Precursor nanoparticles that form spontaneously on hydrolysis of tetraethylorthosilicate in aqueous solutions of tetrapropylammonium (TPA) hydroxide evolve to TPA-silicalite-1, a molecular-sieve crystal that serves as a model for the self-assembly of porous inorganic materials in the presence of organic structure-directing agents. The structure and role of these nanoparticles are of practical significance for the fabrication of hierarchically ordered porous materials and molecular-sieve films, but still remain elusive. Here we show experimental findings of nanoparticle and crystal evolution during room-temperature ageing of the aqueous suspensions that suggest growth by aggregation of nanoparticles. A kinetic mechanism suggests that the precursor nanoparticle population is distributed, and that the 5-nm building units contributing most to aggregation only exist as an intermediate small fraction. The proposed oriented-aggregation mechanism should lead to strategies for isolating or enhancing the concentration of crystal-like nanoparticles.

Thin zeolite films are attractive for a wide range of applications, including molecular sieve membranes, catalytic membrane reactors, permeation barriers, and low-dielectric-constant materials. Synthesis of thin zeolite films using high-aspect-ratio zeolite nanosheets is desirable because of the packing and processing advantages of the nanosheets over isotropic zeolite nanoparticles. Attempts to obtain a dispersed suspension of zeolite nanosheets via exfoliation of their lamellar precursors have been hampered because of their structure deterioration and morphological damage (fragmentation, curling, and aggregation). We demonstrated the synthesis and structure determination of highly crystalline nanosheets of zeolite frameworks MWW and MFI. The purity and morphological integrity of these nanosheets allow them to pack well on porous supports, facilitating the fabrication of molecular sieve membranes.

Shaped zeolite nanocrystals and larger zeolite particles with three-dimensionally ordered mesoporous (3DOm) features hold exciting technological implications for manufacturing thin, oriented molecular sieve films and realizing new selective, molecularly accessible and robust catalysts. A recognized means for controlled synthesis of such nanoparticulate and imprinted materials revolves around templating approaches, yet identification of an appropriately versatile template has remained elusive. Because of their highly interconnected pore space, ordered mesoporous carbon replicas serve as conceptually attractive materials for carrying out confined synthesis of zeolite crystals. Here, we demonstrate how a wide range of crystal morphologies can be realized through such confined growth within 3DOm carbon, synthesized by replication of colloidal crystals composed of size-tunable (about 10-40 nm) silica nanoparticles. Confined crystal growth within these templates leads to size-tunable, uniformly shaped silicalite-1 nanocrystals as well as 3DOm-imprinted single-crystal zeolite particles. In addition, novel crystal morphologies, consisting of faceted crystal outgrowths from primary crystalline particles have been discovered, providing new insight into constricted crystal growth mechanisms underlying confined synthesis.

A seeded growth method for the fabrication of high-permeance, high-separation-factor zeolite (siliceous ZSM-5, [Si96O192]-MFI) membranes is reported. The method consists of growing the crystals of an oriented seed layer to a well-intergrown film by avoiding events that lead to a loss of preferred orientation, such as twin overgrowths and random nucleation. Organic polycations are used as zeolite crystal shape modifiers to enhance relative growth rates along the desirable out-of-plane direction. The polycrystalline films are thin (approximately 1 micrometer) with single grains extending along the film thickness and with large in-plane grain size (approximately 1 micrometer). The preferred orientation is such that straight channels with an open diameter of approximately 5.5 angstroms run down the membrane thickness. Comparison with previously reported membranes shows that these microstructurally optimized films have superior performance for the separation of organic mixtures with components that have small differences in size and shape, such as xylene isomers.

aThe latest developments in zeolite membranes are reviewed, with an emphasis on the synthesis techniques, including seed assembly and secondary growth methods. This review also discusses the current industrial applications of zeolite membranes, the feasibility of their use in membrane reactors and their hydrothermal stability. Finally, zeolite membranes are compared with metal-organic framework (MOF) membranes and the latest advancements in MOF and mixed matrix membranes are highlighted.

A zeolite with structure type MFI is an aluminosilicate or silicate material that has a three-dimensionally connected pore network, which enables molecular recognition in the size range 0.5-0.6 nm. These micropore dimensions are relevant for many valuable chemical intermediates, and therefore MFI-type zeolites are widely used in the chemical industry as selective catalysts or adsorbents. As with all zeolites, strategies to tailor them for specific applications include controlling their crystal size and shape. Nanometre-thick MFI crystals (nanosheets) have been introduced in pillared and self-pillared (intergrown) architectures, offering improved mass-transfer characteristics for certain adsorption and catalysis applications. Moreover, single (non-intergrown and non-layered) nanosheets have been used to prepare thin membranes that could be used to improve the energy efficiency of separation processes. However, until now, single MFI nanosheets have been prepared using a multi-step approach based on the exfoliation of layered MFI, followed by centrifugation to remove non-exfoliated particles. This top-down method is time-consuming, costly and low-yield and it produces fragmented nanosheets with submicrometre lateral dimensions. Alternatively, direct (bottom-up) synthesis could produce high-aspect-ratio zeolite nanosheets, with improved yield and at lower cost. Here we use a nanocrystal-seeded growth method triggered by a single rotational intergrowth to synthesize high-aspect-ratio MFI nanosheets with a thickness of 5 nanometres (2.5 unit cells). These high-aspect-ratio nanosheets allow the fabrication of thin and defect-free coatings that effectively cover porous substrates. These coatings can be intergrown to produce high-flux and ultra-selective MFI membranes that compare favourably with other MFI membranes prepared from existing MFI materials (such as exfoliated nanosheets or nanocrystals).

Zeolites and related crystalline microporous oxides-tetrahedrally coordinated atoms covalently linked into a porous framework-are of interest for applications ranging from catalysis to adsorption and ion-exchange. In some of these materials (such as zeolite rho) adsorbates, ion-exchange, and dehydration and cation relocation can induce strong framework deformations. Similar framework flexibility has to date not been seen in mixed octahedral/tetrahedral microporous framework materials, a newer and rapidly expanding class of molecular sieves. Here we show that the framework of the titanium silicate ETS-4, the first member of this class of materials, can be systematically contracted through dehydration at elevated temperatures to 'tune' the effective size of the pores giving access to the interior of the crystal. We show that this so-called 'molecular gate' effect can be used to tailor the adsorption properties of the materials to give size-selective adsorbents suitable for commercially important separations of gas mixtures of molecules with similar size in the 4.0 to 3.0 A range, such as that of N2/CH4, Ar/O2 and N2/O2.

Hydrogen sulfide removal is a long-standing economic and environmental challenge faced by the oil and gas industries. HS separation processes using reactive and non-reactive absorption and adsorption, membranes, and cryogenic distillation are reviewed. A detailed discussion is presented on new developments in adsorbents, such as ionic liquids, metal oxides, metals, metal-organic frameworks, zeolites, carbon-based materials, and composite materials; and membrane technologies for HS removal. This Review attempts to exhaustively compile the existing literature on sour gas sweetening and to identify promising areas for future developments in the field.