Monodispersed CuO nanoparticles supported on mineral substrates for groundwater remediation via a nonradical pathway

Nonradical oxidation based on singlet oxygen (¹O₂) has attracted great interest in groundwater remediation due to the selective oxidation property and good resistance to background constituents. Herein, recoverable CuO nanoparticles (NPs) supported on mineral substrates (SiO₂) were prepared by calcination of surface-coated metal-plant phenolic networks and explored for peroxymonosulfate (PMS) activation to generate ¹O₂ for degrading organic pollutants in groundwater. CuO NPs with a close particle size (40 nm) were spatially monodispersed on SiO₂ substrates, allowing highly exposure of active sites and consequently leading to outstanding catalytic performance. Efficient removal of various organic pollutants was obtained by the supported CuO NPs/PMS system under wide operation conditions, e.g., working pH, background anions and natural organic matters. Chemical scavenging experiments, electron paramagnetic resonance tests, furfuryl alcohol decay and solvent dependency experiments confirmed the formation of ¹O₂ and its dominant role in pollutants removal. In situ characterization with ATR-FTIR and Raman spectroscopy and computational calculation revealed that a redox cycle of surface Cu(II)-Cu(III)-Cu(II) was responsible for the generation of ¹O₂. The feasibility of the supported CuO NPs/PMS for actual groundwater remediation was evaluated via a flow-through test in a fixed-bed column, which manifested long-term durability, high mineralization ratio and low metal ion leaching.