Efficient activation of ferrate by Ru(III): Insights into the major reactive species and the multiple roles of Ru(III)

J Hazard Mater. 2023 Sep 15:458:131927. doi: 10.1016/j.jhazmat.2023.131927. Epub 2023 Jun 24.

Abstract

Ferrate (Fe(VI)) has aroused great research interest in recent years due to its environmental benignancy and lower potential in disinfection by-product generation. However, the inevitable self-decomposition and lower reactivity under alkaline conditions severely restrict the utilization and decontamination efficiency of Fe(VI). Here, we discovered that Ru(III), a representative transition metal, could effectively activate Fe(VI) to degrade organic micropollutants, and its performance on Fe(VI) activation exceeded that of previously reported metal activators. The high-valent metal species (i.e., Fe(IV)/Fe(V) and high-valent Ru species) made a major contribution to SMX removal by Fe(VI)-Ru(III). Density functional theory calculations indicated the function of Ru(III) as a two-electron reductant, leading to the production of Ru(V) and Fe(IV) as the predominant active species. The characterization analyses proved that Ru species was deposited on ferric (hydr)oxides as Ru(III), indicating the possibility of Ru(III) as an electron shuttle with the rapid valence circulation between Ru(V) and Ru(III). This study not only develops an efficient way to activate Fe(VI) but also offers a thorough understanding of Fe(VI) activation induced by transition metals.

Keywords: Ferrate; High-valent Ru species; Ru(III); Sulfamethoxazole; Two-electron transfer.