Wang Anqi, Liu Xingxin, Wen Yukai, Qiu Yongfu, Lv Sihao, Xu Manman, Meng Cuilin, Wang Kai, Lin Fengjie, Xie Shuibo, Zhuo Qiongfang
Research Center for Eco-environmental Engineering, School of Environment and Civil Engineering, Dongguan University of Technology, Dongguan 523808, China.
Research Center for Eco-environmental Engineering, School of Environment and Civil Engineering, Dongguan University of Technology, Dongguan 523808, China; School of Civil Engineering, University of South China, Hengyang 421001, China.
Water Res. 2023 Oct 15;245:120596. doi: 10.1016/j.watres.2023.120596. Epub 2023 Sep 8.
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 TiO (Zr/TiO) and hierarchical CuFeO (CFO) microspheres were used as anode and microelectrodes, respectively. In the optimal reaction system, the degradation efficiencies of 40 mg L atenolol, florfenicol, and diclofenac sodium could achieve up to 98.8%, 93.4%, and 85.5% in 120 min with 0.1 g L CFO at current density of 25 mA cm. 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, with a lower energy consumption (25.67 kWh/m). 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/TiO 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、传质缓慢和能耗高的限制。在此,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,以及实际制药废水,其中新设计的单原子Zr嵌入TiO(Zr/TiO)和分级CuFeO(CFO)微球分别用作阳极和微电极。在最佳反应体系中,在电流密度为25 mA/cm²、CFO为0.1 g/L的条件下,40 mg/L的阿替洛尔、氟苯尼考和双氯芬酸钠在120分钟内的降解效率分别可达98.8%、93.4%和85.5%。更重要的是,在流通式反应器中,持续150分钟的电氧化可将实际制药废水的化学需氧量从432降至88.6 mg/L,且能耗较低(25.67 kWh/m³)。同时,电氧化系统保持了优异的稳定性和环境适应性。密度泛函理论计算表明,该电氧化系统的优异性能可归因于单原子Zr负载降低反应能垒以及Zr/TiO表面大量氧空位的显著特征。此外,表征和实验结果表明,CFO独特的分级结构以及电极之间的协同效应也是提高系统性能的重要因素。这些发现为提高电化学氧化性能的单原子材料设计提供了启示。