Electrocatalytic oxidation is commonly restricted by low degradation efficiency, slow mass transfer, and high energy consumption. Herein, a synergetic electrocatalysis system was developed for removal of various drugs, i.e., atenolol, florfenicol, and diclofenac sodium, as well as actual pharmaceutical wastewater, where the newly-designed single-atom Zr embedded Ti₄O₇ (Zr/Ti₄O₇) and hierarchical CuFe₂O₄ (CFO) microspheres were used as anode and microelectrodes, respectively. In the optimal reaction system, the degradation efficiencies of 40 mg L^–1 atenolol, florfenicol, and diclofenac sodium could achieve up to 98.8%, 93.4%, and 85.5% in 120 min with 0.1 g L^–1 CFO at current density of 25 mA cm^–2. More importantly, in the flow-through reactor, the electrooxidation lasting for 150 min could reduce the COD of actual pharmaceutical wastewater from 432 to 88.6 mg L⁻¹, with a lower energy consumption (25.67 kWh/m³). Meanwhile, the electrooxidation system maintained superior stability and environmental adaptability. DFT theory calculations revealed that the excellent performance of this electrooxidation system could be ascribed to the striking features of the reduced reaction energy barrier by single-atom Zr loading and abundant oxygen vacancies on the Zr/Ti₄O₇ surface. Moreover, the characterization and experimental results demonstrated that the CFO unique hierarchical structure and synergistic effect between electrodes were also the important factors that could improve the system performance. The findings shed light on the single-atom material design for boosting electrochemical oxidation performance.

电催化氧化通常受到降解效率低、传质慢和能耗高的限制。本文开发了一种协同电催化系统，用于去除各种药物，即阿替洛尔、氟苯尼考和双氯芬酸钠以及实际的制药废水，其中新设计的单原子Zr嵌入Ti 4 O 7 ₍ Zr _/ Ti ₄ O ₇）和分级CuFe ₂ O ₄ (CFO)微球分别用作阳极和微电极。在最佳反应体系中，电流密度为25时， 0.1 g L ^{–1 CFO在120 min内对40 mg L –1}阿替洛尔、氟苯尼考和双氯芬酸钠的降解效率分别达到98.8%、93.4%和85.5%。mA cm ^–2。更重要的是，在流通式反应器中，持续150 min的电氧化可以将实际制药废水的COD从432降低至88.6 mg L ^-1，且能耗较低（25.67 kWh/m ³）。同时，电氧化系统保持了优异的稳定性和环境适应性。DFT理论计算表明，该电氧化体系的优异性能可归因于单原子Zr负载和Zr/Ti 4 O 7 表面上丰富的氧空位降低反应能垒的_显着_特征。此外，表征和实验结果表明，CFO独特的层次结构和电极之间的协同效应也是提高系统性能的重要因素。这些发现揭示了用于提高电化学氧化性能的单原子材料设计。