Zeolite Crystals Research Articles

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.

Preparation of Novel Hierarchical Catalysts by Simultaneous Generation of β-Zeolite and Mesoporous Silica for Catalytic Cracking.

The gel skeletal reinforcement (GSR) method was applied at the preparation stage of β-zeolite to prepare a novel hierarchical catalyst. A solution of hexamethyldisiloxane (HMDS) and acetic anhydride, a GSR reagent, was added to the mixture of colloidal silica, sodium aluminate, tetraethylammonium hydroxide, sodium hydroxide and water, and successive aging and hydrothermal treatment gave microporous β-zeolite surrounded by mesoporous silica like core-shell structure. Its properties were characterized by XRD, nitrogen adsorption and desorption, NH3-TPD, TEM, and TG-DTA measurements, and further characteristics of the catalysts produced were clarified by the catalytic cracking of n-dodecane. The hierarchical structure of microporous zeolite and mesoporous silica was shown from GSR-2.9HS-H-Beta to GSR-3.2HS-H-Beta, where the molar ratio of HMDS and silica source of β-zeolite was 2.9~3.2 : 100. It was found that in the catalytic cracking of n-dodecane, the relative activity (the conversion per the amount of zeolite crystals) increased with the increase in mesopore volume and surface area. The result indicated that the introduction of mesopores was effective even in catalytic cracking of small molecule of n-dodecane.

Directional Transport in Hierarchically Aligned ZSM-5 Zeolites with High Catalytic Activity.

Zeolites, the most technically important crystalline microporous materials, are indispensable cornerstones of chemical engineering because of their remarkable catalytic properties and adsorption capabilities. Numerous studies have demonstrated that the hierarchical engineering of zeolites can maximize accessible active sites and improve mass transport, which significantly decreases the internal diffusion limits to achieve the desired performance. However, the construction of hierarchical zeolites with ordered alignments and size-controlled substructures in a convenient way is highly challenging. Herein, we develop a facile procedure using two common structure-directing agents, tetrapropylammonium hydroxide (TPAOH) and tetraethylammonium hydroxide (TEAOH), to synthesize hierarchically aligned ZSM-5 (Hie-ZSM-5) crystals with a-axis alignment substructures of controllable size. The control of the substructure size (α) in the range of 10-60 nm and the corresponding similarity (r = α/β, where β is the size of Hie-ZSM-5) ranging from 0.004 to 0.033 can be tuned by varying the Si/Al ratios (40-120). A systematic investigation of the overall crystallization process, using time-dependent XRD, SEM, TEM, and solid-state magic-angle spinning NMR (13C, 27Al, 29Si) methods, enable us to construct a solid mechanism for the generation of Hie-ZSM-5. Most importantly, directional transport in the unique structures of Hie-ZSM-5 efficiently enhances mass diffusion, as well as catalytic activity and stability. These findings improve our understanding of the zeolite crystallization process and inspire novel methods for the rational design of hierarchical zeolites.

Zeolite Crystallization Inside Chemically Recyclable Ordered Nanoporous Co3O4 Scaffold: Precise Replication and Accelerated Crystallization.

The synthesis of mesoporous zeolites has garnered attention with regard to improving their catalytic and adsorption performances. While the hard-templating method provides opportunities to design precisely controlled hierarchical micro- and mesoporous structures, synthesizing mesoporous zeolites without external precipitation requires significant work. This is mainly due to the absence of usable templates other than carbon with hydrophobic surfaces. Herein, it is demonstrated that the Co3O4 template is valuable in preparing mesoporous silicalite-1 and ZSM-5 with a precisely controlled porous structure through hydrothermal synthesis. Unlike conventional carbon templates, the Co3O4 template is relatively hydrophilic, effective in suppressing external precipitation, and is reusable by dissolving in an acidic solution. The crystallization process also differs from that of the carbon template, as the silicate precipitates on a 3D ordered nanoporous Co3O4 scaffold, followed by crystallization and crystal growth. Furthermore, it is unexpectedly observed that the zeolite crystallization is accelerated in the Co3O4 template. The synthetic approach utilizing nanoporous metal oxides opens new doors for the control of the hierarchical structure of zeolites, as well as for the design of metal oxide-zeolite nanocomposite catalysts, due to the potential extensibility of the combination of metal oxides and zeolites.

