Regulating the peroxymonosulfate activation on N doped δ-MnO2 nanosheets for tetracycline degradation: N species as the degradation pathways switcher to convert radical to nonradical

Although the free radical pathway can obtain high organic degradation efficiency during advanced oxidation processes, it is difficult to cater the diverse degradation environment due to the coexistence of various inter-ference. Here, the delta-MnO2 nanosheets are prepared to regulate the reactive oxidation species converting from radical-dominated to nonradical-dominated through the nitrogen doped operation in a gentle mechanical stirring method. The optimal 0.5 N-MnO2 materials present 91.2 % TC degradation efficiency in the presence of per-oxymonosulfate (PMS) with the apparent rate constant is 0.63 min(-1), which is 1.66 and 4.2 times higher than that of in delta-MnO2/PMS (0.38 min(-1)) and alone PMS (0.15 min(-1)) systems, respectively. Radicals quenching experiments, electron paramagnetic resonance spectra and competing kinetics experiments indicate that the delta-MnO2 nanosheets promote PMS decomposition with attaining a high radical (SO4 center dot-, center dot OH and center dot O-2(-)) oxidation path contribution (74.5 %) for TC degradation. Meanwhile, the doping of N species and electrons contribute to the generation of O-1(2), allowing the whole reactive system dominated by a nonradical species (e- and O-1(2)) pathway (80.3 %). Importantly, electrochemical tests verify the participation of electrons and the electrons transfer from TC to the 0.5 N-MnO2 surface for PMS activation via 0.5 N-MnO2-PMS* surface complex. Overall, it is practical to cater the specific application of advanced oxidation processes through N as the degradation pathways switcher.