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

doi:10.15541/jim20240222

Abstract

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

CLC Number:

TB332

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.

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

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