| This research (Chapter 2) involves the development of household bleaching products that are environmentally safe. This work is of particular interest, given the growing concern of legislators, public health officials, and environmental groups about the deleterious environmental impact of halogenated oxidants. The goal of this research is to examine polyoxometalates that can potentially catalyze the oxidation, or bleaching, of stains such as ink, pinacyanol chloride dye (monomer, λmax = 600 nm; dimer, λmax = 550 nm; ϵ = 38,800) by hydrogen peroxide in basic water at room temperature, thus obviating the need for chlorine-containing oxidants. Base-stable niobium containing polyoxometalates covalently attached to oxidizing cations such as iron (III) were investigated.; The aim of a second line of research (Chapter 3) is to determine if appropriate (colored, strongly oxidizing) polyoxometalates (POMs) could be added to perfluoropolyether topical skin protectants (TSPs) currently available or under development to give these TSPs the additional capability of detecting and in some cases catalytically decontaminating HD and perhaps other chemical warfare agents (CWA) at ambient temperatures. Detection would be based on significant color changes in the POM upon reduction by the CWA, while catalytic decontamination would be based on the ability of some families of POMs to catalyze O2-based oxidations by more than one mechanism. Results from representative systems indicate that these reactions are thermodynamically favorable, and that the reduced species is stable. The oxidation of CWA model compounds in a microemulsion model for TSP and in a homogeneous fluid model of the TSP is described. Kinetic and mechanistic analyses are presented. |
