Sulfur or nitrogen-doped rGO supported Fe-Mn bimetal – organic frameworks composite as an efficient heterogeneous catalyst for degradation of sulfamethazine via peroxydisulfate activation

Abstract

In this work, sulfur/nitrogen modified reduced graphene oxide (S/N-rGO) was employed as both electron shuttle and support to fabricate Fe-Mn bimetallic organic framework@S/N-rGO hybrids (BOF@S/N-rGO) via a facile two-step solvothermal route. Compared with the transition metal ions (Fe2+/Mn2+), the classical metal oxide catalyst (Fe2O3 and Fe3O4) and nano zero-valent iron (nZVI), BOF@S/N-rGO catalyst can more effectively activate peroxydisulfate (PDS) with ultra-low concentration (0.05 mM) to degrade sulfamethazine (SMT). Quenching experiments, electron paramagnetic resonance (EPR) measurement and linear sweep voltammetry (LSV) showed that the activation pathways of PDS between the two catalysts were different. In BOF@N-rGO+PDS system, the degradation of SMT was mainly attributed to the oxidation of radicals including SO4•− and •OH, especially SO4•− . However, in BOF@S-rGO+PDS system, in addition to the radical pathway, there are also non-radical pathways, namely 1O2 and direct electron transfer. Furthermore, the applicability of BOF@S/N-rGO used in the PDS-mediated advanced oxidation processes (AOPs) was systematically investigated in terms of the effects of operating parameters and coexisting substance (anions and humic acid (HA)), the degradation of other pollutants, as well as the stability and reusability of the catalyst. This study proved that BOF@S/N-rGO was a promising activator of PDS with ultra-low concentration for the degradation of SMT.