High yield M-BTC type MOFs as precursors to prepare N-doped carbon as peroxymonosulfate activator for removing sulfamethazine: The formation mechanism of surface-bound SO4•- on Co-Nx site

Abstract

M-BTCs (M = Fe, Co and Mn)/melamine were used to prepare N-doped carbon materials, and their performances as activator of peroxymonosulfate (PMS) for sulfamethazine (SMZ) removal were compared. M-BTC type metal-organic frameworks (MOFs) were synthesized under room temperature, with their yield about 7.5 times of ZIF-67 which is the most used MOFs to prepare N-doped carbon materials as the catalyst of persulfate-based advanced oxidation processes. Co-BTC/melamine derived N-doped carbon materials (Co-BTC/5MNC) performed the best, even better than that of ZIF-67 derived N-doped carbon materials. Initial pH (3–9), 0–10 mM inorganic anions (Cl−, NO3−, HCO3− and H2PO42−) and humic acid (5 and 10 mg/L) had no obvious inhibition on SMZ removal with Co-BTC/5MNC as catalyst. The results of both X-ray photoelectron spectroscopy and density functional theory (DFT) calculations indicated that N-coordinated cobalt single atom site (Co−Nx) was the possible active site of Co-BTC/5MNC. Importantly, surface-bound SO4•- was identified as the dominant reactive oxygen species for SMZ removal. The SO4•- generated through the charge transfer between PMS and catalyst, and was tightly adsorbed on Co-Nx site.