Quantification of the Influence of Citrate/Fe(II) Molar Ratio on Hydroxyl Radical Production and Pollutant Degradation during Fe(II)-Catalyzed O 2 and H 2 O 2 Oxidation Processes.

Ligand-enhanced hydroxyl radical (•OH) production is an important strategy for Fe(II)-catalyzed O 2 and H 2 O 2 oxidation processes. However, the influence of the molar ratio of ligands to Fe(II) on •OH production remains elusive. This study employed citrate and inorganic dissolved Fe(II) (Fe(II) dis ) as the representative ligand and Fe(II) species, respectively, to quantify this relationship. Results showed that •OH production was highly dependent on the citrate/Fe(II) molar ratio. For instance, for the oxygenation of Fe(II) dis , the •OH accumulations were 2.0-8.5, 3.4-28.5 and 8.1-42.3 μM at low (0.25-0.5), moderate (0.5-1), and high (1-2) citrate/Fe(II) molar ratios, respectively. At low citrate/Fe(II) molar ratio (<0.5), inorganic Fe(II) dis mainly contributed to •OH production, with the increase in the citrate/Fe(II) molar ratio to a high level (1-2), Fe(II)-citrate complex turned to the electron source for •OH production. The change in Fe(II) speciation with the increase of citrate/Fe(II) molar ratio elevated •OH production. For pollutant degradation, 1 mg/L phenol was degraded by 53.6% within 40 min during oxygenation of Fe(II)-citrate system (1:1) at pH 7. Our results suggest that a moderate molar ratio of ligand/Fe(II) (0.5-1) may be optimal for Fe(II)-catalyzed O 2 and H 2 O 2 oxidation processes.