Bio-FeMnCeO x 活化PMS降解四环素效能与机制

doi:10.16085/j.issn.1000-6613.2023-0891

摘要/Abstract

摘要：

鉴于生物合成材料在水环境修复中成本低、环境友好、高效等优势，制备了Ce掺杂生物铁锰氧化物（Bio-FeMnCeO _x ），以盐酸四环素（TC）为目标污染物，研究了Bio-FeMnCeO _x 制备参数（Ce剂量、培养时间及样品处理方式等）和工艺条件（pH、PMS浓度、Bio-FeMnCeO _x 剂量等）对Bio-FeMnCeO _x 活化PMS降解TC的影响。通过自由基猝灭实验和电子顺磁共振（EPR）分析TC降解的主要活性氧物质种类和贡献率，推测了TC的降解路径和降解机制，验证了Bio-FeMnCeO _x 的循环稳定性。结果表明：①通过生物合成法成功制备了Bio-FeMnCeO _x，将其用于活化PMS降解TC具有良好的催化活性，在pH为11.0、PMS浓度200mg/L、Bio-FeMnCeO _x 剂量为100mg/L、反应时间为60min时，TC的降解效率可达93.75%；②通过自由基猝灭和EPR鉴定的实验发现，Bio-FeMnCeO _x /PMS体系主要的活性物质为·SO $4 -$ 和¹O₂；③Bio-FeMnCeO _x 具有良好的实验稳定性，重复使用8次后，TC的降解效率仍高达75.71%。该研究的发现为抗生素废水治理提供了新的催化技术路线。

关键词: 复合材料, 废水, 四环素, 降解, 自由基

Abstract:

In view of the low cost, environmentally friendly and high efficiency of biosynthetic materials in water environmental remediation, Ce-doped biogenic Fe/Mn oxides (Bio-FeMnCeO _x ) was prepared to degrade tetracycline hydrochloride (TC). The effects of preparation parameters (Ce dosage, cultivation time and polishing methods, i.e.) and procedure parameters (pH, PMS concentration, and Bio-FeMnCeO _x dosage, i.e.) of Bio-FeMnCeO _x on the degradation of TC by Bio-FeMnCeO _x activated PMS were explored. The main species and contribution of reactive oxygen of TC degradation were analyzed by free radical quenching experiments and electron paramagnetic resonance (EPR). The degradation pathway and mechanism of TC was confirmed and the cyclic stability of Bio-FeMnCeO _x were verified. The research results indicated that Bio-FeMnCeO _x was successfully prepared by biosynthesis, and it was used to activate PMS to degrade TC with good catalytic activity, and the degradation efficiency of TC could reach 93.75%. pH of 11.0, PMS concentration of 200mg/L, Bio-FeMnCeO _x dose of 100mg/L when the reaction time were 60min. The results of free radical quenching and EPR identification experiments indicated that the main active species in this system were ·SO $4 -$ and ¹O₂. The cyclic stability experiment showed that Bio-FeMnCeO _x had good stability. The degradation efficiency of TC was still as high as 75.71% after 8 times repetition. The results of this study provide a new technology for antibiotic wastewater treatment.

Key words: composites, waste water, tetracycline, degradation, radical

中图分类号:

刘梦凡, 王华伟, 王亚楠, 张艳茹, 蒋旭彤, 孙英杰. Bio-FeMnCeO _x 活化PMS降解四环素效能与机制[J]. 化工进展, 2024, 43(6): 3492-3502.

LIU Mengfan, WANG Huawei, WANG Yanan, ZHANG Yanru, JIANG Xutong, SUN Yingjie. Efficiency and mechanism of Bio-FeMnCeO _x activated PMS for degradation of tetracycline[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3492-3502.

图/表 10

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制备参数	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
Ce剂量
Ce-5	17.79	0.015	3.38
Ce-10	19.13	0.018	2.52
Ce-25	26.15	0.030	2.00
Ce-50	26.22	0.031	2.19
Ce-100	21.23	0.022	2.52
培养时间
3d	36.57	0.037	1.75
5d	23.56	0.022	1.63
7d	22.09	0.025	2.19
9d	45.34	0.048	1.88
11d	52.07	0.043	1.63

制备参数	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
Ce剂量
Ce-5	17.79	0.015	3.38
Ce-10	19.13	0.018	2.52
Ce-25	26.15	0.030	2.00
Ce-50	26.22	0.031	2.19
Ce-100	21.23	0.022	2.52
培养时间
3d	36.57	0.037	1.75
5d	23.56	0.022	1.63
7d	22.09	0.025	2.19
9d	45.34	0.048	1.88
11d	52.07	0.043	1.63

催化剂	条件	效率	参考文献
磁性生物炭	TC 20mg/L，PMS 0.07mmol/L，催化剂0.75g/L，120min	85.50%	[35]
B-NC	TC 20mg/L，PMS 0.16mmol/L，催化剂0.13g/L，60min	90.00%	[36]
PFSC-900	TC 20mg/L，PMS 0.3g/L，催化剂0.4g/L，120min	90.10%	[37]
Fe-N-CS-800	TC 20mg/L，PMS 1mmol/L，催化剂0.2g/L，12min	93.74%	[38]
Bio-FeMnCeO _x	TC 20mg/L，PMS 10.2g/L，催化剂0.1g/L，60min	93.75%	本研究

催化剂	条件	效率	参考文献
磁性生物炭	TC 20mg/L，PMS 0.07mmol/L，催化剂0.75g/L，120min	85.50%	[35]
B-NC	TC 20mg/L，PMS 0.16mmol/L，催化剂0.13g/L，60min	90.00%	[36]
PFSC-900	TC 20mg/L，PMS 0.3g/L，催化剂0.4g/L，120min	90.10%	[37]
Fe-N-CS-800	TC 20mg/L，PMS 1mmol/L，催化剂0.2g/L，12min	93.74%	[38]
Bio-FeMnCeO _x	TC 20mg/L，PMS 10.2g/L，催化剂0.1g/L，60min	93.75%	本研究

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