Textile/Metal–Organic‐Framework Composites as Self‐Detoxifying Filters for Chemical‐Warfare Agents

The current technology of air‐filtration materials for protection against highly toxic chemicals, that is, chemical‐warfare agents, is mainly based on the broad and effective adsorptive properties of hydrophobic activated carbons. However, adsorption does not prevent these materials from behaving as secondary emitters once they are contaminated. Thus, the development of efficient self‐cleaning filters is of high interest. Herein, we report how we can take advantage of the improved phosphotriesterase catalytic activity of lithium alkoxide doped zirconium(IV) metal–organic framework (MOF) materials to develop advanced self‐detoxifying adsorbents of chemical‐warfare agents containing hydrolysable P? F, P? O, and C? Cl bonds. Moreover, we also show that it is possible to integrate these materials onto textiles, thereby combining air‐permeation properties of the textiles with the self‐detoxifying properties of the MOF material.     

Instantaneous Hydrolysis of Nerve‐Agent Simulants with a Six‐Connected Zirconium‐Based Metal–Organic Framework

A nerve‐agent simulant based on a phosphate ester is hydrolyzed using a MOF‐based catalyst. Suspensions of MOF‐808 (6‐connected), a material featuring 6‐connected zirconium nodes, display the highest hydrolysis rates among all MOFs that have been reported to date. A plug‐flow reactor was also prepared with MOF‐808 (6‐connected) as the active layer. Deployed in a simple filtration scheme, the reactor displayed high hydrolysis efficiency and reusability.     

Simple and Compelling Biomimetic Metal–Organic Framework Catalyst for the Degradation of Nerve Agent Simulants

Inspired by biology, in which a bimetallic hydroxide‐bridged zinc(II)‐containing enzyme is utilized to catalytically hydrolyze phosphate ester bonds, the utility of a zirconium(IV)‐cluster‐containing metal–organic framework as a catalyst for the methanolysis and hydrolysis of phosphate‐based nerve agent simulants was examined. The combination of the strong Lewis‐acidic Zr^IV and bridging hydroxide anions led to ultrafast half‐lives for these solvolysis reactions. This is especially remarkable considering that the actual catalyst loading was a mere 0.045 % as a result of the surface‐only catalysis observed.