Homogeneous to heterogeneous redox mediator enhancing ferrate(VI) oxidation of sulfamethoxazole: Role of ferrate(VI) activation and electron shuttle.

ABSTRACT

Ferrate (Fe(VI)) is a promising oxidant for water remediation, yet it has limited reactivity towards certain recalcitrant but important emerging contaminants, such as sulfamethoxazole. Here, this study demonstrates that nitroxide redox mediators, specifically 9-azabicyclo[3.3.1]nonasne N-oxyl (ABNO), can catalyze Fe(VI) reaction with sulfamethoxazole by functioning both as Fe(VI) activator and electron shuttle. The underlying mechanism is explained as (i) Fe(VI) activation a series of one-electron transfers between Fe(VI) and ABNO produces highly reactive Fe(V)/Fe(IV) and ABNO+; (ii) electron shuttle the newly formed active ABNO+ reacts with the sulfamethoxazole, contributing to its removal. Concurrently, ABNOH is generated and subsequently converted back to ABNO by reactive species, thereby completing the redox cycle. The as-developed heterogeneous redox mediator, ABNO@SiO2, retained its catalytic properties and effectively catalyzed Fe(VI) to remove sulfamethoxazole at environmentally relevant pH levels.