Co_(3)S_(4)/PES催化膜反应器氧化降解水中罗丹明B  

Co_(3)S_(4)/PES Catalytic Membrane Reactor for Oxidative Degradation of Rhodamine B in Water

作　　者：肖泽仪[1] 孟佳欣 樊森清 陈渝 陈皎皎 XIAO Zeyi;MENG Jiaxin;FAN Senqing;CHEN Yu;CHEN Jiaojiao(School of Chemical Engineering,Sichuan University,Chengdu 610065,China)

机构地区：[1]四川大学化学工程学院,四川成都610065

出　　处：《工程科学与技术》2025年第1期225-233,共9页Advanced Engineering Sciences

基　　金：国家自然科学基金项目(21808144);中央高校基本科研业务费专项资金(0082604151335)。

摘　　要：基于过硫酸氢钾(PMS)的非均相高级氧化工艺(AOPs)在实际应用中一直受到PMS活化效率与活性氧物种(ROS)利用率低下的限制。本文以ZIF-67为前驱体、聚醚砜(PES)多孔膜为基底,采用金属有机框架(MOFs)模板配体交换策略,流动合成构建了Co_(3)S_(4)/PES催化膜反应器(CMR)。通过场发射电子显微镜(FESEM)、X射线衍射(XRD)等方法对催化膜进行了表征。结果显示,平均粒径为23 nm的Co_(3)S_(4)纳米颗粒被原位合成固载在PES膜孔中,负载量为15.9%,并沿膜厚度方向均匀分布。以活化PMS降解典型芳香族有机化合物罗丹明B(RhB)为例,研究了该催化膜的催化性能及反应机理。实验结果表明,浓度为20 mg/L的RhB溶液,在初始溶液pH为7、温度为25℃以及膜通量为0.80 mL/(min·cm^(-2))(对应于停留时间0.68 s)的条件下,Co_(3)S_(4)/PES催化膜具有90%以上的降解率,表观反应速率常数为97.83 min^(-1),转化频率达到了489.15 L/(min·g^(-1)),均高出Co_(3)S_(4)粉末传统悬浮间歇处理模式两个数量级,并且Co_(3)S_(4)/PES催化膜能够保持良好的稳定性。膜孔道的分散性有效防止了Co_(3)S_(4)纳米颗粒的聚集,过膜流动反应限域在微纳尺度的膜孔道内,强化了反应物与催化剂之间的质量传递与接触,加快了PMS的活化,从而实现了单线态氧(^(1)O_(2))的高效生成,并在RhB的快速降解中起主导作用。Peroxymonosulfate(PMS)-based heterogeneous advanced oxidation processes are restricted in practice by the low activation efficiency of PMS and the utilization rate of reactive oxygen species(ROS).A Co_(3)S_(4)/PES catalytic membrane reactor(CMR)is constructed using a flowing synthesis approach,employing a metal-organic frameworks(MOFs)template exchange strategy with ZIF-67 as the precursor and a polyethersulfone(PES)porous membrane as the substrate.The catalytic membrane is characterized by field-emission scanning electron microscopy(FESEM)and X-ray diffraction(XRD).The results indicated that Co_(3)S_(4)nanoparticles with an average particle size of 23 nm are synthetically immobilized in situ within the pores of the PES membrane and are uniformly distributed along the membrane thickness,achieving an immobilization amount of 15.9%.The catalytic performance and reaction mechanism of the catalytic membrane are investigated by activating PMS to degrade a typical aromatic organic compound,Rhodamine B(RhB),as a model pollutant.Experimental results demonstrate that the Co_(3)S_(4)/PES catalytic membrane exhibits a RhB degradation rate exceeding 90%under conditions of a RhB solution concentration of 20 mg·L^(–1),an initial solution pH of 7,a temperature of 25°C,and a membrane flux of 0.80 mL·min^(–1)·cm^(–2)(corresponding to a residence time of 0.68 s).The apparent reaction rate constant is 97.83 min–1,and the turnover frequency(TOF)reaches 489.15 L·min^(–1)·g^(–1),both of which are 2 orders of magnitude higher than those achieved using the conventional suspension batch treatment mode with Co_(3)S_(4)powder.The Co_(3)S_(4)/PES catalytic membrane also maintains good stability.The dispersion of membrane pores effectively prevents the aggregation of Co_(3)S_(4)nanoparticles while confining the reaction within the micro-nanoscale membrane pores under flow-through conditions.This enhances mass transfer and contact between reactants and catalysts,accelerates PMS activation,and facilitates the efficient genera

关 键 词：催化膜反应器 高级氧化 罗丹明B 过硫酸氢钾 流动反应 ZIF-67 Co_(3)S_(4) 

分 类 号：X703[环境科学与工程—环境工程]