2D MOF derived cobalt and nitrogen-doped ultrathin oxygen-rich carbon nanosheets for efficient Fenton-like catalysis: Tuning effect of oxygen functional groups in close vicinity to Co-N sites

Abstract

Developing highly efficient catalysts for peroxymonosulfate (PMS) activation is an important issue in advanced oxidation processes (AOPs) technology. In this work, cobalt and nitrogen-doped ultrathin oxygen-rich carbon nanosheets derived from 2D metal-organic framework (MOF) were successfully fabricated. The as-prepared catalyst can effectively degrade tetracycline (TC) with a high reaction constant (0.088 min^-1). Quenching test, electron paramagnetic resonance (EPR) technology, and the electrochemical test indicate that the radical pathway plays a minor role in the degradation process, the ¹O₂ based nonradical pathway dominates the reaction. Experimental and density functional theory (DFT) studies revealed that the Co-N sites on the carbon structure serve as the dominant active sites, and the oxygen functional groups in close vicinity to Co-N sites can dramatically influence local electronic structure and its interaction with PMS molecule, a high correlation between the reaction constant and hydroxy groups content could be due to the Co-N sites close to hydroxyl groups has a moderate PMS adsorption energy. This work provides new insight into the design of highly efficient Fenton-like catalysts.

Keywords: Advanced oxidation process; Fenton-like catalysis; Oxygen functional groups; PMS activation; Singlet oxygen.