钴氮共掺杂废菌棒生物炭活化PMS去除水中加替沙星

doi:10.16085/j.issn.1000-6613.2024-0199

化工进展 ›› 2025, Vol. 44 ›› Issue (2): 1088-1099.DOI: 10.16085/j.issn.1000-6613.2024-0199

• 资源与环境化工 • 上一篇

钴氮共掺杂废菌棒生物炭活化PMS去除水中加替沙星

杨群¹(), 李红艳¹^,²(), 张峰¹, 毛立波³, 崔佳丽¹, 董颖虹⁴, 郭紫瑞¹

^1.太原理工大学环境科学与工程学院，山西晋中 030600
^2.临县丰林现代农业发展有限公司，山西吕梁 033200
^3.山西大地环境投资控股有限公司科创管理部，山西太原 030032
^4.太原学院建筑与环境工程系，山西太原 030032

收稿日期:2024-01-26 修回日期:2024-05-11 出版日期:2025-02-25 发布日期:2025-03-10
通讯作者: 李红艳
作者简介:杨群（2001—），女，硕士研究生，研究方向为高级氧化水处理技术。E-mail：18402967529@163.com。
基金资助:
吕梁市引进高层次科技人才重点研发项目(2021RC-1-22);山西省自然科学研究面上项目(202203021221060);山西省研究生创新项目(2023SJ085)

Removal of gatifloxacin from water by cobalt-nitrogen co-doped mushroom stick biological carbon activated PMS

YANG Qun¹(), LI Hongyan¹^,²(), ZHANG Feng¹, MAO Libo³, CUI Jiali¹, DONG Yinghong⁴, GUO Zirui¹

^1.College of Environmental Science and Engineering, Taiyuan University of Technology, Jinzhong 030600, Shanxi, China
^2.Linxian Fenglin Modern Agricultural Development Limited Company, Lyuliang 033200, Shanxi, China
^3.Science and Technology Management Department of Shanxi Dadi Environmental Investment Holdings Co. , Limited, Taiyuan 030032, Shanxi, China
^4.Department of Architecture and Environmental Engineering, Taiyuan University, Taiyuan 030032, Shanxi, China

Received:2024-01-26 Revised:2024-05-11 Online:2025-02-25 Published:2025-03-10
Contact: LI Hongyan

摘要/Abstract

摘要：

以农业废弃物废菌棒为原料，采用浸渍-煅烧法制备高性能的钴氮共掺杂废菌棒生物炭（Co-N@MSBC），对其进行扫描电子显微镜（SEM）、比表面积（BET）、红外光谱（FTIR）、X射线光电子能谱（XPS）表征分析，并用Co-N@MSBC活化过一硫酸盐（PMS）去除加替沙星（GAT）。结果表明，与PMS、MSBC、MSBC/PMS、Co-N@MSBC相比，最佳条件下，Co-N@MSBC/PMS体系在60min内对GAT的去除率高达96.5%，且在宽pH（3~11）范围均保持90%以上的GAT去除率；Cl^-、 $N O_{3}^{-}$ 和 $H C O_{3}^{-}$ 对GAT去除有一定抑制作用， $H_{2} P O_{4}^{-}$ 有轻微促进作用。Co-N@MSBC经过3次循环利用后对用自来水和超纯水配置的GAT去除率均高于85%，表明其具有良好的稳定性。淬灭实验表明，硫酸根自由基（ $S O_{4}^{\cdot -}$ ）、羟基自由基（·OH）和单线态氧（¹O₂）共同参与降解。体系存在亚稳态络合物介导的非自由基途径。电化学阻抗谱（EIS）和线性扫描伏安法（LSV）研究表明，GAT去除过程中存在三元体系间的直接电子转移，即PMS、Co-N@MSBC和GAT分别充当电子受体、电子桥和电子供体，且掺杂的Co、N促进PMS与Co-N@MSBC之间的电子转移。

关键词: 钴氮共掺杂废菌棒生物炭, 高级氧化, 加替沙星, 过一硫酸盐, 活化

Abstract:

