Hierarchical mesoporous zeolites: direct self-assembly synthesis in a conventional surfactant solution by kinetic control over the zeolite seed formation

By kinetic control over the zeolite seed formation, we report the direct fabrication of hierarchical mesoporous zeolites using hexadecyl trimethyl ammonium bromide (CTAB) as the soft template in a conventional solution route. Nanometer-sized, subnanocrystal-type zeolite seeds with a high degree of polymerization are essential to prevent the formation of a separate amorphous mesoporous phase and the phase separation between the mesophase and zeolite crystals in the presence of CTAB and a certain amount of ethanol. The mechanisms for the formation of hierarchically porous zeolites in the solution process, including the effect of mother liquid aging, formation of subnanocrystal zeolite seeds and their self-assembly effect with CTAB, and the role of ethanol are proposed and discussed in detail. The prepared mesoporous ZSM-5 zeolite showed much higher catalytic activity than conventional counterparts for aldol condensations involving large molecules, especially in the synthesis of vesidryl.     

Catalytic benzene alkylation over mesoporous zeolite single crystals: improving activity and selectivity with a new family of porous materials

Mesoporous zeolite single-crystal catalysts are shown to be both more active and more selective than conventional zeolite catalysts in the alkylation of benzene with ethene. The superior catalytic properties are ascribed to improved mass transport in the mesoporous zeolite crystals. Thus, mesoporous zeolite single-crystal catalysts combine the high acidity, shape-selectivity, and hydrothermal stability of zeolites with the efficient mass transport that is typically achieved in mesoporous materials.     

Influence of downsizing of zeolite crystals on the orthorhombic ↔ monoclinic phase transition in pure silica MFI-type

The impact of crystal size on the transition orthorhombic ↔ monoclinic phase in MFI-type purely silica zeolites is investigated between 293 and 473 K using ²⁹Si MAS NMR and powder X-ray diffraction. Three silicalite-1 zeolites are synthesized: a material constituted of micron-sized crystals, pseudospherical nanometer-sized crystals and hierarchical porous zeolites with a mesoporous network created by the use of a gemini-type diquaternary ammonium surfactant giving nanosheet zeolites. Our results show for the first time that the orthorhombic ↔ monoclinic phase transition already known for micron-sized particles also occurs in nanometer-sized zeolite crystals whereas our data suggest that the extreme downsizing of the zeolite crystal to one unit cell in thickness leads to an extinction of the phase transition.     

Availability and interconnectivity of pores in mesostructured ZSM-5 zeolites by the adsorption and diffusion of mesitylene

Probing the mesopore architecture in mesoporous zeolites is of importance for large scale applications of the materials. In this work, the adsorption and diffusion of mesitylene with larger molecule size in mesoporous ZSM-5 zeolites were carried out, in order to acquaint the availability and interconnectivity of mesopores in zeolite crystals. The comparisons of the shape of adsorption isotherms and the mesopore volume calculated from mesitylene and N₂ adsorption in mesoporous ZSM-5 zeolites with different mesoporosities can be used to discriminate two cases of mesopores: accessible mesopores connected to external surface of the zeolite crystals and non-accessible meso-voids that are occluded in the microporous matrix. Furthermore, the effective diffusivity and activation energy of mesitylene in mesoporous ZSM-5 extracted from ZLC desorption curves as a function of mesopore volume calculated from mesitylene adsorption reveal the enhancement of mesopore interconnectivity to molecule diffusion in zeolite crystals.     

Hydrogenation Size-Selective Pt/Hollow Beta Catalysts

The aim of the present work is to synthesize a zeolite-based catalyst with a hollow morphology and highly dispersed metal nanoparticles (NPs) encapsulated inside the zeolite micropores. For this purpose, we have studied a treatment using tetraalkylammonium (TAA) bromides for the selective removal of a large Pt particle from the outer surface of a hollow Beta zeolite. TEM analysis reveals that we succeeded in the synthesis of a hollow beta zeolite single crystal with encapsulated particles, with a high dispersion of 50–60 %. The molecular-sieve-type mechanism of the obtained catalysts was evaluated in the model reaction of toluene and mesitylene catalytic hydrogenation. Thanks to the high dispersion. a 10-fold activity enhancement has been obtained with respect to hollow beta zeolites with encapsulated NPs recently described in the literature.     

