硫掺杂生物炭负载铁锰氧化物活化PMS降解四环素及多西环素

doi:10.19965/j.cnki.iwt.2025-0348

摘要/Abstract

摘要：

以废弃甘蔗皮为生物炭前驱体，采用浸渍热解法成功制备了生物炭负载铁锰双金属氧化物（IM-SCBC），采用扫描电镜、X射线衍射仪、X射线光电子能谱仪、拉曼光谱仪、比表面积及孔隙分析仪等对复合材料进行表征，系统探究其活化过硫酸盐（PMS）降解四环素（TC）和多西环素（DOX）的性能、影响因素及作用机理。实验结果表明，当n（Fe）∶n（Mn）=1∶1时，制备的催化剂表面形成立方尖晶石型结构，且金属离子高暴露在材料表面，同时因硫元素成功掺杂形成—C—S—活性位点，对污染物的降解效果最佳。该催化剂在pH为3~9宽酸碱范围内对TC和DOX的去除率均大于80%，且经过5次循环后去除率仍维持在70%以上，展现出优异的稳定性和抗干扰能力。通过单因素及响应面实验确定体系最优工艺参数为温度40 ℃、催化剂投加量0.4 g/L、TC和DOX降解对应的PMS投加量分别为0.065 g/L和0.057 g/L。在最优条件下，TC和DOX的去除率分别达到95.11%和94.87%，相较于同类体系，该催化体系显著降低了PMS消耗。机理研究证实，S掺杂与Fe/Mn双金属协同效应共同促进了催化剂对PMS的活化，通过自由基与非自由基途径共同降解污染物，其中¹O₂和O₂ ^·-为主要活性物种。该研究为农业废弃物的再利用及复杂水体中抗生素污染的治理提供高效、稳定且环境友好的新解决方案。

关键词: 铁锰氧化物, 生物炭, 过硫酸盐, 四环素, 多西环素

Abstract:

Using waste sugarcane bagasse as the biochar precursor,iron-manganese bimetallic oxide (IM-SCBC)loaded on biochar was successfully prepared via impregnation pyrolysis. Characterization of the composite material was conducted using scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and specific surface area and pore size analysis. The composite material was systematically investigated for its performance in activating PMS (peroxymonosulfate) to degrade TC (tetracycline) and DOX (doxycycline), along with the influencing factors and underlying mechanisms. Experimental results indicated that when n(Fe)∶n(Mn)=1∶1, the prepared catalyst exhibited a cubic spinel structure with high surface exposure. —C—S— active sites were successfully formed by sulfur doping, yielding optimal degradation efficiency for pollutants. This catalyst achieved removal rates exceeding 80% for both TC and DOX across wide pH range of 3-9. After five cycles, the removal rate remained above 70%, demonstrating excellent stability and resistance to interference. Through single-factor and response surface experiments, the process parameters were optimized. Under optimal conditions: temperature of 40 ℃, catalyst dosage of 0.4 g/L, and PMS dosages of 0.065 g/L for TC and 0.057 g/L for DOX, the removal rates for TC and DOX reached 95.11% and 94.87%, respectively. This catalytic system significantly reduced PMS consumption compared to similar systems. Mechanism studies confirmed that S doping and Fe/Mn bimetallic synergistic effects jointly promoted catalyst activation of PMS, degrading pollutants through both radical and non-radical pathways, with ¹O₂ and O₂ ^·- as primary active species. This research provided an efficient, stable, and environmentally friendly novel solution for agricultural waste reuse and antibiotic pollution treatment in complex water bodies.

Key words: iron-manganese oxides, biochar, persulfate, tetracycline, doxycycline

中图分类号:

TU993.3
X703

张山桥, 杨继涛, 张军, 张珊珊. 硫掺杂生物炭负载铁锰氧化物活化PMS降解四环素及多西环素[J]. 工业水处理, 2026, 46(3): 184-195.