High performance cobalt-nitrogen co-doped waste microbiochar (Co-N@MSBC) was prepared from agricultural waste mushroom stick by impregnation-calcination method. The biochar was characterized by scanning electron microscopy (SEM), specific surface area (BET), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). Gatifloxacin (GAT) was removed by Co-N@MSBC activated permonosulfate (PMS). The experimental results showed that, compared with PMS, MSBC, MSBC/PMS, Co-N@MSBC, the removal rate of GAT in Co-N@MSBC/PMS system was up to 96.5% within 60min under the best conditions, and remained above 90% removal efficiency at a wide pH range (3—11). Cl^-, $N O_{3}^{-}$ and $H C O_{3}^{-}$ had a certain inhibitory effect on the removal of GAT, while $H_{2} P O_{4}^{-}$ had a slight promotion effect. After three cycles of recycling, the GAT removal rate of Co-N@MSBC for tap water and ultra-pure water was still higher than 85%, indicating that it has good stability. The quenching experiments showed that sulfate radicals ( $S O_{4}^{\cdot -}$ ), ·hydroxyl radicals (·OH), and singlet oxygen (¹O₂) were involved in the degradation. There was a metastable complex mediated non-free radical pathway. Electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) experiments showed that there was direct electron transfer between ternary systems during GAT removal, which meant PMS, Co-N@MSBC and GAT act as electron acceptor, electron bridge and electron donor, respectively, and doped Co and N promote electron transfer between PMS and Co-N@MSBC.

Key words: cobalt-nitrogen co-doped waste bacterial stick biochar (Co-N@MSBC), advanced oxidation, gatifloxacin (GAT), permonosulfate (PMS), activation

中图分类号:

X703

杨群, 李红艳, 张峰, 毛立波, 崔佳丽, 董颖虹, 郭紫瑞. 钴氮共掺杂废菌棒生物炭活化PMS去除水中加替沙星[J]. 化工进展, 2025, 44(2): 1088-1099.

YANG Qun, LI Hongyan, ZHANG Feng, MAO Libo, CUI Jiali, DONG Yinghong, GUO Zirui. Removal of gatifloxacin from water by cobalt-nitrogen co-doped mushroom stick biological carbon activated PMS[J]. Chemical Industry and Engineering Progress, 2025, 44(2): 1088-1099.

图/表 11

图1 MS、MSBC、Co-N@MSBC的SEM图

图2 MS、MSBC、Co-N@MSBC的BET图

表1 MS、MSBC及Co-N@MSBC的孔结构特征

样品	比表面积 /m²·g^-1	平均孔径 /nm	总孔容 /cm³·g^-1	微孔 /cm³·g^-1
MS	1.0721	33.2096	0.006035	0.000068
MSBC	1.7246	42.4599	0.005975	0.000554
Co-N@MSBC	280.7649	7.5762	0.155945	0.094107

图3 MS、MSBC、Co-N@MSBC的FTIR图及吸附前后Co-N@MSBC的FTIR图

图4 Co-N@MSBC的XPS图

图5 不同体系对去除GAT的影响([GAT]=10mg/L，炭投加量=4.0g/L，[PMS]=0.04mol/L，初始pH=6.4，T=25℃，反应时间为1h)

图6 影响GAT去除效果的因素([GAT]=10mg/L，初始pH=6.4，T=25℃，反应时间=1h）(a)、(c)、(d)[PMS]=0.04mol/L；(b)、(c)、(d)[Co-N@MSBC]=6.0g/L

图7 Co-N@MSBC的循环利用效果([GAT]=10mg/L，[Co-N@MSBC]=6.0g/L，[PMS]=0.04mol/L，初始pH=6.4，T=25℃，反应时间为1h)

图8 不同浓度淬灭剂对GAT去除效果的影响([GAT]=10mg/L，[Co-N@MSBC]=6.0g/L，[PMS]=0.04mol/L，初始pH=6.4，T=25℃，反应时间为1h)

图9 电化学分析及不同时间点添加GAT对GAT去除效果的影响([GAT]=10mg/L，[Co-N@MSBC]=6.0g/L，[PMS]=0.04mol/L，初始pH=6.4，T=25℃，反应时间为1h)

图10 Co-N@MSBC/PMS体系去除GAT的机制

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钴氮共掺杂废菌棒生物炭活化PMS去除水中加替沙星

Removal of gatifloxacin from water by cobalt-nitrogen co-doped mushroom stick biological carbon activated PMS

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