多级孔Fe-HBeta分子筛的合成及其催化性能探究

采用软模板法一步合成了一系列铁同晶取代的多级孔Beta分子筛(nFe-HBeta,n=Fe/Al),并通过等体积浸渍法制备出系列Ni基催化剂(10Ni/nFe-HBeta)。结果表明,系列nFe-HBeta均为结晶度高、孔道结构丰富的片状结构。异质铁原子的引入在降低介孔相有序度的同时,促使沸石颗粒粒径下降,中强酸性位点数量显著减少。对于10Ni/nFe-HBeta催化剂而言,骨架铁与NiO之间存在协同作用,可增强活性组分Ni与载体间的作用力,提高活性金属Ni的分散度,降低NiO颗粒粒径。在乙醇水蒸气重整催化反应中,铁元素的引入可规避酸性位以抑制乙醇脱水反应,同时加强CO和CH_4的水蒸气重整反应,有效提高H_2选择性。其中,10Ni/0.15Fe-HBeta催化剂在500℃时,H_2选择性高达72.15%,C_2H_5OH转化率为99.6%,反应12 h后的积炭量仅为4.3%。     

A Pd@Zeolite Catalyst for Nitroarene Hydrogenation with High Product Selectivity by Sterically Controlled Adsorption in the Zeolite Micropores

The adsorption of molecules on metal nanoparticles can be sterically controlled through the use of zeolite crystals, which enhances the product selectivity in hydrogenations of reactants with more than one reducible group. Key to this success was the fixation of Pd nanoparticles inside Beta zeolite crystals to form a defined structure (Pd@Beta). In the hydrogenation of substituted nitroarenes with multiple reducible groups as a model reaction, the Pd@Beta catalyst exhibited superior selectivity for hydrogenation of the nitro group, outperforming both conventional Pd nanoparticles supported on zeolite crystals and a commercial Pd/C catalyst. The extraordinary selectivity of Pd@Beta was attributed to the sterically selective adsorption of the nitroarenes on the Pd nanoparticles controlled by the zeolite micropores, as elucidated by competitive adsorption and adsorbate displacement tests. Importantly, this strategy is general and was extended to the synthesis of selective Pt and Ru catalysts by fixation inside Beta and mordenite zeolites.     

Dispersion and Orientation of Zeolite ZSM‐5 Crystallites within a Fluid Catalytic Cracking Catalyst Particle

Confocal fluorescence microscopy was employed to selectively visualize the dispersion and orientation of zeolite ZSM‐5 domains inside a single industrially applied fluid catalytic cracking (FCC) catalyst particle. Large ZSM‐5 crystals served as a model system together with the acid‐catalyzed fluorostyrene oligomerization reaction to study the interaction of plane‐polarized light with these anisotropic zeolite crystals. The distinction between zeolite and binder material, such as alumina, silica, and clay, within an individual FCC particle was achieved by utilizing the anisotropic nature of emitted fluorescence light arising from the entrapped fluorostyrene‐derived carbocations inside the zeolite channels. This characterization approach provides a non‐invasive way for post‐synthesis characterization of an individual FCC catalyst particle in which the size, distribution, orientation, and amount of zeolite ZSM‐5 aggregates can be determined. It was found that the amount of detected fluorescence light originating from the stained ZSM‐5 aggregates corresponds to about 15 wt %. Furthermore, a statistical analysis of the emitted fluorescence light indicated that a large number of the ZSM‐5 domains appeared in small sizes of about 0.015–0.25 μm², representing single zeolite crystallites or small aggregates thereof. This observation illustrated a fairly high degree of zeolite dispersion within the FCC binder material. However, the highest amount of crystalline material was aggregated into larger domains (ca. 1–5 μm²) with more or less similarly oriented zeolite crystallites. It is clear that this visualization approach may serve as a post‐synthesis quality control on the dispersion of zeolite ZSM‐5 crystallites within FCC particles.     

