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 Zr6 -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.

Experimental Study of the Adsorption and Decomposition of Sarin on Dry Copper(II) Oxide.

Organophosphonates were originally developed as insecticides but were quickly identified as highly toxic acetylcholinesterase inhibitors, leading to their exploitation as chemical warfare agents (CWA). To develop next generation filtration technologies, there must be a fundamental understanding of the molecular interactions occurring with toxic chemicals, such as CWAs. In this paper, we investigate the interaction between dry CuO nanoparticles and sarin (GB), using infrared (IR) spectroscopy in an effort to build an atomic understanding. We show sarin strongly interacts with CuO and then quickly degrades, primarily through the cleavage of the P-F bond, creating a bridging species on the CuO surface with the assistance of lattice oxygen. Upon heating, the decomposition product isopropyl methyl phosphonic acid (IMPA) does not continue to decompose but desorbs from the surface. These observations are further elaborated through theoretical models of sarin on dry CuO (111).

Degradation of Fatal Toxic Nerve Agents on Dry TiO2.

Despite a recent dramatically increased risk of using chemical warfare agents in chemical attacks and assassinations, fundamental interactions of toxic chemicals with other materials are poorly understood, and micromechanisms of their chemical degradation are yet to be established. This represents an outstanding challenge in both fundamental science and practical applications in combat against chemical weapons. One of the most versatile and multifunctional oxides, TiO2, has been suggested as a promising material to quickly adsorb and effectively destroy toxins. In this paper, we explore how sarin (also known as GB) adsorbs and decomposes on dry nanoparticles of TiO2 anatase and rutile phases. We found that both anatase and rutile readily adsorb sarin gas molecules because of a strong electrostatic attraction between the phosphoryl oxygen and surface titanium atoms. The sarin decomposition most likely proceeds via a propene elimination; however, the reaction is exothermic on the rutile (110) surface and endothermic on the anatase (101) surface. High energy barriers suggest that sarin would hardly decompose on pristine dry surfaces of TiO2, and degradation reactions can be triggered by defects or contaminants under realistic operational conditions.

Understanding Dimethyl Methylphosphonate Adsorption and Decomposition on Mesoporous CeO2.

The increased risk of chemical warfare agent usage around the world has intensified the search for high-surface-area materials that can strongly adsorb and actively decompose chemical warfare agents. Dimethyl methylphosphonate (DMMP) is a widely used simulant molecule in laboratory studies for the investigation of the adsorption and decomposition behavior of sarin (GB) gas. In this paper, we explore how DMMP interacts with the as-synthesized mesoporous CeO2. Our mass spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy measurements indicate that DMMP can dissociate on mesoporous CeO2 at room temperature. Two DMMP dissociation pathways are observed. Based on our characterization of the as-synthesized material, we built the pristine and hydroxylated (110) and (111) CeO2 surfaces and simulated the DMMP interaction on these surfaces with density functional theory modeling. Our calculations reveal an extremely low activation energy barrier for DMMP dissociation on the (111) pristine CeO2 surface, which very likely leads to the high activity of mesoporous CeO2 for DMMP decomposition at room temperature. The two reaction pathways are possibly due to the DMMP dissociation on the pristine and hydroxylated CeO2 surfaces. The significantly higher activation energy barrier for DMMP to decompose on the hydroxylated CeO2 surface implies that such a reaction on the hydroxylated CeO2 surface may occur at higher temperatures or proceed after the pristine CeO2 surfaces are saturated.

Spectroscopically Resolved Binding Sites for the Adsorption of Sarin Gas in a Metal-Organic Framework: Insights beyond Lewis Acidity.

Here we report molecular level details regarding the adsorption of sarin (GB) gas in a prototypical zirconium-based metal-organic framework (MOF, UiO-66). By combining predictive modeling and experimental spectroscopic techniques, we unambiguously identify several unique bindings sites within the MOF, using the P═O stretch frequency of GB as a probe. Remarkable agreement between predicted and experimental IR spectrum is demonstrated. As previously hypothesized, the undercoordinated Lewis acid metal site is the most favorable binding site. Yet multiple sites participate in the adsorption process; specifically, the Zr-chelated hydroxyl groups form hydrogen bonds with the GB molecule, and GB weakly interacts with fully coordinated metals. Importantly, this work highlights that subtle orientational effects of bound GB are observable via shifts in characteristic vibrational modes; this finding has large implications for degradation rates and opens a new route for future materials design.

Flexible SIS/HKUST-1 Mixed Matrix Composites as Protective Barriers against Chemical Warfare Agent Simulants.

We fabricated and demonstrated, for the first time, metal-organic framework (MOF), polymer mixed-matrix composites (MMCs) as effective, low burden barriers against chemical warfare agent (CWA) simulants. We incorporated the MOF HKUST-1 into elastomeric triblock copolymers of polystyrene- block-polyisoprene- block-polystyrene (SIS) for use as semipermeable barrier against the CWA simulant 2-chloroethyl ethyl sulfide (CEES). MMCs containing up to 50 wt % HKUST-1 were cast and evaluated for CEES permeation, moisture vapor transport rate (MVTR), and mechanical properties, such as elastic modulus and percent elongation. Increasing the MOF content resulted in longer protection against CEES with breakthrough times ranging from immediate breakthrough for the baseline SIS to over 4000 min for the best-performing MMC. MVTRs of high-MOF-content MMCs were approximately 5-10 times higher than either SIS or typical laboratory gloves made from nitrile and latex. The elastic moduli increased with increased MOF content corresponding to a reduction in percent elongation. The triblock copolymer also was found to protect the MOF crystal structure after exposure to CEES and liquid water, which may lead to longer usage time and shelf life. The ability to resist degradation due to moisture shows the potential utility of these composites when exposed to rain, sweat, or other moisture-rich environments. Finally, the MOF-containing composites functioned as robust colorimetric indicators of CEES exposure. Thus, these MMC materials present a potential route toward next-generation personal protective equipment with a combination of detoxification, sensing, environmental stability, and thermal/user-comfort properties not present in current materials solutions.

Reduced chemical warfare agent sorption in polyurethane-painted surfaces via plasma-enhanced chemical vapor deposition of perfluoroalkanes.

Perfluoralkalation via plasma chemical vapor deposition has been used to improve hydrophobicity of surfaces. We have investigated this technique to improve the resistance of commercial polyurethane coatings to chemicals, such as chemical warfare agents. The reported results indicate the surface treatment minimizes the spread of agent droplets and the sorption of agent into the coating. The improvement in resistance is likely due to reduction of the coating's surface free energy via fluorine incorporation, but may also have contributing effects from surface morphology changes. The data indicates that plasma-based surface modifications may have utility in improving chemical resistance of commercial coatings.