Characteristics and Sonophotocatalytic Activity of Natural Sphalerite under Ultrasonic (1.7 MHz) and UVA LED (365 nm) Irradiation

Naturally occurring sono- and photoactive minerals, which are abundant on Earth, represent an attractive alternative to the synthesized sonophotocatalysts as cost-effective materials for water and wastewater treatment. This study focuses on characterizing and evaluating the sonophotocatalytic activity of natural sphalerite (NatS) from Dovatka deposit (Siberia) under high-frequency ultrasonic (US, 1.7 MHz) and ultraviolet light-emitting diodes (UVA LED, 365 nm) irradiation towards degradation of 4-chlorophenol as a model organic pollutant. Since raw natural sphalerite did not exhibit a measurable photocatalytic activity, it was calcined at 500, 900 and 1200 °C. The natural sphalerite after calcination at 900 °C (NatS*) was found to be the most effective for sonophotocatalytic degradation of 4-chlorophenol, attaining the highest efficiency (55%, 1 h exposure) in the following row: UV < US ≈ UV/US ≈ US/NatS* < UV/NatS* < UV/US/NatS*. Addition of 1 mM H2O2 increased the removal to 74% by UV/US/NatS*/H2O2 process. An additive effect between UV/NatS* and US/NatS* processes was observed in the sonophotocatalytic system as well as in the H2O2-assisted system. We assume that the sonophotocatalytic hybrid process, which is based on the simultaneous use of high-frequency ultrasound, UVA light, calcined natural sphalerite and H2O2, could provide a basis of an environmentally safe and cost-effective method of elimination of organic pollutants from aqueous media.