微介孔复合分子筛合成及其在汽车冷启动尾气控制中的应用

分别采用稀溶液和浓溶液双模板剂两步水热合成法,以二氧化硅微硅粉和铝酸钠为硅源和铝源,第一步获得β分子筛晶种,第二步以β分子筛晶种为结构单元组装形成兼具MCM-41分子筛和β分子筛结构特点的复合型分子筛β/M(其中β是指β分子筛,M是指MCM-41介孔分子筛).采用X射线衍射(XRD)、傅里叶变换红外(FT-IR)光谱、氮气吸附(BET)和高分辨透射电镜(HRTEM)对样品的物相结构和微观形貌进行了表征,并对复合分子筛的合成过程进行了分析.结果表明:复合分子筛β/M的形成是微孔β结构和介孔MCM-41结构的竞争生长过程,β分子筛晶种的晶化时间和晶粒度大小对β/M复合分子筛的结构有重要影响.此外,我们以甲苯为探针分子,比较研究了三类分子筛β/M、MCM-41和β的原样以及经高温水热处理后样品的吸附性能,结果表明:β/M复合分子筛的热稳定性优于介孔分子筛MCM-41,其甲苯吸附容量比MCM-41和β分子筛的高,其中以浓溶液法合成的复合分子筛吸附容量最高.     

Probing the Different Life Stages of a Fluid Catalytic Cracking Particle with Integrated Laser and Electron Microscopy

While cycling through a fluid catalytic cracking (FCC) unit, the structure and performance of FCC catalyst particles are severely affected. In this study, we set out to characterize the damage to commercial equilibrium catalyst particles, further denoted as ECat samples, and map the different pathways involved in their deactivation in a practical unit. The degradation was studied on a structural and a functional level. Transmission electron microscopy (TEM) of ECat samples revealed several structural features; including zeolite crystals that were partly or fully severed, mesoporous, macroporous, and/or amorphous. These defects were then correlated to structural features observed in FCC particles that were treated with different levels of hydrothermal deactivation. This allowed us not only to identify which features observed in ECat samples were a result of hydrothermal deactivation, but also to determine the severity of treatments resulting in these defects. For functional characterization of the ECat sample, the Brønsted acidity within individual FCC particles was studied by a selective fluorescent probe reaction with 4‐fluorostyrene. Integrated laser and electron microscopy (iLEM) allowed correlating this Brønsted acidity to structural features by combining a fluorescence and a transmission electron microscope in a single set‐up. Together, these analyses allowed us to postulate a plausible model for the degradation of zeolite crystals in FCC particles in the ECat sample. Furthermore, the distribution of the various deactivation processes within particles of different ages was studied. A rim of completely deactivated zeolites surrounding each particle in the ECat sample was identified by using iLEM. These zeolites, which were never observed in fresh or steam‐deactivated samples, contained clots of dense structures. The structures are proposed to be carbonaceous deposits formed during the cracking process, and seem resistant towards burning off during catalyst regeneration.     

Confined space synthesis. A novel route to nanosized zeolites

Confined space synthesis is a novel method in zeolite synthesis. It involves crystallization of the zeolite inside the pore system of an inert mesoporous matrix. In this way it is possible to prepare nanosized zeolites with a controlled size distribution by proper choice of the inert matrix. Here, confined space synthesis was adopted to prepare nanosized ZSM-5, zeolite Beta, zeolite X, and zeolite A with tailored crystal size distributions using mesoporous carbon blacks as inert matrices. All zeolites were characterized by X-ray powder diffraction, transmission electron microscopy, and nitrogen adsorption/desorption prior to and after removal of the carbon matrix. ZSM-5 with Si/Al ratios of 50, 100, and infinity (silicalite-1) were synthesized with controlled average crystal sizes in the range 20-75 nm. Nanosized zeolite Beta (7-30 nm), zeolite X (22-60 nm), and zeolite A (25-37 nm) were prepared similarly. Removal of the carbon matrix by controlled combustion allows a convenient method for isolation of the pure and highly crystalline zeolites. Therefore, confined space synthesis appears to be an attractive method for preparation of zeolites with a controlled size distribution.     

