Structure-dependent catalysis of cuprous oxides in peroxymonosulfate activation via nonradical pathway with a high oxidation capacity

Abstract

Research interests have been recently thrust into the nonradical reactions in persulfate-based advanced oxidation processes (AOPs), whilst the underlying mechanism of the nonradical pathway remains ambiguous especially in metal-based AOPs systems. In this study, we investigated the reactivity of cuprous oxide (Cu₂O) for activating peroxymonosulfate (PMS) to decompose diverse organic contaminants. Cu₂O exhibited a strong catalytic dependence on the crystal morphology, and cubic Cu₂O was more reactive than the octahedral and rhombic dodecahedral structures for catalytic degradation of bisphenol A with PMS. Chemical quenching tests, electron paramagnetic resonance (EPR), solvent exchange and selective oxidation experiment were corporately conducted to illustrate that Cu₂O-catalyzed PMS did not produce free radicals or singlet oxygen. In contrast, a surface-confined metastable intermediate would be formed via outer-sphere interactions between PMS and Cu₂O, which directly attacked the organic substrate. Such a reaction pathway is intrinsically distinct from the electron-shuttling regime in carbon (or noble metal)/persulfate systems via the conductive surface of the catalyst, and the outer-sphere interactions let the activated PMS demonstrate a higher oxidizing capacity toward organic contaminants. Therefore, this study dedicates to providing new insights into the copper-catalyzed AOPs and vital supplementary to the ongoing dialogue of the nonradical catalysis in persulfate-based oxidation.

Keywords: Cuprous oxide; Nonradical pathway; Outer-sphere interaction; Peroxymonosulfate.