Efficient activation of peroxymonosulfate by molybdenum disulfide cocatalysis of Co and N co-doped porous carbon for degrading perfluorooctanoic acid: Synergistic effect of Co and N by molybdenum and its mechanism

In this study, precursor ultrathin molybdenum disulfide nanosheets and ZIF-67 was selected to prepare Co and N co-doped porous carbon by the support of Mo (MoS2/Co@NPC) to activate peroxymonosulfate (PMS) for perfluorooctanoic acid (PFOA) degradation. The morphology, crystal form and composition of MoS2/Co@NPC are studied by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and other methods. In MoS2/Co@NPC/PMS process, PFOA was completely degraded in 180 min at pH 7, 0.3 g/L catalyst, 0.1 mM PMS and reaction temperature of 25 °C. The degradation efficiency was much higher than that in other systems. The oxidative species for PFOA degradation was studied using free radical quenching experiments and electron paramagnetic resonance (ESR) tests. SO−4 plays a major role in the degradation of PFOA, OH plays an auxiliary role, and 1O2 contributes the least. The effect of different types and positions of cobalt‑nitrogen and molybdenum atoms on the electrocatalytic activity was investigated by density functional theory (DFT) calculations. The co-doping of Co and N into carbon-based materials can synergistically enhance by Mo for the activation of PMS. The unsaturated S atoms on the surface of metal sulfides can trap protons to form H2S while exposing the reducing metal active site, which also accelerates the rate-limiting step of the Co3+/Co2+ conversion. The core-shell structure of Co@NPC doped with Mo has the characteristics of improving the electron transfer ability of carbon, promoting the mass transfer of reactants, and preventing cobalt metal agglomeration and metal dissolution. The degradation pathways of PFOA were investigated and three possible pathways were proposed. In addition to PFOA, MoS2/Co@NPC-800/PMS system can also remove contaminant in pharmaceutical wastewater, indicating that the process has potential application value in practical wastewater treatment.