The synthesis of zeolite Y and its application in fluidized catalytic cracking could be taken as a milestone in the field of oil refining and petrochemical industry. It is well-known that the framework SiO2/Al2O3 molar ratio(SAR) of zeolite Y determines its thermal/hydrothermal stability and catalytic properties. To improve the framework SAR of zeolite Y can effectively decrease acid sites density, enhance acid strength and thus ameliorate the thermal/hydrothermal stability and catalytic cracking performance. Currently, the high silica zeolite Y used in industry is prepared by complex post-synthesis treatment. Although direct synthesis is an ideal way to obtain high zeolite Y, it remains a challenging topic in the field of zeolite synthesis. Herein, we review the progress in direct synthesis of high silica zeolite Y, including the syntheses both in inorganic and organic systems. At last, we summarize the crystallization mechanism of zeolite Y.
Zeolites are a vital type of crystalline material with well-defined channel structures and isolated catalytically active sites. However, their microporous nature hinders their applications in the transformation of bulky molecules. Ten years ago, Corma and coworkers provided a historical review of the synthesis, structure, and catalytic performance of extra-large pore(ELP) zeolites. This type of zeolite bridges the gap between traditional zeolites and ordered mesoporous materials. In the last decade, several new ELP zeolites, as well as novel methodologies for preparing them, have been reported. This review provides a renewed view of this topic.
Zeolites have been widely utilized in chemical industry as the most important solid catalysts because of their tunable acidities and shape selective catalysis. Synthesis of zeolites is usually performed via hydrothermal crystallization in a strong basic medium. Hydroxide ions(OH?) are considered to catalyze the depolymerization and polymerization of the silicate and aluminate species. Recently, it was found that the hydroxyl radicals(·OH) existed in the hydrothermal synthesis system. By using physical or chemical methods such as ultraviolet irradiation and Fenton’s reagent, ·OH radicals can be introduced into the zeolite synthesis system, which remarkably accelerated the zeolite crystallization and promoted the formation of zeolites with higher SiO2/Al2O3 ratio. Density functional theory calculations demonstrated that ·OH radicals significantly facilitated the depolymerization of the aluminosilicate gel by breaking the Si—O—Si bonds and the polymerization of the aluminosilicate anions around the hydrated cation species by remaking the Si—O—Si bonds, thus speeding up the nucleation and favoring Si incorporation into the zeolite frameworks. This review summarizes the recent progress in the application of ·OH radicals in the synthesis of zeolites, with an emphasis on the role and advantage of ·OH radicals in zeolite crystallization. The future perspective of the ·OH radical route for the synthesis of zeolites is pointed out.
In recent decades, fabrication of zeolite layers has attracted much research interest due to their potential applications in fields of separation, catalysis, sensing, and anticorrosion. Among them, uniformly oriented zeolite layers which benefit from reduced diffusion path lengths and decreased grain boundary defects have become the focus of researchers’ attention. In this review, major achievements made in oriented zeolite layer preparation were reviewed and commented with particular emphasis on the preparation of two-dimen- sional MFI nanosheets, deposition of b-oriented MFI seed monolayers, and microstructural manipulation of b-oriented MFI layers during secondary growth. Moreover, major problems hindering their bulk production were introduced and possible solutions were proposed. Finally, further development in this research field was highlighted.
Carbohydrates are important biomass feedstock which can be transformed to expected products by catalytic processes. Metal-containing zeolites with Lewis acidity have been found to exhibit excellent reactivity in conversion of carbohydrates. Understanding the nature of active sites and reaction mechanism is essential for the development of highly active catalyst towards carbohydrates conversion. Nuclear magnetic resonance(NMR) spectroscopy is a powerful tool to provide useful information on active site and reaction mechanism in zeolite catalysis. This review focuses on the recent progress of NMR studies of active centers, interactions between catalysts and reactants, reaction mechanisms and product distributions in catalytic conversion of carbohydrates on zeolites. Challenges and opportunities in this field are also discussed.
