Journal of Hazardous Materials ( IF 12.2 ) Pub Date : 2022-09-06 , DOI: 10.1016/j.jhazmat.2022.129912 Yanling Chen 1 , Xue Bai 2 , Yetong Ji 1 , Dandan Chen 1
Herein, ternary metal-organic frameworks (MOFs)-derived MnCoFeO with different levels of oxygen vacancies (Ov) were designed by adjusting the doping amount of Mn and employed to activate peroxymonosulfate (PMS) for sulfamethoxazole (SMX) degradation. The MnCoFeO-2 with the largest Ov content exhibited the highest SMX degradation efficacy. Almost 100% of SMX was removed within 5 min using the MnCoFeO-2/PMS system. The reaction rate constant (kobs) was 1.7321 min−1, which was 4.1 times that of CoFeO (0.4195 min−1). Both the SO4•− and 1O2 were the dominant reactive oxygen species. Significantly, the relationship among Ov, radical pathways, and non-radical pathways was explored for the first time. The results showed that Ov could regulate the radical pathways by promoting the adsorption of PMS onto MnCoFeO-2. Ov was positively correlated with 1O2 (P < 0.05) and facilitated the direct electron transfer. The superior catalytic activity of MnCoFeO was attributed to the Fe, Co, Mn active sites, Lewis basic sites and Ov in MnCoFeO. Mn(II) not only contributed to the formation of Ov, but also facilitated the reduction of Fe(III). Additionally, Ov was mainly concentrated near the low-valent metal ions, thus the synergistic effect between the metal active sites and Ov promoted the activation of PMS.
中文翻译:
使用三元 MOF 衍生的 MnCoFeO 增强过氧单硫酸盐的活化用于磺胺甲恶唑降解:氧空位的作用
在此,通过调整Mn的掺杂量设计了具有不同氧空位(O v)水平的三元金属有机骨架(MOFs)衍生的MnCoFeO,并用于活化过氧单硫酸盐(PMS)以降解磺胺甲恶唑(SMX)。具有最大 O v含量的 MnCoFeO-2表现出最高的 SMX 降解效率。使用 MnCoFeO-2/PMS 系统在 5 分钟内去除了几乎 100% 的 SMX。反应速率常数(k obs)为1.7321 min -1,是CoFeO(0.4195 min -1)的4.1倍。SO 4 •−和1 O 2是主要的活性氧。值得注意的是,首次探索了Ov、自由基途径和非自由基途径之间的关系。结果表明,O v可以通过促进 PMS 在 MnCoFeO-2 上的吸附来调节自由基途径。O v与1 O 2呈正相关(P < 0.05)并促进了直接电子转移。MnCoFeO优异的催化活性归因于MnCoFeO中的Fe、Co、Mn活性位点、Lewis碱性位点和O v。Mn(II)不仅促进了O v的形成,还促进了Fe(III)的还原。此外,O v主要集中在低价金属离子附近,因此金属活性位点与O v的协同作用促进了PMS的活化。