The deformation of short-range order leading to rearrangement of topological network structure in zeolitic imidazolate framework glasses.

In recent years, the study of the glassy structure of zeolitic imidazolate frameworks (ZIFs) has been a key breakthrough in glass science. Yet the theoretical understanding of the structure of these complex materials is still in its infancy, especially the short-range structure. The short-structural disorder of two ZIFs and their corresponding molten structure, namely, ZIF-4 and ZIF-62 are studied, using ab initio simulations. Changes in short-range order are investigated, particularly the changes in bond length, bond angle, and tetrahedral unit volume. Furthermore, the asymmetric distribution of organic groups caused by the benzimidazole functional group leads to the difference in short-range disorder between ZIF-4 and ZIF-62 glasses, which contribute to the glass-forming ability difference.

Relating structural disorder and melting in complex mixed ligand zeolitic imidazolate framework glasses.

We report the formation of zeolitic imidazolate framework glasses incorporating three organic linkers, from their corresponding novel crystalline structures [Zn(Im2-x-ybImxmbImy)]. Structure-property relationships between chemical compositions and thermal properties are analysed, in addition to the effect on the nanoscale porosity of the glasses formed. A probabilistic model is used to explain melting and the glass transition temperatures of the obtained glasses and link to the nanoscale structural disorder of their crystalline starting structures.

Ultraselective Pebax Membranes Enabled by Templated Microphase Separation.

Block copolymer materials have been considered as promising candidates to fabricate gas separation membranes. This microphase separation affects the polymer chain packing density and molecular separation efficiency. Here, we demonstrate a method to template microphase separation within a thin composite Pebax membrane, through the controllable self-assembly of one-dimensional halloysite nanotubes (HNTs) within the thin film via the solution-casting technique. Crystallization of the polyamide component is induced at the HNT surface, guiding subsequent crystal growth around the tubular structure. The resultant composite membrane possesses an ultrahigh selectivity (up to 290) for the CO2/N2 gas pair, together with a moderate CO2 permeability (80.4 barrer), being the highest selectivity recorded for Pebax-based membranes, and it easily surpasses the Robeson upper bound. The templated microphase separation concept is further demonstrated with the nanocomposite hollow fiber gas separation membranes, showing its effectiveness of promoting gas selectivity.