Layer-by-Layer Integration of Zirconium Metal–Organic Frameworks onto Activated Carbon Spheres and Fabrics with Model Nerve Agent Detoxification Properties

Abstract

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.

Porous textile composites (PTCs) for the removal and the decomposition of chemical warfare agents (CWAs) – A review

“…Recently, UiO-66 and UiO-66-NH 2 MOF have been deposited on functionalized ACFs using a layer-by-layer deposition (Fig. 13) [283]. The association of ACFs and MOFs is almost inexistent surprisingly [284], the combination of activated carbons and MOFs being more developed so far [285][286][287][288].…”

“…13. Scheme of UiO-66 and UiO-66-NH 2 synthesis by a layer-by-layer deposition on functionalized activated carbons [283]. Reproduced with permission from the American Chemical Society.…”

“…This was explained by the higher hydrophilic capacity on the modified ACF, which leads to an increased adsorption of H 2 O, instead of DMMP. Recently, UiO-66 and UiO-66-NH 2 MOFs deposited on ACF were used to follow the degradation of diisopropylfluorophosphate (DIFP), with respectively 80 and 40 % of detoxification after 24 h [283]. The proposed mechanism was divided in three steps: (1) the strong adsorption of DIFP on the ACF materials, (2) the slow migration of physisorbed DIFP towards MOFs active sites due to desorption and (3) the hydrolysis by the Zr-MOF pore structure.…”

Zirconium Metal–Organic Polyhedra with Dual Behavior for Organophosphate Poisoning Treatment

“…Zirconium metal–organic frameworks (Zr-MOFs) based on [Zr 6 O 4 (OH) 4 ] secondary building units are being thoroughly studied for organophosphate capture and hydrolytic degradation due to the suitable combination of material robustness, high pore accessibility, and highly Lewis acidic zirconium metal centers. − However, the extended nature of these materials, unless in the nanometric form, make them unsuitable for organophosphate poisoning treatment. In this regard, metal–organic polyhedra (MOPs), − which can be considered downsized units of MOFs, are characterized by both a rich solid chemistry and a rich solution chemistry.…”

Layer-by-layer coating of MIL-100(Fe) on a cotton fabric for purification of water-soluble dyes by the combined effect of adsorption and photocatalytic degradation

“…[10][11][12][13] Among the methods, the layer by layer (LBL) approach has been used to attain a uniform coating by immersing the fabric substrate in a metal ion solution and then an organic ligand solution in sequence. [14][15][16] This LBL method, which proceeds at a relatively low temperature, is suitable for manufacturing the fabric-based MOF adsorbent, used for removal of organic pollutants existing in liquid. Da Silva Pinto et al 17 modied a cellulose fabric into an anionic surface through carboxymethylation, and the MOF (HKUST-1) was chemically bonded to the cellulose surface by the LBL procedure at room temperature.…”