Mechanisms for hydroxyl radical production and arsenic removal in sulfur-vacancy greigite (Fe3S4)

Herein, we systematically investigated the mechanisms of OH production and arsenic (As(III)) oxidation induced by sulfur vacancy greigite (Fe3S4) under anoxic and oxic conditions. Reactive oxygen species analyses revealed that sulfur vacancy-rich Fe3S4 (SV-rich Fe3S4) activated molecular oxygen to produce hydrogen peroxide (H2O2) via a two-electron reduction pathway under oxic conditions. Subsequently, H2O2 was decomposed to OH via the Fenton reaction. Additionally, H2O was directly oxidized to OH by surface high-valent iron (Fe(IV)) resulting from the abundance of sulfur vacancies in Fe3S4 under anoxic/oxic conditions. These differential OH-generating mechanisms of Fe3S4 resulted in higher OH production of SV-rich Fe3S4 compared to sulfur vacancy-poor Fe3S4 (SV-poor Fe3S4). Moreover, the OH production rate of SV-rich Fe3S4 under oxic conditions (19.3 ± 1.0 μM•h-1) was 1.6 times greater than under anoxic conditions (11.8 ± 0.4 μM•h-1). As(III) removal experiments and X-ray photoelectron spectra (XPS) showed that both OH production pathways were favorable for As(III) oxidation, and a higher concentration of As(V) was immobilized on the surface of SV-rich Fe3S4 under oxic conditions. This study provides new insights concerning OH production and environmental pollutants removal mechanisms on surface defects of Fe3S4 under anoxic and oxic conditions.