature (20–350 °C). Two CHA forms (Na- and Cu-CHA) with Si/Al = 2 were analysed. The main objectives were: (i) to shed light on the HT behaviour of Na-CHA, for which contrasting results exist in literature; (ii) define the role of temperature and EF cation-type in the response to the heating stimuli. We show that at 75 °C, Na-CHA undergoes a severe contraction of the unit-cell volume (-12%) accompanied by a symmetry lowering (R-3m to I2/m). The transformation is reversible, if the dehydrated Na-CHA is exposed to ambient conditions. In contrast, Cu-CHA experiences a significant different dehydration path, which involves minor changes of the CHA framework, and a net positive thermal-expansion after dehydration. The implications of the observed transformations for gas separation processes are finally discussed.

Graph Neural Networks for Carbon Dioxide Adsorption Prediction in Aluminum-Substituted Zeolites.

The ability to efficiently predict adsorption properties of zeolites can be of large benefit in accelerating the design process of novel materials. The existing configuration space for these materials is wide, while existing molecular simulation methods are computationally expensive. In this work, we propose a model which is 4 to 5 orders of magnitude faster at adsorption properties compared to molecular simulations. To validate the model, we generated data sets containing various aluminum configurations for the MOR, MFI, RHO and ITW zeolites along with their heat of adsorptions and Henry coefficients for CO2, obtained from Monte Carlo simulations. The predictions obtained from the Machine Learning model are in agreement with the values obtained from the Monte Carlo simulations, confirming that the model can be used for property prediction. Furthermore, we show that the model can be used for identifying adsorption sites. Finally, we evaluate the capability of our model for generating novel zeolite configurations by using it in combination with a genetic algorithm.

Examining the influence of sintering temperatures on the efficiency of 3D-printed natural zeolite for methylene blue dye adsorption

Additive manufacturing technology, with its potential for improved material efficiency, cost reduction, and capability to fabricate complex structures, is increasingly being leveraged in environmental engineering applications. This study harnesses this technology for fabricating natural zeolite adsorbents using an extrusion-based 3D printer, examining the influence of different sintering temperatures (300, 600, 900, and 1200 °C) on the adsorbents' properties. The study finds that samples sintered at 300 °C disintegrated in water, while those at 1200 °C underwent melting, changing their shape. Focus was then shifted to samples sintered at 600 °C (3D-Ze-600) and 900 °C (3D-Ze-900), with the former displaying a remarkable methylene blue (MB) adsorption efficiency of 82.5%, significantly higher than the latter's 20.1%. This disparity in adsorption performance is closely linked to the difference in porosity; the 600 °C samples exhibited a notably higher apparent porosity, which was instrumental in their enhanced adsorption capability. In contrast, the 900 °C samples, despite their lower porosity, showed diminished adsorption efficiency. XRD analysis further revealed that the superior performance of the 600 °C samples could be attributed to their preserved crystalline structure, which was altered in the 900 °C samples. These findings highlight the critical role of sintering temperature in determining the structural and functional properties of 3D-printed zeolites, demonstrating their potential as efficient adsorbents in wastewater treatment and offering valuable insights for optimizing the fabrication process for environmental applications.

Simulation of Structural, Electronic and Pharmacodynamics Properties of Developed Zeolite Docking with Hemoglobin

The study included simulating the preparation of the structure of zeolite with its natural square structure in its simplest form, in addition to the structure of the developed zeolite, where the square zeolite was developed by adding one atom of copper or iron, in addition to the preparation of the cubic zeolite. Simulation of the structural and electronic properties of zeolite and developed zeolite structures was studied, using density functional theory at the B3LYP level and the 6 – 311G(d,p) basis set. The above properties of non-oxidized and oxidized hemoglobin were also simulated, for the purpose of making a comparison between it and the coalescence of developed zeolite with non-oxidized hemoglobin, to know the effect of the developed zeolite structures on hemoglobin as a pharmacodynamics properties. The Gibbs free energy was calculated for the docking of oxygen with non-oxidized heme, which was (-51.624 eV) as well as for the zeolite structures developed after docking with non-oxidized heme, which was (94814.14175 eV) for Fe - zeolite with DHB and (4107.871817 eV) for Cu - zeolite with DHB. Through the thermodynamic results, it was shown that the docking process of the developed zeolite structures with non-oxidized hemoglobin is non-lethal and harmless and is similar to the docking process of oxygen with heme. It can be concluded from this, that the developed zeolite structures can be used in medical applications, such as participating in treatment, delivering medications, or carrying medications inside the human body.

Simulation of Structural, Electronic and Pharmacodynamics Properties of Developed Zeolite Docking with Hemoglobin

The study included simulating the preparation of the structure of zeolite with its natural square structure in its simplest form, in addition to the structure of the developed zeolite, where the square zeolite was developed by adding one atom of copper or iron, in addition to the preparation of the cubic zeolite. Simulation of the structural and electronic properties of zeolite and developed zeolite structures was studied, using density functional theory at the B3LYP level and the 6 – 311G(d,p) basis set. The above properties of non-oxidized and oxidized hemoglobin were also simulated, for the purpose of making a comparison between it and the coalescence of developed zeolite with non-oxidized hemoglobin, to know the effect of the developed zeolite structures on hemoglobin as a pharmacodynamics properties. The Gibbs free energy was calculated for the docking of oxygen with non-oxidized heme, which was (-51.624 eV) as well as for the zeolite structures developed after docking with non-oxidized heme, which was (94814.14175 eV) for Fe - zeolite with DHB and (4107.871817 eV) for Cu - zeolite with DHB. Through the thermodynamic results, it was shown that the docking process of the developed zeolite structures with non-oxidized hemoglobin is non-lethal and harmless and is similar to the docking process of oxygen with heme. It can be concluded from this, that the developed zeolite structures can be used in medical applications, such as participating in treatment, delivering medications, or carrying medications inside the human body.