π–π Interactions Between Aromatic Groups in Amphiphilic Molecules: Directing Hierarchical Growth of Porous Zeolites

The development of hierarchical macro‐ or mesoporous zeolites is essential in zeolite synthesis because the size of the micropores limits mass transport and their use as industrial catalysts for bulky molecules. Although major breakthroughs have been achieved, fabricating crystallographically ordered mesoporous zeolites using a templating strategy is still an unsolved challenge. This minireview highlights our recent efforts on the self‐assembly of amphiphilic molecules to obtain ordered hierarchical MFI zeolites by introducing aromatic groups into the hydrophobic tail of the amphiphilic molecules. Owing to the geometric matching between the self‐assembled aromatic tails and the MFI framework, a) single‐crystalline mesostructured zeolite nanosheets (SCZNs), b) SCZNs with a 90° rotational intergrowth structure, c) a hierarchical MFI zeolite with a two‐dimensional square P4mm mesostructure, and d) a single‐crystalline mesoporous ZSM‐5 with three‐dimensional pores and sheetlike mesopores layered along the a‐axis were successfully synthesized.     

等级孔介孔-微孔TS-1分子筛单晶的合成及催化氯丙烯环氧化性能

针对当前钛硅型分子筛存在的微孔孔道孔径限制导致的流通扩散性能差及催化效率低等关键瓶颈问题, 通过在微孔分子筛中构筑跨尺度贯通高物质传输性能的等级孔道结构, 对钛硅分子筛(TS-1)晶体内等级孔道结构的可控构筑及其催化环氧化进行了研究, 成功制备出具有富含介孔孔道的等级孔介孔-微孔TS-1分子筛单晶材料(HTS-1), 其在氯丙烯催化环氧化反应中表现出了优异的催化活性及稳定性能.     

Effect of Sodium Concentration on the Synthesis of Faujasite by Two-step Synthesis Procedure

The relationship between the concentration of sodium cations and the properties of faujasite(FAU) zeolite was investigated using a two-step synthesis procedure including (1) formation of amorphous aluminosilicate precursors and separation of amorphous nanoparticles, and (2) transformation of these amorphous particles into zeolite crystals by treatment with alkali solutions(NaOH). Three representative samples including two nano-sized zeolites and one micron-sized zeolite were prepared using different concentrations of sodium hydroxide. The crystallization process of these zeolites was studied in detail by Fourier transform infrared(FTIR) spectrometry, nuclear magnetic resonance spectroscopy(NMR), X-ray diffraction(XRD), scanning electron microscopy (SEM), transmission electron microscopy(TEM), and N₂ adsorption. The results indicated that minor changes in the concertation of inorganic cations can significantly shorten the induction period and crystallization time and thus affect the morphology, size and chemical composition of the zeolite crystals.     

NixB/沸石催化剂的分散性和反应性

用晶内形成法制备了Ni_xB/沸石催化剂,用饱和氢化学吸附法结合TEM方法考察了负载金属的分散性,并研究了其己环烷脱氢反应性。结果表明,Ni_xB/沸石样品上负载金属的分散性高,金属粒径分布也相对集中;金属负载量、载体结构和性质以及Ni_xB的制备条件对负载金属的分散性有明显影响。Ni_xB/沸石样品呈现较好的环己烷脱氢反应性。     

Synthesis of Hierarchical MOR-Type Zeolites with Improved Catalytic Properties

Hierarchical MOR-type zeolites were synthesized in the presence of hexadecyltrimethylammonium bromide (CTAB) as a porogen agent. XRD proved that the concentration of CTAB in the synthesis medium plays an essential role in forming pure hierarchical MOR-type material. Above a CTAB concentration of 0.04 mol·L⁻¹, amorphous materials are observed. These hierarchical mordenite possess a higher porous volume compared to its counterpart conventional micrometer crystals. Nitrogen sorption showed the presence of mesoporosity for all mordenite samples synthesized in the presence of CTAB. The creation of mesopores due to the presence of CTAB in the synthesis medium does not occur at the expense of zeolite micropores. In addition, mesoporous volume and BET surface seem to increase upon the increase of CTAB concentration in the synthesis medium. The Si/Al ratio of the zeolite framework can be increased from 5.5 to 9.1 by halving the aluminum content present in the synthesis gel. These synthesized hierarchical MOR-type zeolites possess an improved catalytic activity for n-hexane cracking compared to large zeolite crystals obtained in the absence of CTAB.     

