CoFe2O4/MgAl-LDH催化剂活化过氧一硫酸盐促进抗生素降解

doi:10.15541/jim20240222

无机材料学报 ›› 2025, Vol. 40 ›› Issue (4): 440-448.DOI: 10.15541/jim20240222 CSTR: 32189.14.10.15541/jim20240222

• 研究快报 • 上一篇

CoFe₂O₄/MgAl-LDH催化剂活化过氧一硫酸盐促进抗生素降解

李建军¹^,²^,³(), 陈芳明¹, 张梨梨³, 王磊¹, 张丽亭²^,³, 陈慧雯¹, 薛长国¹, 徐良骥¹^,²

1.安徽理工大学安徽省煤基固体废物新材料通用技术研究中心, 淮南 232001
2.深部煤炭安全开采与环境保护国家重点实验室, 淮南 232001
3.安徽康达检测技术有限公司, 芜湖 241003

收稿日期:2024-04-28 修回日期:2024-07-30 出版日期:2025-04-20 网络出版日期:2024-08-19
通讯作者: 李建军, 教授. E-mail: ljj.hero@126.com
作者简介:李建军(1975-), 教授. E-mail: ljj.hero@126.com

Peroxymonosulfate Activation by CoFe₂O₄/MgAl-LDH Catalyst for the Boosted Degradation of Antibiotic

LI Jianjun¹^,²^,³(), CHEN Fangming¹, ZHANG Lili³, WANG Lei¹, ZHANG Liting²^,³, CHEN Huiwen¹, XUE Changguo¹, XU Liangji¹^,²

1. Anhui Generic Technology Research Center for New Materials from Coal-based Solid Wastes, Anhui University of Science and Technology, Huainan 232001, China
2. National Key Laboratory of Safe Mining of Deep Coal and Environmental Protection, Huainan 232001, China
3. Anhui Kangda Testing Technology Co., Ltd., Wuhu 241003, China

Received:2024-04-28 Revised:2024-07-30 Published:2025-04-20 Online:2024-08-19
Contact: LI Jianjun, professor. E-mail: ljj.hero@126.com
About author:LI Jianjun (1975-), professor. E-mail: ljj.hero@126.com
Supported by:
University Synergy Innovation Program of Anhui Province(GXXT-2022-083);Science and Technology Plan Project of Wuhu City, China(2023kx12);Anhui Provincial Department of Education New Era Education Project(2023xscx070)

摘要/Abstract

摘要：

层状双氢氧化物(LDH)具有优异的亲水性和离子相互作用, 是一种很有前途的高性能催化剂载体。本研究采用简单的共沉淀水热法制备了CoFe₂O₄/MgAl-LDH复合催化剂。结果表明, 纳米级CoFe₂O₄颗粒覆盖在MgAl-LDH表面; CoFe₂O₄/MgAl-LDH的比表面积为82.84 m²·g^-1, 是CoFe₂O₄的2.34倍; CoFe₂O₄/MgAl-LDH的饱和磁化强度为22.24 A·m²·kg^-1, 可实现高效的固液分离。将催化剂用于活化过氧一硫酸盐(PMS)高效降解盐酸四环素(TCH), 发现CoFe₂O₄/MgAl-LDH的催化性能明显优于CoFe₂O₄。在最佳条件下([TCH]=25 mg/L, [PMS]=1.5 mmol/L, CoFe₂O₄/MgAl-LDH=0.20 g/L, pH 7, T=25 ℃), TCH去除率最高可达98.2%; 溶液中共存离子SO₄²⁻、Cl⁻、H₂PO₄⁻和CO₃²⁻对催化性能影响不大; 而且经过5次循环后CoFe₂O₄/MgAl-LDH的催化性能仍保持在67.2%。机理研究发现, O₂^•−和¹O₂在催化降解过程中起主导作用。

关键词: 磁性复合催化剂, 过氧一硫酸盐, CoFe₂O₄/水滑石, 高级氧化技术, 抗生素

Abstract:

Owing to outstanding hydrophilicity and ionic interaction, layered double hydroxides (LDHs) have emerged as a promising carrier for high performance catalysts. However, the synthesis of new specialized catalytic LDHs for degradation of antibiotics still faces some challenges. In this study, a CoFe₂O₄/MgAl-LDH composite catalyst was synthesized using a hydrothermal coprecipitation method. Comprehensive characterization reveals that the surface of MgAl-LDH is covered with nanometer CoFe₂O₄ particles. The specific surface area of CoFe₂O₄/MgAl-LDH is 82.84 m²·g^-1, which is 2.34 times that of CoFe₂O₄. CoFe₂O₄/MgAl-LDH has a saturation magnetic strength of 22.24 A·m²·kg^-1 facilitating efficient solid-liquid separation. The composite catalyst was employed to activate peroxymonosulfate (PMS) for the efficient degradation of tetracycline hydrochloride (TCH). It is found that the catalytic performance of CoFe₂O₄/MgAl-LDH significantly exceeds that of CoFe₂O₄. The maximum TCH removal reaches 98.2% under the optimal conditions ([TCH] = 25 mg/L, [PMS] = 1.5 mmol/L, CoFe₂O₄/MgAl-LDH = 0.20 g/L, pH 7, and T = 25 ℃). Coexisting ions in the solution, such as SO₄²⁻, Cl⁻, H₂PO₄⁻, and CO₃²⁻, have a negligible effect on catalytic performance. Cyclic tests demonstrate that the catalytic performance of CoFe₂O₄/MgAl-LDH remains 67.2% after five cycles. Mechanism investigations suggest that O₂^•−and ¹O₂ produced by CoFe₂O₄/MgAl-LDH play a critical role in the catalytic degradation.

