A solvent-free solid catalyst for the selective and color-indicating ambient-air removal of sulfur mustard.

Bis(2-chloroethyl) sulfide or sulfur mustard (HD) is one of the highest-tonnage chemical warfare agents and one that is highly persistent in the environment. For decontamination, selective oxidation of HD to the substantially less toxic sulfoxide is crucial. We report here a solvent-free, solid, robust catalyst comprising hydrophobic salts of tribromide and nitrate, copper(II) nitrate hydrate, and a solid acid (Nafion) for selective sulfoxidation using only ambient air at room temperature.

Metal-Organic Framework- and Polyoxometalate-Based Sorbents for the Uptake and Destruction of Chemical Warfare Agents.

The threat of chemical warfare agents (CWAs), assured by their ease of synthesis and effectiveness as a terrorizing weapon, will persist long after the once-tremendous stockpiles in the U.S. and elsewhere are finally destroyed.

Multimodal Characterization of Materials and Decontamination Processes for Chemical Warfare Protection.

This Review summarizes the recent progress made in the field of chemical threat reduction by utilizing new in situ analytical techniques and combinations thereof to study multifunctional materials designed for capture and decomposition of nerve gases and their simulants. The emphasis is on the use of in situ experiments that simulate realistic operating conditions (solid-gas interface, ambient pressures and temperatures, time-resolved measurements) and advanced synchrotron methods, such as in situ X-ray absorption and scattering methods, a combination thereof with other complementary measurements (e.g.

Correlated Multimodal Approach Reveals Key Details of Nerve-Agent Decomposition by Single-Site Zr-Based Polyoxometalates.

Development of technologies for protection against chemical warfare agents (CWAs) is critically important. Recently, polyoxometalates have attracted attention as potential catalysts for nerve-agent decomposition. Improvement of their effectiveness in real operating conditions requires an atomic-level understanding of CWA decomposition at the gas-solid interface.

Multi-Tasking POM Systems.

Polyoxometalate (POM)-based materials of current interest are summarized, and specific types of POM-containing systems are described in which material facilitates multiple complex interactions or catalytic processes. We specifically highlight POM-containing multi-hydrogen-bonding polymers that form gels upon exposure to select organic liquids and simultaneously catalyze hydrolytic or oxidative decontamination, as well as water oxidation catalysts (WOCs) that can be interfaced with light-absorbing photoelectrode materials for photoelectrocatalytic water splitting.

Impact of ambient gases on the mechanism of [CsNbO]-promoted nerve-agent decomposition.

The impact of ambient gas molecules (X), NO, CO and SO on the structure, stability and decontamination activity of CsNbO polyoxometalate was studied computationally and experimentally. It was found that CsNbO absorbs these molecules more strongly than it adsorbs water and Sarin (GB) and that these interactions hinder nerve agent decontamination. The impacts of diamagnetic CO and SO molecules on polyoxoniobate CsNbO were fundamentally different from that of NO radical.

Polyoxometalate-based gelating networks for entrapment and catalytic decontamination.

We report the synthesis and characterization of a new class of organic/inorganic hybrid polymers composed of covalently-bound 1,3,5-benzenetricarboxamide linkers and anionic polyoxovanadate clusters with varying counter-cations. These materials form gels within seconds upon contact with polar aprotic organic liquids and catalyze the degradation of odorants and toxic molecules under mild conditions including aerobic oxidation of thiols, hydrogen peroxide-catalyzed oxidation of sulfides, and hydrolysis of organophosphate chemical warfare agent analogues.

Stabilization of Polyoxometalate Water Oxidation Catalysts on Hematite by Atomic Layer Deposition.

Fast and earth-abundant-element polyoxometalates (POMs) have been heavily studied recently as water oxidation catalysts (WOCs) in homogeneous solution. However, POM WOCs can be quite unstable when supported on electrode or photoelectrode surfaces under applied potential. This article reports for the first time that a nanoscale oxide coating (AlO) applied by the atomic layer deposition (ALD) aids immobilization and greatly stabilizes this now large family of molecular WOCs when on electrode surfaces.