Deciphering the Link between Zeolite Crystal Size, Brønsted Acid Site Distribution, and Dual-Cycle Selectivity in Methanol-to-Olefins over Zeolite

Deciphering the Link between Zeolite Crystal Size, Brønsted Acid Site Distribution, and Dual-Cycle Selectivity in Methanol-to-Olefins over Zeolite

A nanoscale investigation of the formation of mesostructured zeolites FAU and LTL

Nanostructured materials can be utilised as potential catalysts for the production of platform chemicals and renewable biofuels from biomass derived molecules. The formation of hierarchical meso-microporous zeolites LTL and FAU via the surfactant assisted tandem acid-base post-synthesis treatment has been investigated by time-resolved in situ synchrotron SAXS and WAXS, providing a new insight into the mechanism of the mesostructuring treatment. Based on the results of TEM and in situ synchrotron measurements, a model for the formation of the core-shell structure of LTL zeolite crystals is proposed. Complementary evaluation using FTIR, NMR and nitrogen adsorption, in conjunction with reaction studies on mesostructured zeolites, demonstrated a potential for enhanced catalytic performance of these materials owing to the increased accessibility of the active sites and reduced transport limitations.

Synchrotron Infrared Microspectroscopy of Zeolite Catalysts

This article reviews recent work undertaken at the beamline B22 of the Diamond Light Source using infrared (IR) microspectroscopy to characterise zeolite catalysts and to study their reactivity in real time. The advantage of vibrational microspectroscopic analysis when linked to the brightness and spectral bandwidth of synchrotron IR light are illustrated. The high spatial resolution means that the uniformity of acid site concentrations within individual large crystals of zeolites and between different crystals can be readily checked and changes to acid site concentrations within crystals resulting from steam treatment mapped. When an in situ reaction cell is coupled with mass spectrometric analysis of evolved gases the rapid time response of the method has provided new insight into the initial stages of the conversion of methanol to hydrocarbons over ZSM-5 and SAPO-34 single crystals. Future prospects for applying the method to other types of zeolite catalysed reactions with improved reaction cell design are also discussed.

Design of physical and functional properties of zeolitic porous monoliths by combining different foaming additives

Self-supporting zeolitic foams were synthesized by a geopolymer gel conversion process, employing silicon powder and hydrogen peroxide as foaming additives. The influence of silicon and hydrogen peroxide combination on the physical properties, mechanical characteristics, and pore distribution was studied. Correlations between these properties were drawn. This approach allows to manufacture porous monoliths tuned in terms of zeolite type and amount and characterized by bulk density ranging between 573 and 762 kg/m3 and thermal conductivity 0.33–0.53 W/mK. Pore structure, size, and distribution were dominated by the type of foaming agent: the foamed samples showed the presence of two classes of pores, the first of the order of magnitude of 1 μm, the second of the order of magnitude of 100 μm. The use of hydrogen peroxide enhanced the porosity in the meso-macropore range (0.1–5 μm). The hydrothermal treatment performed on the foamed geopolymer allowed to achieve the crystallization of zeolites within the solid geopolymer. Mainly FAU and LTA were the zeolitic phases present in the foams, whereas the use of silicon as foaming agent locally increased the Si/Al ratio on the geopolymer surface, promoting the nucleation of FAU.

CPAM-assisted synthesis of NaA zeolite membrane on macroporous mullite hollow fiber for ethanol dehydration by pervaporation

