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Nanoscale zero-valent iron (nZVI): Aspects of the core-shell structure and reactions with inorganic species in water

Yan, Weile, Herzing, Andrew A., Kiely, Christopher J., Zhang, Wei-xian
Journal of contaminant hydrology 2010 v.118 no.3-4 pp. 96-104
X-radiation, X-ray photoelectron spectroscopy, chemical reduction, functional properties, hydrogen sulfide, hydroxides, iron, iron oxides, mercury, pollution, scanning electron microscopes, sorption, zinc
Aspects of the core-shell model of nanoscale zero-valent iron (nZVI) and their environmental implications were examined in this work. The structure and elemental distribution of nZVI were characterized by X-ray energy-dispersive spectroscopy (XEDS) with nanometer-scale spatial resolution in an aberration-corrected scanning transmission electron microscope (STEM). The analysis provides unequivocal evidence of a layered structure of nZVI consisting of a metallic iron core encapsulated by a thin amorphous oxide shell. Three aqueous environmental contaminants, namely Hg(II), Zn(II) and hydrogen sulfide, were studied to probe the reactive properties and the surface chemistry of nZVI. High-resolution X-ray photoelectron spectroscopy (HR-XPS) analysis of the reacted particles indicated that Hg(II) was sequestrated via chemical reduction to elemental mercury. On the other hand, Zn(II) removal was achieved via sorption to the iron oxide shell followed by zinc hydroxide precipitation. Hydrogen sulfide was immobilized on the nZVI surface as disulfide (S₂ ²⁻) and monosulfide (S²⁻) species. Their relative abundance in the final products suggests that the retention of hydrogen sulfide occurs via reactions with the oxide shell to form iron sulfide (FeS) and subsequent conversion to iron disulfide (FeS₂). The results presented herein highlight the multiple reactive pathways permissible with nZVI owing to its two functional constituents. The core-shell structure imparts nZVI with manifold functional properties previously unexamined and grants the material with potentially new applications.