The organic contaminants degradation in Mn-NRGO and peroxymonosulfate system: The significant synergistic effect between Mn nanoparticles and doped nitrogen

A family of graphene-based activators including reduced graphene oxide (RGO), nitrogen doped reduced graphene oxide (NRGO), zero-valent manganese loaded reduced graphene oxide (Mn-RGO) and zero-valent manganese loaded N-doped reduced graphene oxide (Mn-NRGO) were fabricated to activate peroxymonosulfate (PMS) for bisphenol A (BPA) degradation. A significant synergistic effect between loaded manganese nano-particles (Mn-NPs) and doped N was revealed by comparing the apparent reaction rate constants with about 12.4, 7.6 and 10.5-folds enhancement when compared Mn-NRGO with RGO, NRGO, Mn-RGO, respectively. By integrating the results of chemical scavenger experiment, electron paramagnetic resonance test, galvanic oxidation process, PMS stoichiometric efficiency, linear sweep voltammetry and in-situ Raman spectrum, a predominant outer-sphere catalyst-PMS complexes mediated electron transfer pathway was uncovered. Based on kinetic studies, the specific contribution of synergistic effect was quantified to be at least 70%. The calculated Fermi level advanced by 0.03 eV in Mn-NG compared with that in NG, demonstrating that Mn-NG is more liable to donate electrons to PMS. The Eads and lO-O results pointed out that synergistic effect between Mn-NPs and doped N relied on the intimate affinity between Mn-NPs and HSO5– which triggered more uneven distribution of charge on the whole carbon sheets, and more adsorption of HSO5– on carbon framework. These newly created adsorption consequently reinforcing the formation of catalyst-PMS complexes and the elevation of mediated electron transfer pathway. Overall, this study firstly provides a comprehensive and definite insight of the synergistic effect between loaded Mn-NPs and doped-N on carbon materials for promoting PMS activation to degrade organics.