Due to the low transport resistance, mullite hollow fiber (HF) could be regarded as a promising support for preparation of NaA zeolite membranes. However, insufficient coverage and undesired seed penetration often occur in the seeding step of the mullite support due to the rough surfaces with ultra-large macropores (2–4 μm). This leads to poor intergrowth of the membrane layer. To solve this issue, cationic polyacrylamide (CPAM) was employed to modify the chemical and electrostatic properties of the mullite HF surface, where the electrostatic attraction between the surface and seed crystals could significantly promote the coating effect. In the seeding, the original seeds (3.2 μm) were mixed with the ball-milled seeds (0.3 μm) to improve the seed coverage, i.e., the original seed was used to block the macropores on the support surface to prevent the penetration of small seeds, while the decked ball-milled seed was used to provide sufficient active sites to induce the intergrowth of the zeolite crystals. The effects of the concentration of CPAM, mixed mass ratio of seeds, and seed concentration on the preparation of NaA zeolite membranes were systematically examined, where the separation performances were characterized by pervaporation (PV) dehydration of 90% (mass) ethanol/water mixtures at 75 °C. The results indicated that under a CPAM concentration of 0.7% (mass), an equivalent mass ratio of mixed seeds in a seed concentration of 1.0% (mass), the prepared mullite HF supported NaA zeolite membrane yielded the best PV performance, where the permeation flux and separation factor corresponded to 5.45 kg·m−2·h−1 and 10000, respectively, being sufficient for industrial applications.

Capturing Different Intermediate Phases during Zeolite Synthesis.

Despite extensive efforts over the past several decades, the current mechanistic understanding of zeolite crystallization is still far from satisfactory, thus precluding the synthesis of designer zeolites. Here we show that the nucleation and in situ transformation pathways during the synthesis of medium-pore zeolite TNU-9 can be altered by controlling the extent of cooperative structure direction between Na+ and Cs+ ions in the presence of 1,4-bis(N-methylpyrrolidinium)butane cations as an organic structure-directing agent. The intermediate phase selectivity was found to change from bikitaite to analcime to layered MCM-22 precursor when the gel Na/Cs ratio was adjusted to 7, 15, and 20, respectively. We also show that the transformation of bikitaite into TNU-9 begins at the surface of intermediate crystals, unlike that of analcime and MCM-22 precursor by a dissolution-recrystallization process. The force field simulation results suggest that the nucleation of different intermediate phases is not thermodynamically but kinetically controlled. This study provides a new basis for advancing the fundamental understanding of zeolite crystallization pathways.

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.

Breaking the stability limit of zeolite-based alkane dehydrogenation catalysts

Metal catalysts confined inside zeolite micropores or crystals are widely applied in the chemical industry because of their distinctive catalytic functions, especially with regard to the conversion of small and stable alkane molecules [1,2]. Silicalite-1 (S-1), a pure silica zeolite with an MFI topology, has a robust framework capable of withstanding harsh thermal and chemical conditions. Recently, S-1-based catalysts have demonstrated significant advantages in the construction and stabilization of various active metal centers and have attracted considerable attention for their potential in alkane dehydrogenation reactions. The absence of acidic sites prevents various acid-catalyzed side reactions, rendering S-1 a promising candidate for high-temperature reactions such as non-oxidative propane dehydrogenation (PDH). Sun et al. revealed that encapsulating subnanometer bimetallic PtZn clusters in S-1 resulted in a high propylene selectivity of 99%, with no catalyst deactivation even after 200h in the PDH reaction [3]. However, sustaining high stability at high conversion rates is still challenging for PDH reactions, and commercial processes are still based on Pt- and Cr-based catalysts, which need frequent regeneration.

Faujasite/graphene nanoribbon hybrid adsorbent pellet for carbon dioxide capture

Pelletizing zeolite adsorbents is essential for practical applications, but conventional pelletization methods involve binders that can alter material properties. This study presents a one-pot approach to synthesizing FAU-type zeolite/graphene oxide nanoribbon (GONR) composite powders that can be pelletized by simple pressing without binders. This one-pot synthesis can be conducted without structure-directing agents, making the process simpler and more efficient. During zeolite crystallization, the particles decorate the strands of GONRs, effectively generating additional macropores and enhancing the pellets’ mechanical strength. Additionally, GONR suppresses water adsorption while maintaining good CO₂ adsorption, which improves the material’s performance under humid conditions. The FAU/GONR pellets exhibited enhanced mass transport properties compared to neat FAU pellets, as demonstrated by 10 times higher CO₂ permeability. The highest CO₂/N₂ selectivity of 76.5 was observed with 12 wt% GONR-containing pellet, and the performance was comparable to conventional pellets, while the fabrication procedure remained simple.

