Enhanced degradation of micropollutants over iron-based electro-Fenton catalyst: Cobalt as an electron modulator in mesochannels and mechanism insight.

Heterogeneous electro-Fenton (hetero-EF) process is an emerging alternative for effective oxidation of recalcitrant micropollutants, but it is hampered by limited hydroxyl radical (•OH) generation and low stability on the iron-based cathodes. Herein, we demonstrate an enhanced hetero-EF performance via modulation of iron electronic structure in an ordered mesoporous carbon (OMC). By tuning the cobalt incorporation, the highly-dispersed iron-cobalt (FeCo) nanoalloys in mesochannels (Fe0.5Co0.5@OMC) show a 3-fold increase in •OH yield compared with Fe@OMC, achieving degradation efficiency with 92% of sulfamethazine (SMT) and 99% of rhodamine B (RhB), and the corresponding total organic carbon (TOC) removal with 66% of SMT and 85% of RhB within 2 h in neutral pH, respectively. Experimental results and density functional theory (DFT) calculations demonstrate that iron incorporated with cobalt reduces energy barrier for facile generation of H2O2 and •OH from O2 through direct electron transfer, along with decreased overpotential. Meanwhile, cobalt doping promotes H2O2 decomposition by accelerated Fe(II)/Fe(III) cycle and Co(II)/Co(III) redox. Furthermore, spatially confined and half-embedded structure endows the nanocatalyst (8 nm) excellent durability within a wide pH value range and good stability in cycle tests. A plausible reaction mechanism and degradation pathway for SMT are proposed. Moreover, the superiority of Fe0.5Co0.5@OMC cathode is maintained in simulated wastewater, suggesting an enormous potential in practical wastewater treatment.