Understanding the Iron-Cobalt Synergies in ZSM-5: Enhanced Peroxymonosulfate Activation and Organic Pollutant Degradation.

Iron- and cobalt-based heterogeneous catalysts are widely applied for activating peroxymonosulfate (PMS) to degrade organic pollutants. However, few studies have unveiled the clear synergistic mechanism of iron and cobalt in ZSM-5. In this paper, the synergistic mechanism of enhanced PMS activation was revealed by constructing iron and cobalt bimetal modified ZSM-5 zeolite catalysts (FeCo-ZSM-5). The tetracycline hydrochloride (TCH) degradation experiments showed that the catalytic activity of FeCo-ZSM-5-2:3 was much higher than those of Fe-ZSM-5 and Co-ZSM-5. In addition, the influences of catalyst dosage, PMS concentration, reaction temperature, initial pH, and coexisting ions on TCH removal were systematically investigated in this paper. Density functional theory calculations indicated that Co was the main active site for PMS adsorption, and Fe increased the area of Co's positive potential mapped to the electron cloud. The Fe-Co bimetallic doping increased the area of positive potential mapped to the electron cloud and benefited the adsorption of PMS on the catalyst surface, which revealed the synergistic mechanism of bimetals. Electron paramagnetic resonance spectra and quenching experiments showed that sulfate radicals, singlet oxygen, and hydroxyl radicals were involved in the degradation of TCH. Furthermore, liquid chromatography-mass spectrometry was conducted to propose possible degradation pathways. This work provides certain guiding significance in understanding the synergistic effect of heterogeneous catalysts for tetracycline wastewater treatment.