Hydroxyl groups bridge the electron transfer from Fe(II) to carbon tetrachloride.

Reductive dechlorination of chlorinated organic pollutants (COPs) by Fe(II) occurs in natural environments and engineered systems. Fe(II) ions undergo hydroxylation in aqueous solutions to form Ferrous Hydroxyl Complex (FHC), which plays an essential role in Fe(II)-mediated reductive dechlorination. However, how hydroxyl groups of FHC bridge the electron transfer from Fe(II) to COPs is still not fully understood. This work shows that the rate of reductive dechlorination of carbon tetrachloride (CT) by FHC increased with increasing OH- dosage. XRD data shows the increase of OH- dosage transform FHC from Fe2(OH)3Cl to Fe(OH)2, which leads to increased reductive strength of FHC. More non-hydrogen bonded hydroxyl groups coordinate with Fe(II) in FHC with increasing the OH- dosage, which stabilizes the octahedral structure of Fe(II) as shown by Mössbauer data. Electrochemical analysis reveals that the increase of OH- dosage enhances the reductive activity of FHC, which is also confirmed by the decreased HOMO-LUMO gap. It was found that FHC dechlorinated CT to methane, which was attributed to the stabilization of trichlorocarbene anion(˸CCl3-) by [surface-O-Fe(II)-OH]+. This work deepens our understanding on the bridge effect of hydroxyl groups on the electron transfer from Fe(II) to COPs, and provides a theoretical foundation for the reductive dechlorination of COPs in both natural environments and engineered systems.