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用于活化过一硫酸盐以实现环丙沙星近100%降解的耐用氟化羟基氧化钴/海藻酸钙水凝胶。

Durable fluorinated cobalt oxyhydroxide/calcium alginate hydrogels for activating peroxymonosulfate to enable nearly 100% degradation of ciprofloxacin.

作者信息

Zeng Yunxiong, Zhang Zhilong, Zhan Xingyu, Hong Bo, Wang Xinqing, Xia Yingchun

机构信息

College of Materials and Chemistry, Zhejiang Province Key Laboratory of Magnetic Materials, China Jiliang University Hangzhou 310018 People's Republic of China.

Department of Chemical Engineering, Tsinghua University Beijing 100084 People's Republic of China

出版信息

RSC Adv. 2024 Nov 1;14(47):34938-34947. doi: 10.1039/d4ra06321j. eCollection 2024 Oct 29.

DOI:10.1039/d4ra06321j
PMID:39493550
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11528419/
Abstract

Peroxymonosulfate (PMS) activation by solid catalysts for ciprofloxacin (CIP) removal is a promising method for decontaminating wastewater. However, mainstream catalysts suffer from efficiency and durability issues due to mechanical fragility and structural instability. Here, we have developed a durable calcium alginate hydrogel encapsulating fluorinated cobalt oxyhydroxide (FCO/CAH), fabricated by a simple hydrogen-bond-assisted cross-linking reaction, to enhance PMS activation for complete CIP removal. The optimized 2-FCO/CAH could generate abundant singlet oxygen (O) and sulfate radicals (SO˙) with PMS, resulting in 0.433 min kinetic constant and approximately 100% CIP degradation within 10 minutes. This exceptional degradation efficiency is due to the even distribution of 2-FCO, which maximizes catalytic sites for PMS activation, and the multichannel cavity structure of CAH, which effectively enriches both PMS and CIP. Furthermore, the durability of 2-FCO/CAH was proved by its negligible decay in CIP removal efficiency (∼100%) and good microstructure retention after 6 consecutive cycles, facilitated by a stable surface reconstructed interphase on the 2-FCO surface and the strong mechanical property of 2-FCO/CAH. Our work showcases a facile approach to constructing durable hydrogel catalysts that improve PMS-mediated antibiotic degradation.

摘要

通过固体催化剂活化过氧单硫酸盐(PMS)以去除环丙沙星(CIP)是一种很有前景的废水净化方法。然而,由于机械脆性和结构不稳定性,主流催化剂存在效率和耐久性问题。在此,我们开发了一种耐用的海藻酸钙水凝胶包裹氟代羟基氧化钴(FCO/CAH),通过简单的氢键辅助交联反应制备而成,以增强PMS活化作用从而实现CIP的完全去除。优化后的2-FCO/CAH与PMS反应可产生大量的单线态氧(O)和硫酸根自由基(SO˙),动力学常数为0.433 min,10分钟内可使CIP降解约100%。这种卓越的降解效率归因于2-FCO的均匀分布,其使PMS活化的催化位点最大化,以及CAH的多通道空腔结构,其有效地富集了PMS和CIP。此外,2-FCO/CAH的耐久性体现在其CIP去除效率的衰减可忽略不计(约100%),以及连续6个循环后仍保持良好的微观结构,这得益于2-FCO表面稳定的表面重构界面相和2-FCO/CAH的强机械性能。我们的工作展示了一种构建耐用的水凝胶催化剂以改善PMS介导的抗生素降解的简便方法。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/248c70c3a097/d4ra06321j-f8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/d6d58a44974c/d4ra06321j-s1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/7b2ebc4229da/d4ra06321j-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/933d624d7da5/d4ra06321j-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/c86767e35aff/d4ra06321j-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/fd9d7d7a00a0/d4ra06321j-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/248c70c3a097/d4ra06321j-f8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/d6d58a44974c/d4ra06321j-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/b32a6326b0a4/d4ra06321j-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/634e8cd9e16d/d4ra06321j-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/b39f520f0f3e/d4ra06321j-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/7b2ebc4229da/d4ra06321j-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/933d624d7da5/d4ra06321j-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/c86767e35aff/d4ra06321j-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/13c7/11528419/fd9d7d7a00a0/d4ra06321j-f7.jpg
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Fe(II) and Pyridinic N complex sites synergy to activate PMS for specific generation of O to degrade antibiotics with high efficiency.Fe(II) 和吡啶 N 配位协同激活 PMS 以高效产生 O 降解抗生素。
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