This review focuses on the synthesis, crystallization mechanism, and application of colloidal zeolites. The synthesis formulations and features of different zeolite-type structures prepared in nanosized form are summarized. Special attention is paid to zeolites prepared as stable colloidal suspensions. Next, new insights into zeolite crystallization mechanism gained by using colloidal zeolites as model systems are discussed. Further, the methods for deposition of zeolite nanocrystals from suspensions onto supports of different shapes and compositions used for the fabrication of zeolite films and membranes are reviewed. The use of colloidal zeolites for the fabrication of hierarchical macrostructures is also described. Other uses of nanozeolites for the preparation of functionalized materials, for the synthesis of mesoporous silicas of improved hydrothermal stability, and as seeds for zeolite syntheses are illustrated. The emerging applications of nanozeolites in sensing, optoelectronics, and medicine constitute another topic in this review. Finally, some future trends in the area are envisaged.

The formation and growth of crystal nuclei of zeolite A from clear solutions at room temperature were studied with low-dose, high-resolution transmission electron microscopy in field emission mode and with in situ dynamic light scattering. Single zeolite A crystals nucleated in amorphous gel particles of 40 to 80 nanometers within 3 days at room temperature. The resulting nanoscale single crystals (10 to 30 nanometers) were embedded in the amorphous gel particles. The gel particles were consumed during further crystal growth at room temperature, forming a colloidal suspension of zeolite A nanocrystals of 40 to 80 nanometers. On heating this suspension at 80 degrees C, solution-mediated transport resulted in additional substantial crystal growth.

The development of crystalline porous materials (CPMs) with high chemical stability is of paramount importance for their practical uses. Here we report the synthesis of novel polyarylether covalent organic frameworks (PAE-COFs) with high crystallinity, porosity and exceptional chemical stability due to the inert nature of polyarylether building blocks. We demonstrate that these materials can be stable against harsh chemical environments involving boiling water, strong acids/bases, oxidation and reduction conditions, which exceed all known CPMs, including zeolites, metal-organic frameworks (MOFs) and COFs. Furthermore, we explore their advantages as an efficient platform for structural design and functional evolution. The functionalized PAE-COFs combine porosity, high stability, and recyclability, and deliver outstanding performance in the removal of antibiotics from water over a wide pH range.

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The search for new types of membrane materials has been of continuous interest in both academia and industry, given their importance in a plethora of applications, particularly for energy-efficient separation technology. In this contribution, we demonstrate for the first time that a metal-organic framework (MOF) can be grown on the covalent-organic framework (COF) membrane to fabricate COF-MOF composite membranes. The resultant COF-MOF composite membranes demonstrate higher separation selectivity of H2/CO2 gas mixtures than the individual COF and MOF membranes. A sound proof for the synergy between two porous materials is the fact that the COF-MOF composite membranes surpass the Robeson upper bound of polymer membranes for mixture separation of a H2/CO2 gas pair and are among the best gas separation MOF membranes reported thus far.

Nanosized faujasite (FAU) crystals have great potential as catalysts or adsorbents to more efficiently process present and forthcoming synthetic and renewable feedstocks in oil refining, petrochemistry and fine chemistry. Here, we report the rational design of template-free nanosized FAU zeolites with exceptional properties, including extremely small crystallites (10-15 nm) with a narrow particle size distribution, high crystalline yields (above 80%), micropore volumes (0.30 cm(3) g(-1)) comparable to their conventional counterparts (micrometre-sized crystals), Si/Al ratios adjustable between 1.1 and 2.1 (zeolites X or Y) and excellent thermal stability leading to superior catalytic performance in the dealkylation of a bulky molecule, 1,3,5-triisopropylbenzene, probing sites mostly located on the external surface of the nanosized crystals. Another important feature is their excellent colloidal stability, which facilitates a uniform dispersion on supports for applications in catalysis, sorption and thin-to-thick coatings.

This review highlights recent developments in the synthesis of nanosized zeolites. The strategies available for their preparation (organic-template assisted, organic-template free, and alternative procedures) are discussed. Major breakthroughs achieved by the so-called zeolite crystal engineering and encompass items such as mastering and using the physicochemical properties of the precursor synthesis gel/suspension, optimizing the use of silicon and aluminium precursor sources, the rational use of organic templates and structure-directing inorganic cations, and careful adjustment of synthesis conditions (temperature, pressure, time, heating processes from conventional to microwave and sonication) are addressed. An on-going broad and deep fundamental understanding of the crystallization process, explaining the influence of all variables of this complex set of reactions, underpins an even more rational design of nanosized zeolites with exceptional properties. Finally, the advantages and limitations of these methods are addressed with particular attention to their industrial prospects and utilization in existing and advanced applications.

Crystalline microporous solids are an important class of inorganic materials with uses in different areas impacting our everyday lives, namely as catalysts, adsorbents, and ion exchangers. Advancements in synthesis have been invaluable in expanding the classical aluminosilicate zeolites to new unique framework types and compositions, motivating innovative developments. However, the inexhaustible post-synthetic options to tailor zeolite properties have been and will continue to be indispensable to realize emerging and to improve conventional applications. Starting from the routine drying and template removal processes that every zeolite must experience prior to use, a wide spectrum of treatments exists to alter individual or collective characteristics of these materials for optimal performance. This review documents the toolbox of post-synthetic strategies available to tune the properties of zeolitic materials for specific functions. The categorisation is based on the scale at which the alteration is aimed at, including the atomic structure (e.g. the introduction, dislodgment, or replacement of framework atoms), the micropore level (e.g. template removal and functionalisation by inorganic and organic species), and the crystal and particle levels (e.g. the introduction of auxiliary porosity). Through examples in the recent literature, it is shown that the combination of post-synthetic methods enables rational zeolite design, extending the characteristics of these materials way beyond those imposed by the synthesis conditions.