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.

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.

This work investigates the fundamental nature of sulfur mustard surface adsorption by characterizing interfacial hydrogen bonding and other intermolecular forces for the surrogate molecule (simulant) 2-chloroethyl ethyl sulfide (2-CEES). Adsorption at the surface of amorphous silica is the focus of this work because of silica’s low chemical reactivity, well-known properties, and abundance in the environment. 2-CEES has two polar functional groups, the chloro and thioether moieties, available to accept hydrogen bonds from free surface silanol groups. Diethyl sulfide and chlorobutane are also investigated to independently assess the role of the chloro and thioester functionalities in the overall adsorption mechanism and to explore the interplay between the charge transfer and electrostatic contributions to total hydrogen-bond strength. Our approach utilizes infrared spectroscopy to study specific surface–molecule interactions and temperature-programmed desorption to measure the activation energy for desorption of adsorbed molecules. Our results indicate that 2-CEES adsorbs to silica by hydrogen bonding through either the chloro or thioether moieties but is unable to form a more stable configuration in which both polar groups interact simultaneously with adjacent silanol groups. The activation energy for desorption of 2-CEES is nearly 43 kJ/mol, driven by both strong hydrogen bonding and other non-bonding interactions. A systematic study of chloroalkanes reveals that each methylene group contributes approximately 5–8 kJ/mol to the overall desorption energy.

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, TiO 2 , 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 TiO 2 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 TiO 2 , and degradation reactions can be triggered by defects or contaminants under realistic operational conditions.

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.