Application of 3D hierarchical porous NiCo-spinel nanosheet array for enhancement of synergistic activation of peroxymonosulfate: Degradation, Intermediates, mechanism and degradation pathway of tetracycline

Abstract

The rational design of the morphology and structure of bimetallic-based heterogeneous Fenton-like catalyst derived from metal-organic-frameworks (MOFs) for peroxymonosulfate (PMS) activation via a non-radical pathway is attractive but challenging. Herein, a spinel-type 3D hierarchical porous NiCo2O4 nanosheet array for the activation of PMS is rationally designed by surfactant-assisted interfacial engineering. The experimental results showed that the NiCo2O4/PMS system demonstrated remarkable oxidative degradation of tetracycline (TC) through 1O2 attack and electron transfer process. In literature, it was thought that the PMS activation process in above system is dominated by radical pathway. In this work, we employ surfactant modified-nanostructure engineering to design hierarchical mesoporous nanosheet array structures and combined them with intrinsic bimetallic synergy to enhance catalytic activity, and interestingly the strategy transformed the PMS activation pathway into a nonradical (1O2 and electron transfer)-dominated process. This is benefit from the favorable morphological and electronic structure of the designed catalysts to facilitate mass transfer and electron transfer processes. The system also possessed a broad spectrum for degrading other typical contaminants, and was effective in tolerating actual water matrix and pH changes, as well as resisting interference from anions and organic matter. Furthermore, the robust stability of the structure and catalytic activity make it promising for practical water treatment. It can be expected that this proposal will provide insights for the delicate structural design and the understanding of its PMS activation mechanism of bimetallic-based Fenton-like catalysts, as well as for the efficient degradation of emerging organic pollutants.