Selective Degradation of Electron-Rich Organic Pollutants Induced by CuO@Biochar: The Key Role of Outer-Sphere Interaction and Singlet Oxygen.

Efficient degradation of organic pollutants by oxidative radicals is challenging in the complex soil environment because of the invalid consumption of radicals by nontarget background substances and the generation of secondary halogenated organic pollutants. Nonradical-based oxidation is a promising pollutant removal method due to its high selectivity and environmental adaptability. Herein, a biochar-supported sheetlike CuO (e-CuO@BC) was developed, which exhibited efficient activation of peroxydisulfate (PDS) via nonradical pathways. The activation mechanisms were identified as (i) formation of surface-bonding active complexes via an outer-sphere interaction between e-CuO@BC and PDS and (ii) the continuous generation of O by the cycling of the Cu(I)/Cu(II) redox couple. In addition, the activation of PDS primarily occurred at the crystal facet (001) of e-CuO occupied by Cu atoms and was well facilitated by the Cu-O-C bond, which induced electron-rich centers around CuO. Two oxidative species from PDS activation, including surface-bonding active complexes and O, showed a highly selective degradation toward electron-rich pollutants. Moreover, a highly efficient mineralization of organic pollutants and an effective inhibition on the generation of toxic byproducts (i.e., halogenated organics) was indicated by the intermediate and final degradation products. This study provides a comprehensive understanding of the heterogeneous activation process of PS by the e-CuO@BC catalyst for electron-rich organic pollutant removal.