Zeolites have the desired advantages of tunable acidity and shape selectivity for their outstanding performance in heterogeneous catalysis. This review focuses on the recent progress in the understanding of acidity and shape-selectivity in zeolites by solid-state nuclear magnetic resonance(ssNMR) spectroscopy. The number, strength, type, and synergistic effect of the acid sites in zeolites have been explored by ssNMR with/without probe molecules. Moreover, ssNMR investigations provide evidence of the shape-selectivity of zeolites by the direct observation of crucial intermediates in heterogeneous reactions. The synergy of the acidity and shape-selectivity helps the better design of the zeolites for better heterogeneous catalysis.
Zeolites, a class of crystalline microporous materials with unique channels or cavities, have excellent performance in adsorption, separation, and catalysis. In order to correlate the structure-property relationship, it is essential to determine the crystallographic structures of zeolite at the atomic level. In this review, a series of conventional and emerging techniques regarding X-ray crystallography and electron crystallography for characterizing the crystallographic structures of zeolites through real space and reciprocal space are introduced. Furthermore, 85 recently discovered novel zeolites are systemically summarized based on the structure determination approaches and their chemical compositions. Nine zeolites with different framework type codes(FTCs) are further highlighted due to their unique synthetic methodologies or structural features.
Transmission electron microscope has become a powerful tool to solve new zeolite structures, analyze structural defects and study active sites. It has two main functions, imaging and diffraction, including transmission/scanning transmission electron microscopy imaging, selected-area electron diffraction and three-dimensional electron diffraction. Multiple methods were usually combined for a thorough analysis. In recent years, there are breakthrough improvements on hardware of electron microscopes, especially the well- developed spherical aberration correctors and a variety of sensitive detectors, as well as developments of image processing methods. As a result, atomic level imaging of beam sensitive materials such as zeolites has been achievable. Moreover, in situ electron microscopy study of zeolite is also on the way, for a better understanding of zeolites growth and catalytic reaction. In this review we focus on the recent research progresses of zeolites studied by electron microscopy, including new structure analysis, handedness determination, metal@zeolites and so on.
Despite great efforts have been performed for a long time since 1950s’, new achievements for zeolite synthesis in recent years give many examples to overstep the traditional theory for zeolite crystallization, in particular to the template effect, water role, zeolite building units, and crystal transformation in the aluminosilicate zeolites. In this review, authors systemically discuss the essence of the aforementioned factors. By investigation of template effect, it is suggested a new strategy for organotemplate-free synthesis of aluminosilicate zeolites; through understanding the role of water in the zeolite synthesis, it is designed solvent-free synthesis of zeolites; observed by crystal transformation of zeolites, it is proposed that both low to high framework density and high to low framework density could be realized.
As a kind of important catalytic materials, zeolite has been widely used in chemical industry. In this paper, the applications of zeolite catalysts in the fields of petroleum refining, petrochemical, coal chemical, fine chemical and environmental chemical industries was systematically summarized. The significant role of zeolite catalysts in promoting technological progress and development of chemical industry was elucidated, and the future development of zeolite catalysts was prospected.
Recent advances in cooperative catalysis from adjacent acid sites in zeolite HZSM-5 is summarized in this review. The cooperativity is from the Br?nsted acid site and the Lewis acid site as well as from adjacent Br?nsted acid sites. Kinds of characterization are described for molecular adsorption, activation and transformation together with catalysis performance. The theoretical calculation is also performed to prove the cooperative catalysis. The challenge of studying the new facile pathway of cooperative catalysis is also raised up, and accurate measuring the distance of two acid sites and quantifing the amount of adjacent acid sites are pursued as well.
Membrane-based separation is an advanced technology with significantly low energy consumption, and has enormous potential in industrial separation applications. However, commercial gas separation membranes are subjected to the trade-off between selectivity and permeability. Membranes constructed with two- dimensional(2D) nanosheets as building units hopefully break through this bottleneck. To date, the most representative 2D nanosheet membranes are graphene and its derivatives, 2D zeolites, layered double hydro-xides, 2D transition metal dichalcogenides, 2D covalent organic frameworks and metal-organic framework materials. In this review, the developments and progresses of these membrane materials in the field of gas separation will be introduced, presenting their merits and demerits in the practical separation process simultaneously, and the challenges and development prospects of the 2D nanosheet membranes for gas separation applications will be discussed.
