Catalytic oxidation of arsenite and reaction pathways on the surface of CuO nanoparticles at a wide range of pHs

Recently, the wide application of CuO nanoparticles (NPs) in engineering field inevitably leads to its release into various geologic settings, which has aroused great concern about the geochemical behaviors of CuO NPs due to its high surface reactivity and impact on the fate of co-existing contaminants. However, the redox transformation of pollutants mediated by CuO NPs and the underlying mechanism still remain poorly understood. Here, we studied the interaction of CuO NPs with As(III), and explored the reaction pathways using batch experiments and multiple spectroscopic techniques. The results of in situ quick scanning X-ray absorption spectroscopy (Q-XAS) analysis verified that CuO NPs is capable of catalytically oxidize As(III) under dark conditions efficiently at a wide range of pHs. As(III) was firstly adsorbed on CuO NPs surface and then gradually oxidized to As(V) with dissolved O₂ as the terminal electron acceptor. As(III) adsorption increased to the maximum at a pH close to PZC of CuO NPs (~?pH 9.2), and then sharply decreased with increasing pH, while the oxidation capacity monotonically increased with pH. X-ray photoelectron spectroscopy and electron paramagnetic resonance characterization of samples from batch experiments indicated that two pathways may be involved in As(III) catalytic oxidation: (1) direct electron transfer from As(III) to Cu(II), followed by concomitant re-oxidation of the produced Cu(I) by dissolved O₂ back to Cu(II) on CuO NPs surface, and (2) As(III) oxidation by reactive oxygen species (ROS) produced from the above Cu(I) oxygenation process. These observations facilitate a better understanding of the surface catalytic property of CuO NPs and its interaction with As(III) and other elements with variable valence in geochemical environments.