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 (Fe_0.5Co_0.5@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 Fe_0.5Co_0.5@OMC cathode is maintained in simulated wastewater, suggesting an enormous potential in practical wastewater treatment.

非均相电芬顿 (hetero-EF) 工艺是有效氧化顽固性微污染物的新兴替代方法，但它受到羟基自由基 (•OH) 生成有限和铁基阴极稳定性低的阻碍。在此，我们通过在有序介孔碳 (OMC) 中调节铁电子结构来展示增强的异质 EF 性能。通过调整钴的掺入量，与 Fe@OMC 相比，中通道中高度分散的铁钴 (FeCo) 纳米合金 (Fe _0.5 Co _0.5 @OMC) 的 •OH 产率提高了 3 倍，降解效率达到 92%磺胺二甲嘧啶 (SMT) 和 99% 的罗丹明 B (RhB)，以及相应的总有机碳 (TOC) 去除率，其中 66% 的 SMT 和 85% 的 RhB 在 2 内 h 分别在中性 pH 值下。实验结果和密度泛函理论 (DFT) 计算表明，铁与钴的结合降低了能垒，从而通过直接电子转移从 O _{2轻松生成 H 2} O ₂和•OH ，同时降低了过电势。同时，钴掺杂通过加速Fe(II)/Fe(III)循环和Co(II)/Co(III)氧化还原来促进H ₂ O ₂分解。此外，空间受限和半嵌入结构使纳米催化剂（8 nm）在较宽的 pH 值范围内具有出色的耐久性，并在循环测试中具有良好的稳定性。提出了一种合理的 SMT 反应机理和降解途径。而且，Fe _{0.5的优越性} Co _0.5 @OMC 阴极保留在模拟废水中，表明在实际废水处理中具有巨大潜力。