Shanqiao ZHANG, Jitao YANG, Jun ZHANG, Shanshan ZHANG. Degradation of tetracycline and doxycycline by PMS activation over S-doped biochar loaded with iron-manganese oxide[J]. Industrial Water Treatment, 2026, 46(3): 184-195.

https://www.iwt.cn/CN/Y2026/V46/I3/184

图/表 12

图1 IM-SCBC及IM（1∶1）-SCBC催化剂的表征

Fig.1 Characterization of IM-SCBC and IM（1∶1）-SCBC catalysts

图2 IM（1∶1）-SCBC的SEM和EDS

Fig.2 SEM and EDS of the IM（1∶1）-SCBC

图3 不同催化剂体系对TC的去除效果（a）及其降解动力学拟合曲线（b）实验条件：催化剂投加量0.30 g/L，PMS投加量0.05 g/L，pH=5.0，T=25 ℃，吸附30 min，催化降解30 min。

Fig.3 Removal efficiency of TC by different catalyst systems （a） and corresponding degradation kinetic fitting curves（b）

表1 不同催化剂体系吸附TC的动力学拟合参数

Table 1 Kinetic parameters for the adsorption of TC by different catalyst systems

催化剂	准一级吸附动力学			准二级吸附动力学
催化剂	K ₁	Q _e/（mg·g^-1）	R ²	K ₂	Q _e/（mg·g^-1）	R ²
IM（1∶1）-SCBC	0.073 3	38.282 8	0.997 8	0.001 1	54.544 2	0.996 5
IM（1∶2）-SCBC	0.067 2	33.930 0	0.998 1	0.001 0	50.332 8	0.996 7
IM（2∶1）-SCBC	0.061 0	33.878 6	0.990 8	0.000 9	49.778 0	0.989 6
IM（1∶0）-SCBC	0.068 4	22.910 5	0.991 4	0.001 5	33.417 3	0.990 4
IM（0∶1）-SCBC	0.087 5	24.962 9	0.977 0	0.002 5	33.832 0	0.974 0
SCBC	0.079 7	4.117 4	0.987 9	0.002 2	5.604 4	0.994 8

图4 不同条件下IM（1∶1）-SCBC对TC/DOX的降解效果（a~b）催化剂投加量；（c~d）PMS投加量；（e~f）温度；（g~h）pH；（i~j）共存阴离子；（k~l）循环性能。

Fig.4 Degradation of TC/DOX by IM （1∶1）-SCBC under various conditions

表2 响应曲面试验设计水平及因素

Table 2 Response surface experimental design levels and factors

因素	变量	水平
因素	变量	-1	0	+1
温度/℃	A	30	35	40
IM（1∶1）-SCBC/（g·L^-1）	B	0.2	0.3	0.4
PMS/（g·L^-1）	C	0.025	0.050	0.075

图5 BBD实验设计及结果

Fig.5 BBD experimental design and results

图6 IM（1∶1）-SCBC、PMS投加量和温度对TC和DOX降解率的影响

Fig.6 Effects of IM（1∶1）-SCBC，PMS dosage and temperature on TC and DOX degradation rates

表3 不同铁基催化剂活化PMS降解TC的效果

Table 3 Degradation efficiency of TC by activation of PMS with different iron-based catalysts

催化材料	催化剂/（g·L^-1）	PMS/（g·L^-1）	初始pH	TC/（g·L^-1）	反应时间/min	TC降解率/%	参考文献
CoFe₂O₄/MoS₂	0.5	0.400	3.0	20	60	92.23	〔28〕
MnFe₂O₄/CNT	0.1	0.913	5.0	40	120	87.70	〔29〕
FMDS-3	0.2	0.457	5.5	40	60	90.70	〔30〕
MnFe₂O₄-CR	0.5	0.304	5.0	50	90	91.32	〔31〕
350FeOOH-MnO _x	0.1	0.153	5.0	10	60	92.50	〔32〕
IM（1∶1）-SCBC	0.4	0.065	5.0	20	20	95.11	本研究

图7 IM（1∶1）-SCBC使用前后的XPS

Fig.7 XPS spectra of IM（1∶1）-SCBC before and after used

图8 不同猝灭剂对体系降解TC和DOX效果的影响

Fig.8 Effects of different quenchers on degradation of TC and DOX in the system

图9 IM（1∶1）-SCBC/PMS降解TC和DOX的机制

Fig.9 Degradation mechanism of TC and DOX by IM（1∶1）-SCBC/PMS system

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