An insight into metal organic framework derived N-doped graphene for the oxidative degradation of persistent contaminants: formation mechanism and generation of singlet oxygen from peroxymonosulfate

Abstract

The synthesis of carbonaceous materials from a metal organic framework (MIL-100), organic linker and N-precursor was comprehensively investigated, and the structures of the products were characterized. It was found that simple pyrolysis of mixed MIL-100 (Fe)/dicyandiamide (DCDA) could produce nitrogen-doped graphene (N-graphene). The N-graphene showed excellent performances in peroxymonosulfate (PMS) activation, which were superior to those of counterparts of graphene, iron(II, III) oxide, manganese(IV) oxide and cobalt(II, III) oxide. With PMS activation, N-graphene exhibited efficient catalytic degradation of various organic pollutants such as phenol, 2,4,6-trichlorophenol (TCP), sulfachloropyridazine (SCP) and p-hydroxybenzoic acid (PHBA). Electron paramagnetic resonance (EPR) spectroscopy and radical quenching tests were employed to investigate the PMS activation and organic degradation processes. It was found that singlet oxygen (¹O₂) was mainly produced during the activation of PMS by N-graphene, and contributed to the catalytic oxidation instead of sulfate and/or hydroxyl radicals. These findings provide new insights into PMS activation by metal-free carbon catalysis.