Characterization and properties of metallic iron nanoparticles: spectroscopy, electrochemistry, and kinetics.

There are reports that nano-sized zero-valent iron (Fe0) exhibits greater reactivity than micro-sized particles of Fe0, and it has been suggested that the higher reactivity of nano-Fe0 may impart advantages for groundwater remediation or other environmental applications. However, most of these reports are preliminary in that they leave a hostof potentiallysignificant(and often challenging) material or process variables either uncontrolled or unresolved. In an effort to better understand the reactivity of nano-Fe0, we have used a variety of complementary techniques to characterize two widely studied nano-Fe0 preparations: one synthesized by reduction of goethite with heat and H2 (Fe(H2)) and the other by reductive precipitation with borohydride (Fe(BH)). Fe(H2) is a two-phase material consisting of 40 nm alpha-Fe0 (made up of crystals approximately the size of the particles) and Fe3O4 particles of similar size or larger containing reduced sulfur; whereas Fe(BH) is mostly 20-80 nm metallic Fe particles (aggregates of <1.5 nm grains) with an oxide shell/coating that is high in oxidized boron. The FeBH particles further aggregate into chains. Both materials exhibit corrosion potentials that are more negative than nano-sized Fe2O3, Fe3O4, micro-sized Fe0, or a solid Fe0 disk, which is consistent with their rapid reduction of oxygen, benzoquinone, and carbon tetrachloride. Benzoquinone-which presumably probes inner-sphere surface reactions-reacts more rapidly with FeBH than Fe(H2), whereas carbon tetrachloride reacts at similar rates with FeBH and Fe(H2), presumably by outer-sphere electron transfer. Both types of nano-Fe0 react more rapidlythan micro-sized Fe0 based on mass-normalized rate constants, but surface area-normalized rate constants do not show a significant nano-size effect. The distribution of products from reduction of carbon tetrachloride is more favorable with Fe(H2), which produces less chloroform than reaction with Fe(BH).

On the characterization of environmental nanoparticles.

The presence and release of nanoparticles into the environment has important implications for human health and the environment. This article highlights and describes techniques that are effective in the characterization of anthropogenic and naturally occurring nanoparticles. Particle attributes like size, size distribution, shape, structure, microstructure, composition, and homogeneity are critically important to determining the potential impact of such materials on health and the environment. Many techniques yield data for a collection of nanoparticles; while others yield data for individual nanoparticles; and still others yield data showing the size, distribution of chemical species, and variations in structure and microstructure for a single nanoparticle. All are important in the context of environmental nanoparticles. Many of these techniques are complementary, and depending on the information required, the ideal characterization usually employs multiple techniques.