Adsorptive separation, the process of separating and purifying a gas mixture via the selective adsorption of one or more components on a porous solid adsorbent, is of great significance in industry. Zeolites, metal-organic framework materials and activated carbon are known as common solid adsorbents. Zeolites show significant advantages such as high specific surface area, high stability and low production cost to satisfy the requirements of highly efficient, energy-saving and environmentally friendly adsorptive separation processes. Therefore, zeolites have been established as most promising adsorbents for the separation of small molecules. In this review article, the existing materials, the fundamental mechanisms and the evaluation methods in adsorptive separation are firstly outlined. The applications of zeolites in air separation, hydrocarbon separation, carbon dioxide capture, aromatic sulfide removal, carbon monoxide adsorption, nitrogen oxides adsorption, hydrogen storage and hydrogen isotope separation are then summarized. Finally, the current status of small molecule separation based on zeolite membranes are briefly discussed. The relationship between the adsorption performance and the topology, framework composition, and modification methods of zeolites are focused, and the future research prospects are discussed on the basis of current achievements.
Zeolite membranes have been widely attractive in gas and liquid separations between small molecules for their advantages of well-defined sub-nanometer pores, good tolerance against high temperature, high pressure and organic solvents. Zeolite membrane reactor that integrates zeolite membrane and catalyst into one unit, where the reaction and component diffusion occur simultaneously, can shift the equilibrium so as to intensify the reaction process. In this review, we give a brief introduction on the significant progress of different kinds of zeolite membrane reactors in catalytic reactions in the last decade. Furthermore, the development trend of zeolite membrane reactors in future are discussed.
Germanosilicates with (extra)-large pores have shown significant potential in the bulky molecules-involved catalytic reactions. However, the Ge―O bonds are easily hydrolyzed even in humid environment and induced structural collapse, which restricts the practical application of germanosilicates. However, the weak Ge―O bonds also endow germanosilicates structural modifiable properties for possible construction of novel zeolite frameworks by partial or full removing framework Ge atoms to induce structural deconstruction and reconstruction. The review summarizes recent progresses achieved in field of germanosilicates, including structural stabilization of germanosilicates, structural modification of germanosilicates, and their promising catalytic applications. Last but not the least, future challenges in the field of germanosilicates are also proposed.
This review summarizes the recent progress on photoluminescent zeolite-based composite mate- rials, including the preparation and assembly strategies of composite materials based on encapsulating guests(e.g. rare earth metals, metal clusters, quantum dots/carbon dots and other luminescent emitters), photoluminescent properties and potential applications, as well as the possible host-guest interactions such as quantum confinement, intermolecular forces, energy/electron transfer. Finally, the further development and challenges of such composite materials are discussed.
Thisreview summarizes the latest progresses on the synthesis of zeolites using industrial solid wastes as raw materials. The industrial solid wastes include fly ash, perlite waste, coal gangue, spent FCC ca-talyst, lithium slag, bauxite residue, waste porcelain and glass. The zeolites crystallized from these industrial sold wastes are LTA, FAU, MFI, CHA, GIS, SOD, ANA and KFI. The key in the pretreatment of each solid waste was presented. Finally, the trend and challenges in the synthesis of zeolites using the industrial solid wasteswere discussed.
Hierarchical zeolites with intracrystalline mesopores exhibit the characteristic features of microporous zeolites and mesoporous materials, offering improved mass transport property and catalytic performance for zeolite materials. Development of mesoporous zeolites for catalysis, adsorption and separation has been significantly advanced in the past decades. In particular, several new synthesis strategies have been invented, which provided a wide range of flexibility and turnability to control the mesoporosity, composition and morpho-logy of mesoporous zeolites. In the short review, we focus on the recent advances in different synthesis strategies. Particular emphasis is given to the recently developed post-synthetic methods for the synthesis of low Si/Al ratio mesoporous zeolites, synthesis of mesoporous zeolites by supramolecular self-assembly and in situ synthesis of mesoporous zeolites using small organic molecules. The formation mechanisms associated with the synthesis approaches are discussed in order to provide insights into future development of mesoporous zeolites. At the end of this review, we discuss some critical challenges regarding the synthesis of mesoporous zeolites using the different synthesis strategies.