MnxCo3-xO4 spinel activates peroxymonosulfate for highly effective bisphenol A degradation with ultralow catalyst and persulfate usage

Abstract

Persulfates-based advanced oxidation processes are highly efficient in degrading refractory organic contaminants in wastewater. However, their practical application is often limited by the extensive consumption of catalysts and oxidants. Therefore, constructing catalysts with abundant and efficient reaction interfaces is essential for improving the efficiency of persulfate activation. In this work, we develop a novel Mn_xCo_3-xO₄ spinel with highly exposed surface active sites by etching Mn-based precursors with Co ions. This process forms sufficient interface Co-O-Mn bonds, which effectively activate peroxymonosulfate (PMS) for bisphenol A (BPA) degradation. A clear structure-activity relationship is observed between the Co/Mn content ratio and the BPA degradation rate in the Mn_xCo_3-xO₄/PMS system. Notably, Mn_0.1Co_2.9O₄ demonstrates superior PMS activation efficiency, achieving 100 % degradation of 10 mg/L BPA within 2 minutes with 0.05 g/L catalyst and 0.05 g/L persulfate usage. Experimental analyses combined with theoretical calculations identify the interface Co-O-Mn as the active site, which plays a crucial role in accelerating PMS molecule adsorption and O-O bond activation. Additionally, the spatially adjacent Co-O-Mn sites promote redox cycling for efficient interface electron transfer during the PMS activation process. Furthermore, Zebrafish toxicity studies revealed a considerable reduction in the toxicity of the BPA treatment residue in the Mn_xCo_3-xO₄/PMS system. Overall, this work presents a novel strategy for constructing spatially adjacent redox sites in dual-metal spinel materials, offering valuable insights into reducing chemical input and advancing persulfate-based environmental remediation technology.