碳布生长Nim(Mo3S11)n配位聚合物及其活化过硫酸盐降解四环素性能

Nim(Mo3S11)n coordination polymers grown on carbon cloth for enhanced PMS activation to degrade antibiotics

摘要:

通过[Mo3S13]2-团簇与Ni2+离子配位,在碳布(CC)上生长无序连接的聚合物链(Nim(Mo3S11)n)。该催化剂丰富的硫活性位点提供了更多的活性中心,实现了高效活化过硫酸盐(PMS)降解四环素(TC)。采用SEM、TEM、XRD、Raman和XPS对Nim(Mo3S11)n-CC进行了表征,探究了不同反应体系,催化剂含量、不同PMS含量、pH、常见阴离子( (Br-, Cl-, HCO32-, HPO42-))和不同水源对降解效率的影响；通过自由基淬灭实验、EPR测试,推测Nim(Mo3S11)n-CC-Light活化PMS的机理。实验结果表明:Nim(Mo3S11)n-CC+PMS-Light体系在60 min内对TC的降解率达到97.50%；当制备催化剂比例为5:1、PMS含量0.3 g/L、pH=7时为最佳实验条件；不同阴离子存在下对降解TC存在不同程度的抑制作用,在不同水源中的TC降解率均达到85%以上；五次循环实验后,Nim(Mo3S11)n-CC+PMS-Light的降解率仍保持在90%以上；Nim(Mo3S11)n-CC-Light活化PMS氧化去除TC的机理和1发挥主要作用,而SO4·-和·OH在其中发挥次要作用。

Abstract:

The disordered link polymer chain (Nim(Mo3S11)n) was grown on carbon cloth (CC) surfaces by coordinating [Mo3S13]2- clusters and Ni2+ ions. The abundant sulfur active sites of the catalyst provide more active centers for efficient activating persulfate (PMS) to degrade tetracycline (TC). Nim(Mo3S11)n-CC was thoroughly characterized by SEM, TEM, XRD, Raman and XPS. The influence of various reaction systems, catalyst loadings, PMS dosages, pH values, common anions (Br-, Cl-, HCO32-, HPO42-) and various water sources were systematically investigated. The mechanism underlying PMS activation by Nim(Mo3S11)n-CC-Light was elucidated through radical quenching experiments and EPR spectroscopy. The experimental results showed that Nim(Mo3S11)n-CC+PMS-Light system reached 97.50% degradation of TC within 60 min. The optimal experimental conditions were determined to be a catalyst ratio of 5:1, PMS concentration of 0.3 g/L, and pH = 7. The presence of different anions exhibited varying degrees of inhibition on TC degradation, while the TC degradation rate exceeded 85% in all water sources tested. After five cycles of experimentation, the degradation rate of the Nim(Mo3S11)n-CC+PMS-Light system remained above 90%. The mechanism of TC removal by Nim(Mo3S11)n-CC-Light involves the primary roles of O2·- and 1O2, while SO4·-and ·OH play secondary roles.