Liu Shitong, Liu Junwu, Wang Jun, Liu Yang, Yang Baojun, Hong Maoxin, Yu Shichao, Qiu Guanzhou, Fang Yingchun
School of Minerals Processing & Bioengineering, Central South University, Changsha, 410083, China; Key Laboratory of Biohydrometallurgy, Ministry of Education, Central South University, Changsha, 410083, China.
Engineering and Technology Research Center of Heavy Pollution Industrial Wastewater Treatment and Recycling of Hunan Province, China.
J Environ Manage. 2025 Feb;375:124356. doi: 10.1016/j.jenvman.2025.124356. Epub 2025 Feb 3.
Loading catalysts onto carriers to prepare supported catalysts is an important strategy for improving dispersion, stability and catalytic performance. In this study, we synthesized a supported red mud (RM)-based Fe-Co Prussian blue analogue (RM-Co PBA) catalyst using RM as iron source and carrier by acid dissolution-reduction-coprecipitation method to activate HO for the degradation of ciprofloxacin (CIP). The RM-Co PBA obtained under the synthesis conditions of HCl concentration of 2.4 M and potassium cobalt cyanide addition of 4 mM exhibited the best dispersibility and regular shape, resulting in high catalytic performance. The degradation efficiency of RM-Co PBA/HO system reached 75.79% in 10 min, which was 10.54 times and 1.21 times of that of RM/HO system and Fe-Co PBA/HO system, respectively. The RM-Co PBA/HO system was almost unaffected by pH and was suitable for treating low concentration CIP wastewater. Additionally, the system can be reused well and possessed certain resistance to inorganic anions. The results showed that superoxide radical (⋅O) was the main ROS attacking CIP, which accumulated continuously in the cycling process of Co(III)/Fe(III) and Co(II)/Fe(II). On the other hand, the presence of a large number of oxygen vacancies in RM-Co PBA enhanced the production of ⋅O by endowing it with good electron transfer performance. Finally, we proposed possible CIP degradation pathways and demonstrated the toxicity reduction of each pathway by a quantitative structure-activity relationship analysis. This study provides guidance for the resource utilization of RM and the efficient treatment of antibiotic wastewater.
将催化剂负载到载体上制备负载型催化剂是提高分散性、稳定性和催化性能的重要策略。在本研究中,我们以赤泥(RM)为铁源和载体,采用酸溶-还原-共沉淀法合成了一种负载型赤泥基铁-钴普鲁士蓝类似物(RM-Co PBA)催化剂,用于活化H₂O₂降解环丙沙星(CIP)。在HCl浓度为2.4 M和氰化钴钾添加量为4 mM的合成条件下获得的RM-Co PBA表现出最佳的分散性和规则形状,从而具有高催化性能。RM-Co PBA/H₂O₂体系在10分钟内的降解效率达到75.79%,分别是RM/H₂O₂体系和Fe-Co PBA/H₂O₂体系的10.54倍和1.21倍。RM-Co PBA/H₂O₂体系几乎不受pH影响,适用于处理低浓度CIP废水。此外,该体系可良好地重复使用,并对无机阴离子具有一定抗性。结果表明,超氧自由基(·O₂⁻)是攻击CIP的主要活性氧物种,其在Co(III)/Fe(III)和Co(II)/Fe(II)的循环过程中不断积累。另一方面,RM-Co PBA中大量氧空位的存在通过赋予其良好的电子转移性能增强了·O₂⁻的产生。最后,我们提出了可能的CIP降解途径,并通过定量构效关系分析证明了各途径的毒性降低情况。本研究为赤泥的资源利用和抗生素废水的高效处理提供了指导。