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硫修饰零价铁活化高碘酸盐去除磺胺嘧啶:反应性物种生成的性能和主要途径。

Sulfide-modified zero-valent iron activated periodate for sulfadiazine removal: Performance and dominant routine of reactive species production.

机构信息

College of Biology and the Environment, Nanjing Forestry University, Nanjing 210037, China.

State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023, China.

出版信息

Water Res. 2022 Jul 15;220:118676. doi: 10.1016/j.watres.2022.118676. Epub 2022 May 26.

Abstract

In this work, sulfide-modified zero-valent iron (S-Fe) was used to activate periodate (IO, PI) for sulfadiazine (SDZ) removal. 60 μM SDZ could be completely removed within only 1 min by S-Fe/PI process. Compared with other oxidants including HO, peroxymonosulfate (PMS), peroxydisulfate (PDS), S-Fe activated PI exhibited better performance for SDZ removal but with lower Fe leaching. Compared with Fe/PI process, S-Fe/PI process could reduce more than 80% Fe and PI dosage. Inorganic ions and nature organic matters had negligible effect on SDZ removal in S-Fe/PI system inducing its good SDZ removal efficiency in natural fresh water. 80.2% SDZ still could be removed within 2 min after 7th run. S-Fe/PI process also exhibited 2.5 - 20.1 folds enhancement for various pollutants removal compared with Fe/PI process. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), electrochemical tests, and density functional theory (DFT) calculation were conducted to confirm the presence of sulfurs could enhance the reactivity of S-Fe thus increased the efficiency of PI activation for antibiotics removal. Electron paramagnetic resonance spectroscopy (EPR) tests, radical quenching experiments, quantitative detection and DFT calculation were performed to illustrate the role of multiple reactive species in SDZ removal and the dominant pathway of multiple reactive species production. IO, OH, O, O, Fe, and SO all participated in SDZ removal. OH played the major role in SDZ removal and the dominant routine of OH production was IO → O → HO → OH. Meanwhile, S-Fe/PI process could efficiently mineralize SDZ and reduce the toxicity. Comparison with other PI activation approaches and SDZ treatment techniques further demonstrated S-Fe was an efficient catalyst for PI activation and present study process was a promising approach for antibiotics removal.

摘要

在这项工作中,使用硫化零价铁 (S-Fe) 来激活高碘酸盐 (IO,PI) 以去除磺胺嘧啶 (SDZ)。仅需 1 分钟,S-Fe/PI 工艺即可完全去除 60 μM 的 SDZ。与其他氧化剂(包括 HO、过一硫酸盐 (PMS)、过二硫酸盐 (PDS))相比,S-Fe 激活 PI 对 SDZ 的去除具有更好的性能,但铁浸出量较低。与 Fe/PI 工艺相比,S-Fe/PI 工艺可以减少超过 80%的铁和 PI 用量。在 S-Fe/PI 体系中,无机离子和天然有机物对 SDZ 的去除几乎没有影响,这使其在天然淡水中具有良好的 SDZ 去除效率。在第 7 次运行后,2 分钟内仍可去除 80.2%的 SDZ。与 Fe/PI 工艺相比,S-Fe/PI 工艺对各种污染物的去除率提高了 2.5-20.1 倍。扫描电子显微镜 (SEM)、X 射线光电子能谱 (XPS)、电化学测试和密度泛函理论 (DFT) 计算证实了硫的存在可以增强 S-Fe 的反应性,从而提高 PI 激活去除抗生素的效率。电子顺磁共振 (EPR)测试、自由基猝灭实验、定量检测和 DFT 计算表明,多种活性物质在 SDZ 去除中的作用以及多种活性物质产生的主导途径。IO、OH、O、O、Fe 和 SO 都参与了 SDZ 的去除。OH 在 SDZ 去除中起主要作用,OH 生成的主要途径是 IO→O→HO→OH。同时,S-Fe/PI 工艺可以有效地矿化 SDZ 并降低毒性。与其他 PI 激活方法和 SDZ 处理技术的比较进一步表明,S-Fe 是一种有效的 PI 激活催化剂,本研究工艺是一种很有前途的抗生素去除方法。

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