Nanofusion: mesoporous zeolites made easy

A new path to zeolites: Nanofusion is a template-free, one-step process that gives mesoporous zeolite beta with tunable mesopore diameters in very short reaction times. The hierarchical materials are built from zeolite beta nanocrystals in concentrated gels. The nanocrystals can either be retrieved as individual particles in a colloidal suspension or are directly fused into mesoporous zeolitic materials (see scheme).     

In situ SAXS/WAXS of zeolite microwave synthesis: NaY, NaA, and beta zeolites.

A custom waveguide apparatus is constructed to study the microwave synthesis of zeolites by in situ small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). The WR-284 waveguide is used to heat precursor solutions using microwaves at a frequency of 2.45 GHz. The reaction vessels are designed to include sections of thin-walled glass, which permit X-rays to pass through the precursor solutions with minimal attenuation. Slots were machined into the waveguide to provide windows for X-ray energy to enter and scatter from solutions during microwave heating. The synthesis of zeolites with conventional heating is also studied using X-ray scattering in the same reactor. SAXS studies show that the crystallization of beta zeolite and NaY zeolite is preceded by a reorganization of nanosized particles in their precursor solutions or gels. The evolution of these particles during the nucleation and crystallization stages of zeolite formation depends on the properties of the precursor solution. The synthesis of NaA and NaX zeolites and sodalite from a single zeolite precursor is studied by microwave and conventional heating. Microwave heating shifts the selectivity of this synthesis in favor of NaA and NaX over sodalite; conventional heating leads to the formation of sodalite for synthesis from the same precursor. The use of microwave heating also led to a more rapid onset of NaA zeolite product crystallization compared to conventional heating. Pulsed and continuous microwave heating are compared for zeolite synthesis. The resulting rates of formation of the zeolite products, and the relative amounts of the products determined from the WAXS spectra, are similar when either pulsed or continuous microwave heating is applied in the reactor while maintaining the same synthesis temperature. The consequences of these results in terms of zeolite synthesis are discussed.     

The Link between ZSM-5 Zeolite Crystallization and Mesopore Formation by Leaching

Acid or base leaching are well-established tools in the synthesis of mesoporous zeolites. Previous studies suggest an inherent link between the structure-property relationship of mesoporous zeolites, that is, chemical resistance, pore diameter and distribution, with zeolite synthesis or crystallization conditions. The exact nature and/or origin of this link is currently however, poorly established. Here, we provide evidence how zeolite crystallization conditions influence the leaching behavior and thus structure of mesoporous zeolites. Electron microscopy and in situ small angle X-ray scattering both confirmed the crystallization of ZSM-5 to utilize both nanoparticles and oligomers as elemental building blocks. Utilization of these species is highly depended on supersaturation. The precursor solution of decreased water content favored a faster consumption of nanoparticles compared to its oligomers at the early stage of crystallization. Then the addition of oligomers can heal the surface imperfections and thus the resulting zeolite showed a higher resistance against acid leaching. In contrast, within the precursor solution of increased water content the slower consumption of nanoparticles led to crystals with a less robust rim. Defects existed in the rim due to limited healing by oligomers and, as such, mesopores can be created by the following post-treatment. Precise control over selected crystallization conditions can therefore further aid the design of optimized mesoporous zeolites.     

Tailor and Control of Acidic Strength in Ordered Mesoporous Aluminosilicates by Using Preformed Zeolite Precursors

The acidic strength of ordered mesoporous aluminosilicates of MAS-2, MAS-3, MAS-7 and MAS-9 and microporous crystals of Y, L, beta, and ZSM-5 zeolites was systemically investigated by temperature-programmed desorption of ammonia (NH3-TPD). Due to the use of preformed zeolite precursors of Y, L, beta and ZSM-5, the ordered mesoporous aluminosilicates with distinguished acidic strength were obtained, being dependent on the type of preformed zeolite precursors. Therefore, the acidic strength of these mesoporous aluminosilicates could be tailored and controlled.