Key words: magnetic composite catalyst, peroxymonosulfate, CoFe₂O₄/MgAl-LDH, advanced oxidation process, antibiotic

中图分类号:

TB332

李建军, 陈芳明, 张梨梨, 王磊, 张丽亭, 陈慧雯, 薛长国, 徐良骥. CoFe₂O₄/MgAl-LDH催化剂活化过氧一硫酸盐促进抗生素降解[J]. 无机材料学报, 2025, 40(4): 440-448.

LI Jianjun, CHEN Fangming, ZHANG Lili, WANG Lei, ZHANG Liting, CHEN Huiwen, XUE Changguo, XU Liangji. Peroxymonosulfate Activation by CoFe₂O₄/MgAl-LDH Catalyst for the Boosted Degradation of Antibiotic[J]. Journal of Inorganic Materials, 2025, 40(4): 440-448.

图/表 15

Fig. 1 XRD patterns (a) and hysteresis loop (b) of CoFe2O4/MgAl-LDH Insert in (b) showing the magnetic recovery of the sample by a hand magnet

Fig. 2 SEM images of MgAl-LDH and CoFe2O4/MgAl-LDH, and EDS mappings of CoFe2O4/MgAl-LDH (a, b) SEM images of MgAl-LDH; (c, d) SEM images of CoFe2O4/ MgAl-LDH; (e) EDS scanning area; (f-j) EDS mappings of CoFe2O4/ MgAl-LDH

Fig. 3 TEM (a) and HRTEM (b) images of CoFe2O4/MgAl- LDH

Fig. 4 XPS spectra of CoFe2O4/MgAl-LDH (a) Survey spectrum; (b-d) Spectra of (b) Fe2p, (c) Co2p, and (d) O1s

Fig. 5 N2 adsorption-desorption isotherms of CoFe2O4 (a), MgAl-LDH (b) and CoFe2O4/MgAl-LDH (c)

Fig. 6 Effects of different factors on TCH removal (a) Mass ratio of CoFe2O4 to MgAl-LDH; (b) Catalyst dosage; (c) PMS concentration; (d) pH ([TCH]=25 mg/L, [PMS]=1.5 mmol/L, CoFe2O4/MgAl-LDH=0.20 g/L, pH 7 and T=25 ℃)

Fig. 7 Effects of coexisting anions on TCH removal (a) and cyclic experiments (b) ([TCH]=25 mg/L, [PMS]=1.5 mmol/L, CoFe2O4/MgAl-LDH=0.20 g/L, pH 7 and T=25 ℃)

Fig. 8 Effects of ROS quenching tests on TCH removal (a) and EPR spectra of (b) DMPO-•OH and DMPO-SO4•−, (c) DMPO-O2•−, and (d) TEMP-1O2 ([TCH]=25 mg/L, [PMS]=1.5 mmol/L, CoFe2O4/MgAl-LDH=0.20 g/L, pH 7, T=25 ℃ and [Scavenger]=100 mmol/L)

Fig. 9 Schematic illustration of catalytic oxidation process to remove pollutants

Fig. S1 Functional relationship of TCH concentration and its absorbancy

Fig. S2 EDS-mapping result of CoFe2O4/MgAl-LDH

Table S1 SBET and pore size analysis data of the prepared CoFe2O4, MgAl-LDH and CoFe2O4/MgAl-LDH

Sample	S_BET/(m²·g^-1)	Pore volume/ (cm³·g^-1)	Pore size/nm
CoFe₂O₄	35.42	0.15	10.76
MgAl-LDH	138.78	0.16	5.76
CoFe₂O₄/MgAl-LDH	82.84	0.25	23.26

Fig. S3 Comparison of different systems (a) TCH removal; (b) Corresponding reaction rate constant

Table S2 Comparison of the effects of different catalysts on degrading TCH

Catalyst	Tetracycline concentration/(mg·L^-1)	Reactant conditions/(g·L^-1)	Time/min	Degradation efficiency/%	Ref.
MIL-53(Fe)@AC	20	[catalyst]=0.20 [PMS]=2.00	120	92.4	[S1]
Fe-N/BC	30	[catalyst]=0.05 [PMS]=0.50	60	89.9	[S2]
Mn-MoS₂@AABs	20	[catalyst]=0.40 [PMS]=2.50	90	82.4	[S3]
Co@N-MC	25	[catalyst]=0.04 [PMS]=0.20	30	91.2	[S4]
ZCO-CN	20	[catalyst]=0.13 [PMS]=0.10	30	91.0	[S5]
MIL-88A/CoFe₂O₄	10	[catalyst]=0.25 [PMS]=1.00	60	90.0	[S6]
CoFe₂O₄/MgAl-LDH	25	[catalyst]=0.20* [PMS]=0.23*	45	98.2	This work

Fig. S4 Adsorption cyclic experiment of CoFe2O4/MgAl-LDH

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CoFe₂O₄/MgAl-LDH催化剂活化过氧一硫酸盐促进抗生素降解

Peroxymonosulfate Activation by CoFe₂O₄/MgAl-LDH Catalyst for the Boosted Degradation of Antibiotic

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