Study on High-Ductility Geopolymer Concrete: The Influence of Oven Heat Curing Conditions on Mechanical Properties and Microstructural Development.

Low carbon and high performance have become key trends in the development of construction materials. Understanding the mechanism by which curing conditions affect the mechanical properties of high-ductility geopolymer concrete (HDGC) is of significant importance. This study investigated three sealing curing temperatures (room temperature, 45 °C, and 60 °C) and four curing durations (1 day, 3 days, 5 days, and 7 days), while considering two final curing ages (7 days and 28 days) to explore their effects on the axial tensile and compressive properties of HDGC. The results showed that both 45 °C and 60 °C could improve the brittle failure of HDGC under axial compressive loading. However, curing at 60 °C and for durations longer than 1 day in an oven would catalyze the formation of eight-faced zeolite crystals within the slag-fly ash geopolymer matrix, and it could weaken the matrix's pore structure and subsequently affect the material's later strength development. Nevertheless, oven heat curing enhanced the bridging effect between the fibers and the matrix, partially compensating for the reduction in the initial tensile strength of HDGC. This follows the pseudo-strain-hardening material's saturation cracking criterion to enhance the strain-hardening behavior of HDGC and improve its tensile energy absorption capacity. A curing condition of 45 °C for 5 days is recommended to maximize the ductility of HDGC. This study provides important theoretical support for the design and promotion of green, low-carbon, high-ductility composite materials.

Durable superhydrophobic LTA-zeolite coating on PDMS surface with excellent self-cleaning property

Superhydrophobicity is a fundamental characteristic that plays a vital role in various applications, such as self-cleaning coatings, water vapor barriers for flexible electronics, and microfluidic chip fabrication. In this study, we developed a superhydrophobic surface coating on polydimethylsiloxane (PDMS) using Linde Type A (LTA) zeolite crystals, employing a silane coupling strategy. As part of this study, the LTA-zeolite-coated PDMS surface is characterized using various techniques to elucidate its superhydrophobic behavior, and a functionalization mechanism is proposed. The resulting substrate exhibited high surface roughness, with a water contact angle exceeding 155°, a sliding angle below 1°, and a contact angle hysteresis under 10°. This superhydrophobic surface coating effectively repelled water, confirming its excellent self-cleaning properties. Furthermore, the coating withstood three cycles of the Kapton adhesive tape peeling test, 5 h of water-jet hitting, and 72 h of UV light exposure, demonstrating its robustness and strong adhesion to PDMS.

Correction to: Remarkably facilitated crystallization of MSE-type zeolite by using an efficient organic structure-directing agent

Correction to: Remarkably facilitated crystallization of MSE-type zeolite by using an efficient organic structure-directing agent

Lysine-assisted synthesis of plate-like TS-1 zeolite for 1-hexene epoxidation

Plate-like TS-1 zeolites offering a short diffusion pathway along the b-axis are highly desirable catalysts in the reaction of alkene epoxidation. Herein, we successfully developed a simple synthetic strategy toward reducing the thickness along the b-axis of TS-1 zeolite crystals, l-lysine adopted as a zeolite growth modifier was firstly proposed to prepare plate-like TS-1 zeolite. Meanwhile, through tuning the preliminary aging time, plate-like TS-1 zeolites with thickness in the range of 80–1000 nm can be controllable obtained. In this work, the synthesis parameters controlling the formation of plate-like TS-1 zeolites are studied, and the factors controlling the zeolite growth were well elucidated. Compared with the conventional TS-1 zeolite as well as the plate-like TS-1 synthesized in the fluoride-containing medium, the obtained plate-like TS-1 shows improved catalytic performances in catalyzing epoxidation of 1-hexene.

