Enhanced Cr(VI) reduction on natural chalcopyrite mineral modulated by degradation intermediates of RhB

Wastewater with complex compositions of both heavy metals and organic pollutants is of critical environmental and socioeconomic threat worldwide, which urgently requires feasible remediation technologies to target this challenge. In this study, natural chalcopyrite (CuFeS2, NCP), the most abundant copper-based mineral in the Earth's crust, has been discovered to be a heterogeneous catalyst that can activate peroxydisulfate (PDS) for the simultaneous degradation of organic pollutant Rhodamine B (RhB) and reduction of hexavalent chromium (Cr(VI)). Batch experimental results indicate that both RhB and Cr(VI) could be simultaneously removed under a near-neutral condition in NCP/PDS combined system. The radicals SO4•− and •OH generated from PDS activation are the main oxidative species detected by electron paramagnetic resonance (EPR) spectroscopy. SO4•− acted as a predominant role in RhB degradation, while Cr(VI) reduction is mainly attributed to the oxidization of S2− and S22− species on NCP surface, as well as the photoreduction performance of NCP, which could be enhanced by the intermediates generated from RhB degradation. Density functional theory (DFT) calculation results disclose that Fe is the critical catalytic site for PDS activation. This work demonstrates a user-friendly strategy for remediation of complex wastewater containing both heavy metal and organic pollutants by combining photoreduction and advanced oxidation processes (AOPs) with natural minerals. It paves a way for wastewater treatment by utilizing low-cost natural abundant minerals as catalysts.