Embedded growth of colorful CsPbX3 (X = Cl, Br, I) nanocrystals in metal−organic frameworks at Room Temperature

Herein, we develop a novel strategy for preparing all-inorganic cesium lead halide (CsPbX3, X= Cl, Br, I) perovskite nanocrystals (NCs)@Zn-based metal-organic framework (MOF) composites through interfacial synthesis. The successful embedding of fluorescent perovskite NCs in Zn-MOFs is due to the in-situ confined growth, which is attributed to the re-nucleation of water-triggered phase transformation from Cs4PbBr6 to CsPbBr3. The controllable synthesis of mixed-halide based composites with various emission wavelength can be achieved by adding the desired amount of halide (Cl or I) salts in the re-nucleation process. More importantly, the anion exchange reaction is inhibited among various composites with different halogen atoms by being trapped in MOFs. Besides, a white light-emitting diode (WLED) is produced using a blue LED chip with the green-emitting and red-emitting composites, which has a color coordinate of (0.3291, 0.3272) and a wide color gamut. This work provides a novel route to achieving perovskite NCs growth in MOFs, which also can be extended to the other NCs embedded in frames as well.

A smart and responsive crystalline porous organic cage membrane with switchable pore apertures for graded molecular sieving

Membranes with high selectivity offer an attractive route to molecular separations, where technologies such as distillation and chromatography are energy intensive. However, it remains challenging to fine tune the structure and porosity in membranes, particularly to separate molecules of similar size. Here, we report a process for producing composite membranes that comprise crystalline porous organic cage films fabricated by interfacial synthesis on a polyacrylonitrile support. These membranes exhibit ultrafast solvent permeance and high rejection of organic dyes with molecular weights over 600 g mol−1. The crystalline cage film is dynamic, and its pore aperture can be switched in methanol to generate larger pores that provide increased methanol permeance and higher molecular weight cut-offs (1,400 g mol−1). By varying the water/methanol ratio, the film can be switched between two phases that have different selectivities, such that a single, ‘smart’ crystalline membrane can perform graded molecular sieving. We exemplify this by separating three organic dyes in a single-stage, single-membrane process.

Templated interfacial synthesis of metal-organic framework (MOF) nano- and micro-structures with precisely controlled shapes and sizes

Metal-organic frameworks (MOF) are an emerging class of microporous materials with promising applications. MOF nanocrystals, and their assembled super-structures, can display unique properties and reactivities when compared with their bulk analogues. MOF nanostructures of 0-D, 2-D, and 3-D dimensions can be routinely obtained by controlling reaction conditions and ligand additives, while formation of 1-D MOF nanocrystals (nanowires and nanorods) and super-structures has been relatively rare. We report here a facile templated interfacial synthesis methodology for the preparation of a series of 1-D MOF nano- and micro-structures with precisely controlled shapes and sizes. Specifically, by applying track-etched polycarbonate (PCTE) membranes as the templates and at the oil/water interface, we rapidly and reproducibly synthesize zeolitic imidazolate framework-8 (ZIF-8) and ZIF-67 nano- and micro structures of sizes ranging from 10 nm to 20 μm. We also identify a size confinement effect on MOF crystal growth, which leads to single crystals under the most restricted conditions and inter-grown polycrystals at larger template pore sizes, as well as surface directing effects that influence the crystallographic preferred orientation. Our findings provide a potentially generalizable method for controlling the size, morphology, and crystal orientations of MOF nanomaterials, as well as offering fundamental understanding into MOF crystal growth mechanisms.

Interfacial Synthesis: Morphology, Structure, and Properties of Interfacial Formations in Liquid–Liquid Systems

The results of studies in the field of interfacial synthesis and interfacial formations in liquid–liquid systems are summarized. The mechanisms of the processes of interfacial synthesis are considered. Data on the self-assembly of nanoparticles, films, and 3D materials are given. The properties of materials of interfacial formations in systems with rare-earth elements and di(2-ethylhexyl)phosphoric acid, obtained both in the presence and absence of local vibrations, are described. It was established that materials obtained in the presence of local vibrations in the interfacial layer have higher density, melting point, and magnetic susceptibility and lower electric conductivity. The effect of force field parameters on the properties of interfacial formations is considered. Practical applications and prospects for research in the field of interfacial formations are discussed.