Estimation of catalytic cracking of vacuum gas oil by ZSM-5- and β-zeolite-containing two-layered and novel three-layered hierarchical catalysts using Curie point pyrolyzer

ZSM-5- and β-zeolite-containing two-layered hierarchical catalysts (2 L-Z and 2 L-β) were prepared using a template of malic acid and novel three-layered hierarchical catalysts were also prepared combining mesoporous silica derived from the gel skeletal reinforcement (GSR) method with hexamethyldisiloxane (HMDS) - acetic anhydride (AA) as reinforcing agents. 2 L-Z and 2 L-β catalysts contained mesoporous silica of 50 wt% and microporous zeolite of 50 wt% and were called 2 L-Z-(Z50) and 2 l-β-(Z50) in which the amount of zeolite is shown in parenthesis. 3 L-co-gel and 3 L-mix, two types of three-layered hierarchical catalysts, were prepared by making GSR-silica in the presence of a 2 L catalyst for the former and by combining GSR-silica-gel with 2 L catalyst for the latter. 3 L catalysts contained 50 wt% of the 2 L catalyst and 50 wt% large-mesoporous GSR-silica and revealed three layered properties of microporous zeolite, small mesoporous silica and large mesoporous silica. Signals of zeolite crystals and amorphous phase were observed in XRD measurement for 3 L catalysts. Both smaller size of mesopores and larger size of mesopores were observed in N2 adsorption-desorption measurement. Vacuum gas oil (VGO) was catalytically cracked using 2 L and 3 L hierarchical catalysts with the use of Curie point pyrolyzer (CPP) method. ZSM-5-containing 3 L catalysts exhibited the lower conversions than corresponding 2 L catalyst, kaolin-mixed catalyst and ZSM-5 single while 3 L-co-gel-β-(Z25), which included 25 wt% of β-zeolite, exhibited the highest activity among β-zeolite-containing catalysts. The higher selectivity for p-xylene in xylene mixture was detected in catalytic cracking using 3 L-co-gel-Z-(Z25) and 3 L-mix-Z-(Z25) catalysts. When the relative activity against XRD integral intensity and amounts of acid sites was plotted against average pore diameter derived from N2 adsorption-desorption measurement, the strong correlation was observed, suggesting that the intrinsic activity of active sites of zeolite could be related to the pore size of the whole catalyst.

Insights into the nature of Zr-species in MFI-type Zr-metallosilicates by using bulk and surface techniques

The purpose of this study is to prepare Zr-metallosilicates with MFI-type framework via direct hydrothermal approach, by varying Si and Zr precursors. First, a set of routine characterization techniques was applied to confirm the presence of the targeted structure as well as their intrinsic properties. Results suggest the formation of MFI-type materials with large specific surface areas (up to 421 m2 g−1). Then, a combination of advanced spectroscopic techniques (XPS, ToF-SIMS, EPR), high-resolution microscopy, and periodic Density Functional Theory (DFT) calculations were applied to study their bulk and surface properties as well as the nature and localization of Zr-species. It appears that the insertion of zirconium atoms within a MFI framework is energetically unfavorable, leading to the formation of an amorphous silica-zirconia shell coating the zeolite crystals.

Engineering in ceramic albite morphology by the addition of additives: Carbon nanotubes and graphene oxide for energy applications

Abstract The synthesis of zeolite nanoparticles is studied comprehensively by adding an organic template as a reflux method, extracted from crystals. The zeolite nano-crystals are quite effectively synthesized by incorporating silica, organic template, and alkali metal. The tetrapropylammoniumhydroxide, tetrapropylammoniumbromide and tetraethyl orthosilicate (TEOS) as organic templates are added for the assistance of zeolite (albite) crystals. A cross-linker TEOS is also mixed. Adding carbon nanotubes and graphene oxide made the morphology of albite more interesting. Nucleation time is an important feature for the formation of albite crystals. The albite nano-shaped crystal is developed for instance when reaction time is less than 240 h, after this period crystal size increases with time. Batch 1 of zeolite is prepared with additives for testing its morphology, like surface area, particle size shape, and crystal geometry. The general trend (e.g., pore volume, percentage composition, particle size, geometry) of zeolite nano-crystal is explained by the help of robust techniques such as Fourier transform infrared spectroscopy, X-ray diffraction, Brunauer–Emmett–Teller, energy-dispersive X-ray spectroscopy, and scanning electron microscopy.