Insight into synergetic mechanism of CuyMn5-yOx/hG-activated peroxydisulfate enhances tetracycline antibiotics degradation and toxicity assessment
Insight into synergetic mechanism of CuyMn5-yOx/hG-activated peroxydisulfate enhances tetracycline antibiotics degradation and toxicity assessment
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DOI：
10.1016/j.seppur.2022.121066
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发表时间：
2022-04
影响因子：
8.6
通讯作者：
Yong-gang Sun;Ruijia Xiong;Juan Zhang;Yulong Ma;Yuanyuan Li;Wen-xin Ji;Yuhui Ma;Zhen Wang
中科院分区：
文献类型：
--
作者：
Yong-gang Sun;Ruijia Xiong;Juan Zhang;Yulong Ma;Yuanyuan Li;Wen-xin Ji;Yuhui Ma;Zhen Wang
四环素是一种典型的生态毒性抗生素，易造成环境污染。基于硫酸根的高级氧化工艺（SO 4·--AOPs）是一种有吸引力的污染控制方法，在这方面，通过优良的催化体系产生和稳定高氧化性物种来降解四环素类抗生素是至关重要的。在这项工作中，我们研究了一种策略，采用协同作用的CuOx扩大MnSBnO的共价性和定制的缺陷位点，这可以提高固有的活性的CuyMn 5-yOx/hG催化剂的增强过二硫酸盐（PDS）的活化和四环素降解通过自由基和非自由基的过程。综合表征表明，Mn单键O键减弱，而CuyMn 5-yOx氧化还原循环为PDS自由基活化提供了主要活性中心。此外，碳基助催化剂的丰富的缺陷位点促进PDS和四环素的吸附，因此，它们的催化通过非自由基过程。结构表征表明，固相法制备的Cu2.5Mn2.5Ox/hG催化剂明显增加了缺陷位的比例，增大了MnSnO的共价性，提高了PDS的活性.其中OH·和SO 4·-自由基是关键活性氧物种，Mn（Cu）sbnO键弱化，缺陷是关键活化位点。此外，还对CuyMn 5-yOx/hG催化四环素降解的降解途径、中间产物的毒性以及反应机理进行了研究。去除单键C双键O单键NH 2官能团和C2-C3结构位开环对四环素的降解起着至关重要的作用。结果表明，Cu2.5Mn2.5Ox/hG催化剂对四环素具有良好的降解效果，且对环境影响较小，为进一步开发高效SO 4·--AOPs催化剂提供了新的思路.
Tetracycline is a typical ecologically toxic antibiotic that easily causes environmental contamination. An attractive approach toward pollution control is the implementation of sulfate radical-based advanced oxidation processes (SO4·--AOPs), and in that regard, it is critical to generate and stabilize highly-oxidative species over an excellent catalytic system to degrade tetracycline antibiotics. In this work, we investigated a strategy for employing a synergetic role of CuOxto enlarge the MnsbnO covalency and tailor defect sites, which could enhance the intrinsic activity of CuyMn5-yOx/hG catalysts for boosted peroxydisulfate (PDS) activation and tetracycline degradation via radical and nonradical processes. Comprehensive characterization revealed that Mnsingle bondO bonds weakened, while the CuyMn5-yOxredox cycling provided the main active center for PDS activation by radical processes. Moreover, abundant defect sites of the carbon-based co-catalyst promoted the adsorption of PDS and tetracycline and, thus, their catalysis via nonradical processes. Structural characterization indicated that Cu2.5Mn2.5Ox/hG catalysts prepared using the solid-phase method significantly increased the ratio of defects sites and enlarged the MnsbnO covalency, enhancing PDS activation. Particularly, OH·and SO4·-radicals were critical reactive oxygen species, Mn(Cu) sbnO bond weakening, and defects are the key activation sites. Furthermore, degradation pathways, the toxicity of intermediate species, and the reaction mechanisms of the tetracycline degradation catalyzed by CuyMn5-yOx/hG were determined. Removing single bondCdouble bondOsingle bondNH2functional groups and the C2-C3structural sites ring-opening played a vital role in tetracycline degradation. The Cu2.5Mn2.5Ox/hG catalyst was demonstrated to be effective in tetracycline degradation with a low environmental impact, and our findings provide valuable novel insights for further development of efficient SO4·--AOPs catalysts.