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Aerogels are porous ultralight materials known for their high porosity, wide range of pore sizes, low density, and good macroscopic mechanical properties, all of which make them promising candidates for shaped adsorbents, catalysts, and insulators, among other applications. Here, this work reports a new approach that enables both the formation of modular aerogels, via dynamic covalent chemistry, and their post‐synthetic modification, via coordination chemistry. To demonstrate this strategy, this work first polymerizes porous amino‐functionalized Rh(II)‐based metal‐organic polyhedra (MOPs) with aldehydes, which afforded robust imine‐gel networks that is then converted into aerogels. Next, this work functionalizes these aerogels through the coordination of ligands on the axial site of Rh(II) paddlewheels of the MOP. Interestingly, in this chemistry, the local changes in the coordination site of the MOPs are transferred to the overall aerogel, thereby altering its macroscopic physicochemical properties. Importantly, this feature enables the synthesis of optimized adsorbents tailored to specific guests, as this work demonstrates through a series of experiments using ligands of different electrostatic and hydrophobic characters. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) based on high-connected nets are generally very attractive due to their combined robustness and porosity. Here, we describe the synthesis of BCN-348, a new high-connected Zr-MOF built from an 8-connected (8-c) cubic Zr-oxocluster and an 8-c organic linker. BCN-348 contains a minimal edge-transitive 3,4,8-c eps net, and combines mesoporosity with thermal and hydrolytic stability. Encouraging results from preliminary studies on its use as a catalyst for hydrolysis of a nerve-agent simulant suggest its potential as an agent for detoxification of chemical weapons and other pernicious compounds. [ABSTRACT FROM AUTHOR]

The use of covalent organic frameworks (COFs) in practical applications demands shaping them into macroscopic objects, which remains challenging. Herein, we report a simple three‐step method to produce COF aerogels, based on sol‐gel transition, solvent‐exchange, and supercritical CO2 drying, in which 2D imine‐based COF sheets link together to form hierarchical porous structures. The resultant COF aerogel monoliths have extremely low densities (ca. 0.02 g cm−3), high porosity (total porosity values of ca. 99 %), and mechanically behave as elastic materials under a moderate strain (<25–35 %) but become plastic under greater strain. Moreover, these COF aerogels maintain the micro‐ and meso‐porosity of their constituent COFs, and show excellent absorption capacity (e.g. toluene uptake: 32 g g−1), with high removal efficiency (ca. 99 %). The same three‐step method can be used to create functional composites of these COF aerogels with nanomaterials. [ABSTRACT FROM AUTHOR]

Herein, we describe a new class of porous composites comprising metal–organic framework (MOF) crystals confined in single spherical matrices made of packed covalent‐organic framework (COF) nanocrystals. These MOF@COF composites are synthesized through a two‐step method of spray‐drying and subsequent amorphous (imine‐based polymer)‐to‐crystalline (imine‐based COF) transformation. This transformation around the MOF crystals generates micro‐ and mesopores at the MOF/COF interface that provide far superior porosity compared to that of the constituent MOF and COF components added together. We report that water sorption in these new pores occurs within the same pressure window as in the COF pores. Our new MOF@COF composites, with their additional pores at the MOF/COF interface, should have implications for the development of new composites. [ABSTRACT FROM AUTHOR]

Controlling the shape of metal–organic framework (MOF) crystals is important for understanding their crystallization and useful for myriad applications. However, despite the many advances in shaping of inorganic nanoparticles, post‐synthetic shape control of MOFs and, in general, molecular crystals remains embryonic. Herein, we report using a simple wet‐chemistry process at room temperature to control the anisotropic etching of colloidal ZIF‐8 and ZIF‐67 crystals. Our work enables uniform reshaping of these porous materials into unprecedented morphologies, including cubic and tetrahedral crystals, and even hollow boxes, by an acid–base reaction and subsequent sequestration of leached metal ions. Etching tests on these ZIFs reveal that etching occurs preferentially in the crystallographic directions richer in metal–ligand bonds; that, along these directions, the etching rate tends to be faster on the crystal surfaces of higher dimensionality; and that the etching can be modulated by adjusting the pH of the etchant solution.Post‐synthetic wet‐chemical anisotropic etching of colloidal ZIF‐8 and ZIF‐67 crystals enables uniform reshaping of them into unprecedented shapes, including cubic and tetrahedral crystals, and even hollow boxes, by an acid–base reaction and subsequent sequestration of leached metal ions. [ABSTRACT FROM AUTHOR]