Persulfate Activation on Crystallographic Manganese Oxides: Mechanism of Singlet Oxygen Evolution for Nonradical Selective Degradation of Aqueous Contaminants

TLDR

Earth‑abundant minerals and transitional metal oxides are promising catalysts for in situ chemical oxidation in environmental remediation, yet activation of peroxydisulfate by manganese oxides has been scarcely studied. This study investigates the mechanism of peroxydisulfate activation over manganese oxides and introduces a novel catalytic system for selective removal of organic contaminants from wastewater. The authors employed electron paramagnetic resonance, chemical probes, radical scavengers, and solvent variations to identify the reactive oxygen species involved. α‑ and β‑MnO₂ serve as effective peroxydisulfate activators, with β‑MnO₂ nanorods achieving the highest phenol degradation rate, and singlet oxygen is identified as the primary reactive species generated through superoxide recombination or direct oxidation from a metastable manganese intermediate.

Abstract

Minerals and transitional metal oxides of earth-abundant elements are desirable catalysts for in situ chemical oxidation in environmental remediation. However, catalytic activation of peroxydisulfate (PDS) by manganese oxides was barely investigated. In this study, one-dimension manganese dioxides (α- and β-MnO2) were discovered as effective PDS activators among the diverse manganese oxides for selective degradation of organic contaminants. Compared with other chemical states and crystallographic structures of manganese oxide, β-MnO2 nanorods exhibited the highest phenol degradation rate (0.044 min–1, 180 min) by activating PDS. A comprehensive study was conducted utilizing electron paramagnetic resonance, chemical probes, radical scavengers, and different solvents to identity the reactive oxygen species (ROS). Singlet oxygen (1O2) was unveiled to be the primary ROS, which was generated by direct oxidation or recombination of superoxide ions and radicals from a metastable manganese intermediate at neutral pH. The study dedicates to the first mechanistic study into PDS activation over manganese oxides and provides a novel catalytic system for selective removal of organic contaminants in wastewater.