Impact of Phosphate on Ferrate Oxidation of Organic Compounds: An Underestimated Oxidant.

Abstract

Ferrate (K2FeO4) is a powerful oxidant and up to 3 mol of electrons could be captured by 1 mol of ferrate in the theoretical conversion of Fe(VI)-Fe(V)-Fe(IV)-Fe(III). However, it is reported that the utilization efficiency of the ferrate oxidation capacity is quite low because of the rapid autodecomposition of intermediate iron species, which negatively influences the potential of ferrate on organic pollutants control. We accidentally found that for the ferrate oxidation of carbamazepine (CBZ), bisphenol S (BPS), diclofenac (DCF), and ciprofloxacin (CIP), the determined reaction rate constants were 1.7-2.4 times lower in phosphate buffer than those in borate buffer at pH 8.0. For the reaction of ferrate with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) at pH 7.0, the determined reaction stoichiometries were 1:1.04 in 100 mM phosphate buffer, 1:1.18 in 10 mM phosphate buffer, and 1:1.93 in 10 mM borate buffer, respectively. The oxidation ability of ferrate seems depressed in phosphate buffer. A kinetic model involving the oxidation of ABTS by Fe(VI), Fe(V) and Fe(IV) species was developed and fitted the ABTS•+ formation kinetics well under different buffer conditions. The results showed that phosphate exhibited little influence on the oxidation ability of Fe(VI) and Fe(IV) species, but decreased the specific rate constants of ABTS with Fe(V) species by 1-2 orders of magnitude, resulting in the outcompeting of Fe(V) autodecomposition pathway. The complexation between phosphate anions and Fe(V) species may account for the inhibition effect of phosphate buffer. Considering that many studies regarding ferrate oxidation were carried out in phosphate buffer, the actual oxidation ability of ferrate may be underestimated.