UiO-66, MOF-808 and NU-1000 metal–organic frameworks exhibit a differentiated reactivity toward [Mg­(OMe)2(MeOH)2]4 related to their pore accessibility. Microporous UiO-66 remains unchanged while mesoporous MOF-808 and hierarchical micro/mesoporous NU-1000 materials yield doped systems containing exposed MgZr5O2(OH)6 clusters in the mesoporous cavities. This modification is responsible for a remarkable enhancement of the catalytic activity toward the hydrolytic degradation of P–F and P–S bonds of toxic nerve agents, at room temperature, in unbuffered aqueous solutions.

We report the controlled synthesis of thin films of p r o t o t y p i c a l z i r c o n i u m m e t a l − o r g a n i c f r a m e w o r k s [Zr 6 O 4 (OH) 4 (benzene-1,4-dicarboxylate-2-X) 6 ] (X = H, UiO-66 and X = NH 2 , UiO-66-NH 2 ) over the external surface of shaped carbonized substrates (spheres and textile fabrics) using a layer-by-layer method. The resulting composite materials contain metal−organic framework (MOF) crystals homogeneously distributed over the external surface of the porous shaped bodies, which are able to capture an organophosphate nerve agent simulant (diisopropylfluorophosphate, DIFP) in competition with moisture (very fast) and hydrolyze the P−F bond (slow). This behavior confers the composite material self-cleaning properties, which are useful for blocking secondary emission problems of classical protective equipment based on activated carbon.

Organophosphate nerve agents and pesticides are extremely toxic compounds because they result in acetylcholinesterase (AChE) inhibition and concomitant nerve system damage. Herein, we report the synthesis, structural characterization, and proof-of-concept utility of zirconium metal−organic polyhedra (Zr-MOPs) for organophosphate poisoning treatment. The results show the formation of robust tetrahedral cages [((n-butylCpZr) 3 (OH) 3 O) 4 L 6 ]Cl 6 (Zr-MOP-1; L = benzene-1,4dicarboxylate, n-butylCp = n-butylcyclopentadienyl, Zr-MOP-10, and L = 4,4′-biphenyldicarboxylate) decorated with lipophilic alkyl residues and possessing accessible cavities of ∼9.8 and ∼10.7 Å inner diameters, respectively. These systems are able to both capture the organophosphate model compound diisopropylfluorophosphate (DIFP) and host and release the AChE reactivator drug pralidoxime (2-PAM). The resulting 2-PAM@ Zr-MOP-1(0) host−guest assemblies feature a sustained delivery of 2-PAM under simulated biological conditions, with a concomitant reactivation of DIFP-inhibited AChE. Finally,

A simple yet powerful strategy of carrying out free radical polymerization of methacrylate monomers using a MOF-based initiator. The obtained composites maintain high catalytic activity towards a chemical warfare agent (CWA) simulant.