Novel Synthesis Pathways for Highly Oxidative Iron Species: Generation, Stability, and Treatment Applications of Ferrate(IV/V/VI).

Abstract

Difficulties arise related to the economy-of-scale and practicability in applying conventional water treatment technologies to small and remote systems. A promising oxidation technology better suited for these applications is that of electro-oxidation (EO), whereby contaminants are degraded via direct, advanced, and/or electrosynthesized oxidant-mediated reactions. One species of oxidants of particular interest includes ferrates (Fe(VI)/(V)/(IV)), where only recently has their circumneutral synthesis been demonstrated, using high oxygen overpotential (HOP) electrodes, namely boron-doped diamond (BDD). In this study, the generation of ferrates using various HOP electrodes (BDD, NAT/Ni-Sb-SnO2, and AT/Sb-SnO2) was investigated. Ferrate synthesis was pursued in a current density range of 5-15 mA cm-2 and initial Fe3+ concentrations of 10-15 mM. Faradaic efficiencies ranged from 11-23%, depending on operating conditions, with BDD and NAT significantly outperforming AT electrodes. Speciation tests revealed that NAT synthesizes both ferrate(IV/V) and ferrate(VI), while the BDD and AT electrodes synthesized only ferrate(IV/V) species. A number of organic scavenger probes were used to test the relative reactivity, including nitrobenzene, carbamazepine, and fluconazole, whereby ferrate(IV/V) was significantly more oxidative than ferrate(VI). Finally, the ferrate(VI) synthesis mechanism by NAT electrolysis was elucidated, where coproduction of ozone was found to be a key phenomenon for Fe3+ oxidation to ferrate(VI).