Graphene Oxide and Metal-Organic Framework-Based Breathable Barrier Membranes for Toxic Vapors.

Garments protective against chemical warfare agents (CWAs) or accidently released toxic chemicals must block the transport of toxic gases/vapors for a substantial time and allow moisture transport for breathability. These demands are challenging: either the barriers block CWAs effectively but have poor breathability or barriers have excellent breathability but cannot block CWAs well. Existing protective garments employ large amounts of active carbon, making them quite heavy.

Solid-Phase Detoxification of Chemical Warfare Agents using Zirconium-Based Metal Organic Frameworks and the Moisture Effects: Analyze via Digestion.

Zirconium-based metal organic frameworks (Zr-MOFs) are highly chemically and thermally stable and have been of particular interest as reactive sorbents for chemical warfare agent (CWA) removal due to their fast and selective reactivity toward CWAs reported in buffer solutions. However, we find that decontamination of neat CWAs directly on Zr-MOFs, UiO-66, UiO-66-NH, and NU-1000 is rather slow, and the reactivity trend and products generated are very different from those in solution. Furthermore, we show that their decontamination rates are affected by the amount of moisture present in the MOFs.

Photocatalytic Oxidation of Sulfur Mustard and Its Simulant on BODIPY-Incorporated Polymer Coatings and Fabrics.

Sulfur mustard is one of the most toxic chemical warfare agents worldwide. We report the use of 4,4-difluoro-4-bora-3a,4a-diaza- s-indacene (BODIPY) photosensitizers as a fast and effective sulfur mustard decontaminant and their incorporation into various polymer coatings and fabrics, including army combat uniform. These BODIPY-embedded materials are capable of generating singlet oxygen under visible light irradiation and effectively detoxifying sulfur mustard by converting it into nontoxic sulfoxides as the major products.

Postsynthetic Incorporation of a Singlet Oxygen Photosensitizer in a Metal-Organic Framework for Fast and Selective Oxidative Detoxification of Sulfur Mustard.

A fullerene-based photosensitizer is incorporated postsynthetically into a Zr -based MOF, NU-1000, for enhanced singlet oxygen production. The structural organic linkers in the MOF platform also act as photosensitizers which contribute to the overall generation of singlet oxygen from the material under UV irradiation. The singlet oxygen generated by the MOF/fullerene material is shown to oxidize sulfur mustard selectively to the less toxic bis(2-chloroethyl)sulfoxide with a half-life of only 11 min.

Efficient and selective oxidation of sulfur mustard using singlet oxygen generated by a pyrene-based metal-organic framework.

A pyrene-based metal-organic framework (MOF) NU-1000 was used as a heterogeneous photocatalyst for the degradation of a sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). Using irradiation from a commercially available and inexpensive ultraviolet (UV) light-emitting diode (LED), singlet oxygen (O) is generated by NU-1000 and selectively oxidizes CEES to the nontoxic product 2-chloroethyl ethyl sulfoxide (CEESO). More importantly, this method was tested on the warfare agent sulfur mustard (HD) for the first time using O and a MOF catalyst, and this method proved to be effective in oxidizing sulfur mustard to nontoxic products without forming the toxic sulfone by-product.

Mass transfer and adsorption equilibrium for low volatility alkanes in BPL activated carbon.

The structure of a molecule and its concentration can strongly influence diffusional properties for transport in nanoporous materials. We study mass transfer of alkanes in BPL activated carbon using the concentration-swing frequency response method, which can easily discriminate among mass transfer mechanisms. We measure concentration-dependent diffusion rates for n-hexane, n-octane, n-decane, 2,7-dimethyloctane, and cyclodecane, which have different carbon numbers and geometries: straight chain, branched chain, and cyclic.