Covalent organic frameworks@ZIF-67 derived novel nanocomposite catalyst effectively activated peroxymonosulfate to degrade organic pollutants

Abstract

Metal organic frameworks-Covalent organic frameworks (MOFs-COFs) nanocomposites could improve the catalytic performance. Herein, a novel nanocomposite catalyst (CC@Co₃O₄) derived from MOFs-COFs (COF@ZIF-67) was prepared on peroxymonosulfate (PMS) activation for bisphenol A (BPA) and rhodamine B (RhB) degradation. Owing to the Co species, oxygen vacancy (O_V), surface hydroxyl (-OH), graphite N and ketone groups (C=O), the CC@Co₃O₄ exhibited higher catalytic degradation performance and total organic carbon (TOC) for BPA (93.8% and 22.3%) and RhB (98.2% and 82.5%) with a small quantity of catalyst (0.10 g/L) and low concentration of PMS (0.20 g/L) even without pH adjustment. Sulfate radicals (•SO₄^-), hydroxyl radicals (•OH), single oxygen (¹O₂), superoxide radicals (•O₂^-) and electron transfer process were all involved in the degradation of BPA and RhB. Among them, the degradation of BPA and RhB mainly depended on •O₂^- and ¹O₂, respectively. Meanwhile, the degradation pathways of BPA and RhB were proposed, and the biotoxicity of the degradation products was evaluated by freshwater chlorella. The results illustrated that the degradation products were environmentally friendly to organisms. In addition, the role of COF in the nanocomposites was also studied. The addition of COF remarkably improved the catalytic performance of CC@Co₃O₄ due to the faster electron transfer, more graphite N and C=O. Overall, this work may open the door to the development of COF-based catalysts in the field of water pollutant remediation.

Keywords: Covalent organic framework; Degradation; Organic pollutant; Peroxymonosulfate; ZIF-67.