Ligand-enhanced reactive oxidant generation by nanoparticulate zero-valent iron and oxygen

The reaction of zero-valent iron or ferrous iron with oxygen produces reactive oxidants capable of oxidizing organic compounds. However, the oxidant yield in the absence of ligands is too low for practical applications. The addition of oxalate, nitrilotriacetic acid (NTA), or ethylenediaminetetraacetic acid (EDTA) to oxygen-containing solutions of nanoparticulate zero-valent iron (nZVI) significantly increases oxidant yield, with yields approaching their theoretical maxima near neutral pH. These ligands improve oxidant production by limiting iron precipitation and by accelerating the rates of key reactions, including ferrous iron oxidation by oxygen and hydrogen peroxide. Product yields indicate that the oxic nZVI system produces hydroxyl radical (OH*) over the entire pH range in the presence of oxalate and NTA. In the presence of EDTA, probe compound oxidation is attributed to OH under acidic conditions and a mixture of OH* and ferryl ion (Fe[IV]) at circumneutral pH.