Efficient selenate removal from impaired waters with TiO₂-assisted electrocatalysis

Aquatic selenium (Se) oxyanions have profound ecosystem and human health impacts, necessitating their conversion and immobilization into elemental Se(0) to mitigate the aquatic Se pollution. While thermodynamically favorable, this transformation encounters kinetic limitations, especially for selenate (SeO₄^2-) or Se(VI). To lower the activation barrier, we investigated the electrocatalytic Se(VI) transformation using five affordable catalysts on graphite cathodes, including TiO₂, underpotentially deposited Cu (UPD Cu), underpotentially deposited Cd (UPD Cd), Co, and CuFe. Among these five catalysts, we identified characteristic Se(VI) reduction peaks for TiO₂ through cyclic voltammetry. Other catalysts removed less than 5% of 1-mM Se(VI) in 24-h chronoamperometry tests while leaching ppm-level metal cations in the treated water. In contrast, TiO₂ as the electrocatalyst could remove more than 80% of 1-mM Se(VI) with negligible catalyst dissolution. Mechanistic investigations revealed a six-electron Se(VI)/Se(0) reduction pathway at -0.30 V (vs. Ag/AgCl), resulting in red Se(0) deposits on the TiO₂-coated graphite cathode. Further potential decrease to more negative than -0.45 V led to Se(-II) formation, triggering cathodic Se(0) dissolution and surface regeneration. Electrochemical impedance spectroscopy indicated that Se(VI) reduction was optimal with a moderate TiO₂ loading of 0.55 mg cm^-2 and acidic environments (pH=1.0∼2.5), achieving an optimized removal of 88.7 ± 2.3% under -0.70 V and an energy input of 3.6 kWh kg^-1 Se. These findings lay the foundation for efficient selenate removal from impaired waters. Future efforts should evaluate catalyst performance over time and refine electrode and reactor designs to improve efficiency.