5Porous metal-organic frameworks (MOFs) are highly ordered crystalline materials prepared by the selfassembly of metal ions with organic linkers to yield low density network structures of diverse topology. MOFs have attracted considerable attention over the last decade due to their facile preparation, tunable pore metrics and the ease of functionalisation of their internal surfaces, such that designer frameworks with exceptional properties for application in gas-storage, separation of small molecules, heterogeneous 10 catalysis and drug delivery are becoming commonplace. For any material to find practical utility however there is a need for processing and formulation into application-specific configurations. One way to do this is to prepare composite materials where the MOF is supported on a planar substrate or some other shaped body through interaction with functional groups at the support interface. This is a rapidly developing research area, and this review provides an overview of the diverse MOF composite materials prepared up 15 to now, organised by interface type. The importance of the interface is explored within each section and while the overall emphasis is on applications of the composites, coatings and MOF-based devices, the most widely-used and successful synthetic strategies for composite formation are also presented. (183 references)

Hollow composite microcapsules are prepared by the assembly of pre-formed nanocrystals of metal-organic frameworks (MOFs) around emulsion droplets, followed by interfacial polymerisation of the interior. The micropores of the MOF crystals embedded within a semipermeable hierarchically structured polymeric membrane are an effective combination for the retention of encapsulated dye molecules. Release can be triggered however by acid dissolution of the MOF component.

Here we report the grafting of N,N-dimethylaminoethyl methacrylate (DMAEMA) directly from poly(vinylidene fluoride) (PVDF) backbone in solution phase by atom transfer radical polymerization (ATRP). The graft length is same for different times of polymerization but graft density increases with increasing polymerization time. Four graft copolymers are prepared and depending on the time of conversion they are designated as PD-6, PD-12, PD-18, and PD-24, the number indicates time (h) of polymerization. A maximum of 36% (w/w) conversion with respect to monomer is achieved in the PD-24 sample. Gel permeation chromatography (GPC), nuclear magnetic resonance (NMR), and polymerization kinetics study conclude the ATRP nature of the polymerization. The graft copolymer shows induced solubility in water and the effective particle diameter in aqueous medium decreases from PD-6 to PD-24 samples. The enthalpy of fusion values are same in graft copolymers with more than 50% reduction and the melting points reduce by 5−6 °C than that of pure PVDF. WAXS patterns of graft copolymers indicate the formation of mixture of α and β phases in dimethyl formamide cast films and also suggest the existence of self-organized short-range ordering from supramolecular interaction between the >CO group and the nitrogen atom of the substituted amino group of the grafting component as is evident from the FTIR study. The absence of any lamellar peak than that of pure PVDF in the SAXS data suggests the formation of fringed micelle crystals in the graft copolymers. Storage modulus of graft copolymers decreases more than that of PVDF due to a decrease in crystallinity. The tensile stress−strain experiment of the PD samples indicates 700−750% elongation, which is 45 times higher than that of PVDF. The toughness increases by 1970% in the graft copolymers over that of pure PVDF, and the gluing property is significantly larger. The graft copolymers produce and stabilize gold nanoparticles in aqueous medium; produce amphiphilic membranes and on its modification to trimethyl ammonium ion it shows 2.2 × 10−6 S/cm dc-conductivity. Because of its water solubility, the polymer promises great use in biotechnology, nanotechnology, energy research, and separation processes.

A facile aqueous room temperature synthesis method has been developed to synthesize HKUST-1 from nano-materials to micro-and hierarchical porous structures by tuning either the copper source or the reaction time. The synthesis is readily scalable, with space-time yield >2000 kg m À3 day À1 .Scheme 1 One-pot synthetic routes to nano-, micro-and hierarchically porous HKUST-1 from a wholly aqueous reaction mixture.

Polyaniline (PANI)-dinonylnaphthalene disulfonic acid (DNNDSA) form a thermoreversible gel when prepared from formic acid medium. Mixing of organically modified montmorillonite (om-MMT) clay during PANI-DNNDSA gel preparation produces the PANI-DNNDSA gel nanocomposites (GNCs). WAXS and TEM pictures indicate GNC-1 (number indicates percentage (w/w) of om-clay in the nanocomposite) has an exfoliated structure, whereas GNC-3 and GNC-5 have an intercalated structure. FTIR spectra indicate an interaction between om-clay and PANI-DNNDSA shifting the QdN + H-B or B-N + H-B (Q ) quinonoid and B ) benzonoid unit of PANI) vibration of quinonoid structure to lower energy. The exfoliated GNC-1 has higher thermal stability than that of the intercalated GNC-3 and GNC-5 samples. The storage modulus (G′) has increased dramatically on addition of clay to the gel and its relative increase is larger with increase in temperature until the gel melts. The highest increase (445%) of G′ is observed for GNC-1 at 60 °C. The π band-polaron band position remains unaffected by the addition of clay in the gel and so also the dc conductivity. PANI-DNNDSA gel shows emission at 353 nm when excited with a radiation of 262 nm. But in the GNCs, fluorescence quenching occurs and it is maximum for the exfoliated GNC-1 sample. These GNCs of PANI are easily processable due to its thermoreversible nature.