Enhancing catalytic pyrolysis of polypropylene using mesopore-modified HZSM-5 catalysts: insights and strategies for improved performance

Designing an active, selective, and stable catalyst for catalytic polyolefin pyrolysis is crucial for enhancing energy efficiency and economic viability in chemical processes. In this study, two synthesis methods—NaOH and NaOH/CTAB treatments—were employed to modify the physicochemical properties of CBV23, CBV55, and CBV80 zeolites. The catalytic performance of both parent and modified zeolites was evaluated for polypropylene pyrolysis using a two-stage micro-pyrolyzer coupled with two-dimensional GC-FID/MS. The NaOH/CTAB treatment preserved and enhanced strong acid sites while promoting a more uniform mesopore distribution. Among the catalysts tested, the hierarchical CBV80-ZM exhibited the best performance, achieving a propylene yield of 41 wt% and total light olefin and MA yields of 92 wt%. The improved catalytic performance was attributed to optimized acidity and larger pore size, which reduced the number of weak acid sites. These findings offer valuable insights for designing tailored zeolites based on specific target products for catalytic pyrolysis of plastic waste, particularly in the production of propylene and other high-value chemicals.

Solvent-free synthesis of hierarchical tungsten-doped MFI zeolite for cyclohexene epoxidation reaction

Solvent-free synthesis method in zeolite preparation can largely decrease the generation of wastewater and improve the zeolite yield by simply grinding and hydrothermal treatment for the solid raw materials, and accordingly is considered as one of the most promisingly green and sustainable synthesis strategy for the metal-doped zeolite materials. However, there are scarcely any reports on the solvent-free synthesis and catalytic application of tungsten-doped zeolite materials. In this work, tungsten-doped MFI zeolites were prepared with solvent-free synthesis method and used as heterogeneous catalyst for cyclohexene epoxidation reaction. The synthesized tungsten-doped MFI zeolites displayed a monoclinic (P21/n) space group attributed to the successful incorporation of tungsten atom into MFI framework and meanwhile possessed an enormous number of irregular mesopores ranging from 2 nm to 50 nm. The influence of TPAOH addition amount on the mesopore structure and properties of tungsten-doped MFI zeolite was further investigated. In addition, the crystallization process of tungsten-doped MFI zeolite sample was tracked and analyzed with SEM, XRD and BET characterizations, and accordingly possible formation process for hierarchical zeolite was proposed. Furthermore, the prepared hierarchical tungsten-doped MFI zeolite displayed eminent cyclohexene epoxidation performance and re-usability for more than five times. This work provides some guidance for the solvent-free synthesis of metallosilicate zeolites, decreasing the generation of wastewater and improving the zeolite yield.

Assessment of acid catalytic properties of ferrosilicate MFI zeolite by methanol-to-hydrocarbon conversion.

Four representative synthetic methods were employed to prepare Fe-containing siliceous MFI zeolites. The obtained Fe-MFI zeolites exhibited markedly different catalytic performances in the methanol-to-hydrocarbon (MTH) conversion reaction depending on the type of Fe incorporation within the siliceous framework. The catalytically active Brønsted acid sites were analyzed using pyridine adsorption experiments combined with Fourier transform infrared spectroscopy, providing characteristic signal intensities according to the acid-base interactions. Based on the MTH conversion results and acidity analyses, a suitable synthetic method was identified for the incorporation of Fe within the MFI zeolite framework. However, compared to other catalytic reactions, structural analyses by transmission electron microscopy, ultraviolet-visible spectroscopy, and X-ray absorption spectroscopy were much less conclusive.

Deactivation and regeneration dynamics in hierarchical zeolites: Coke characterization and impact on catalytic cracking of vacuum gas oil

This study investigated the deactivation and regeneration of hierarchical zeolites in vacuum gas oil conversion, aiming to reach the equilibrium state seen in fluidized bed catalytic cracking (FCC). The research utilized various characterization techniques to analyze the properties of zeolites before and after coking and regeneration. Zeolite Y-0.20-S was found to have the highest gasoline selectivity and quality, mirroring industrial yields, and displayed notable stability across deactivation/regeneration cycles. Higher mesopore concentration in zeolites led to increased coke selectivity and better resistance to deactivation. The study observed a dominance of aromatic coke with a higher degree of condensation in these zeolites. Despite coke deposition affecting acid and textural properties, the regeneration process effectively restored these characteristics, proving its efficiency. The zeolites with greater mesoporosity retained their fundamental properties responsible for activity and selectivity, highlighting the importance of selecting materials that provide high conversions and maintain stability and product selectivity over multiple cycles. The Y-0.20-S zeolite, in particular, was identified as a promising candidate for commercial catalyst development for gasoline production, contributing to the FCC process's energy efficiency.

Influence of Extra-Framework Aluminum Species on the Catalytic Properties of Acidic USY Zeolite in (Hydro)cracking Reactions

Influence of Extra-Framework Aluminum Species on the Catalytic Properties of Acidic USY Zeolite in (Hydro)cracking Reactions