Roles of structure defect, oxygen groups and heteroatom doping on carbon in nonradical oxidation of water contaminants

Abstract

A rational design of structure-tailored and functionalized nanocarbons for peroxymonosulfate (PMS) activation is important in metal-free catalysis for degradation of water contaminants. In this work, we employed ionic liquids (ILs) for synthesis of porous carbon materials (PCMs) as a PMS activator for oxidative removal of naproxen and systematically investigated the functions of structure defects, oxygen functional groups and heteroatom doping toward the catalytic oxidation. A positive linear correlation between reaction rate constants and carbon defect ratios of PCMs revealed that the structural defects played an important role in PMS activation. Electron paramagnetic resonance (EPR) spectra, radical quenching experiments and electrochemical analysis tests verified nonradical-dominated oxidations via electron transfer and 1O2. Structural vacancies, ketonic C=O groups and graphitic-N atoms on carbons have been revealed to be the active sites for the nonradical pathways via direct electron transfer or generation of O2•−/1O2. This work provides new insight into the reaction mechanism and structure-performance relationships of the catalytic centers in nonradical oxidation.