The Reaction Specificity of Nanoparticles in Solution: Application to the Reaction of Nanoparticulate Iron and Iron-Bimetallic Compounds with Chlorinated Hydrocarbons and Oxyanions

The prospect for better remediation technologies using nanoparticles of iron, iron oxides, and iron with catalytic metals (i.e., bimetallics) has potentially transformative implications for environmental management of DOE sites across the country. Of particular interest is the potential to avoid undesirable products from the degradation of chlorinated solvents by taking advantage of the potential selectivity of nanoparticles to produce environmentally benign products from CCl{sub 4}. Chlorinated solvents are the most frequently reported subsurface contaminants across the whole DOE complex, and carbon tetrachloride (CCl{sub 4}) is the chlorinated solvent that is of greatest concern at Hanford (U. S. Department Energy 2001). In evaluating technologies that might be used at the site, a critical concern will be that CCl{sub 4} reduction usually occurs predominantly by hydrogenolysis to chloroform (CHCl{sub 3}) and methylene chloride (CH{sub 2}Cl{sub 2}), both of which are nearly as problematic as CCl{sub 4} (National Research Council, 1978). Competing reaction pathways produce the more desirable products carbon monoxide (CO) and/or formate (HCOO{sup -}), and possibly CO{sub 2}, but the proportion of reaction that occurs by these pathways is highly variable. Iron-based metallic and oxide nanoparticles have been shown to have enhanced reactivity towards a variety of chemical species, including chlorinated hydrocarbons and reducible oxyanions. Possibly of greater importance is the ability of nanoparticles to select for specific reaction products, potentially facilitating the formation of more environmentally acceptable products. The purpose of this study is to develop a fundamental understanding of the mechanism responsible for the overall particle reactivity and reaction selectivity of reactive metal and oxide nanoparticles. To achieve this objective the project involves the synthesis (using solution and vacuum synthesis methods) and characterization of well-defined nanoparticles, measurements of particle reactivity in solution or vacuum environments, and theory and modeling efforts to rationalize particle structure and reactivity