In situ anodic induction of low-valence copper in electro-Fenton system for effective nitrobenzene degradation.

To achieve superior advanced oxidation processes (AOPs), transitional state activators are of great significance for the production of active radicals by H₂O₂, while instability limits their activation efficiency. In this study, density functional theory calculation (DFT) results showed that Cu⁺ exhibits excellent H₂O₂ activation performance, with Gibbs free energy change (ΔG) of 33.66 kcal/mol, two times less than that of Cu²⁺ (77.83 kcal/mol). Meanwhile, an electro-Fenton system using Cu plate as an anode was proposed for in situ generation of Cu⁺. The released Cu with low-valence state can be well-confined on the surface of the exciting electrode, which was confirmed by X-ray photoelectron spectroscopy (XPS), Raman, and UV-vis spectroscopy. The hydroxyl radicals in this Cu-based electro-Fenton system were determined by the electron spin resonance (ESR). The nitrobenzene degradation ratio was greatly increased by 43.90% with the introduction of the proposed in situ electrochemical Cu⁺ generation process. Various characterization results indicated that the production of Cu⁺ was the key factor in the highly efficient Cu-based electro-Fenton reaction. [ABSTRACT FROM AUTHOR]