Enhanced Degradation of Methyl Orange with CoFe2O4@Zeolite Catalyst as Peroxymonosulfate Activator: Performance and Mechanism

doi:10.15541/jim20220591

Abstract

Abstract:

CoFe₂O₄@zeolite (CFZ) was prepared by using a co-precipitation hydrothermal method and used for synthetic dyes degradation by activating peroxymonosulfate (PMS). Comprehensive characterizations suggest that CoFe₂O₄ nanoparticles composing porous shell layer is uniformly covered on Na-A zeolite. The specific surface area of CFZ is 107.06 m²/g, three times that of the original zeolite. Since CFZ has a saturation magnetization of 29.0 A·m²·kg^-1, it could be separated efficiently by magnetic separation. Catalytic degradation experiments indicate that the removal of methyl orange (MO) in the CFZ/PMS system is much higher than that using CFZ or PMS alone. Under the optimum condition ([MO]=50 mg/L, [PMS]=1.0 mmol/L, 0.2 g/L CFZ, pH 8 and T=25 ℃), MO removal efficiency is up to 97.1%. Effect of various factors, including pH, PMS and CFZ dosage, MO concentration and presence of coexisting anions, on the catalytic performance of CFZ is carefully studied. Reactive oxygen species quenching experiments suggest that ¹O₂ and O₂^•- play a dominant role in the degradation process. CFZ shows excellent recycling performance that the MO removal is declined by only 2.4% after 5 cycles. Catalytic degradation mechanism of the CFZ/PMS system is explored in detail.

Key words: advanced oxidation processe, peroxymonosulfate activation, magnetic catalyst, CoFe₂O₄@Zeolite, reactive oxygen species, degradation

CLC Number:

TB332

WANG Lei, LI Jianjun, NING Jun, HU Tianyu, WANG Hongyang, ZHANG Zhanqun, WU Linxin. Enhanced Degradation of Methyl Orange with CoFe₂O₄@Zeolite Catalyst as Peroxymonosulfate Activator: Performance and Mechanism[J]. Journal of Inorganic Materials, 2023, 38(4): 469-476.

Figures/Tables 13

Fig. 1 (a) XRD patterns and (b) magnetic hysteresis loops of the zeolite and CFZ, and (c) size distribution of CoFe2O4 nanoparticles

Fig. 2 SEM images of (a) zeolite and (b-c) CFZ, as well as EDS-mappings of (d) O, (e) Si, (f) Al, (g) Fe, and (h) Co

Fig. 3 (a) TEM image and (b) elemental line scanning spectra of CFZ, as well as XPS spectra of (c) survey, (d) Fe2p, (e) Co2p, and (f) O1s of CFZ Colorful figures are available on website

Fig. 4 (a) N2 adsorption-desorption isotherms and (b) pore size distributions of the prepared zeolite and CFZ, (c) removal of MO in different systems (0.2 g/L CFZ, [PMS] = 0.6 mmol/L, [MO] = 0.2 g/L, pH 8, T = 25 ℃), and effects of (d) catalyst dosage, (e) initial solution pH and (f) PMS concentration on MO removal (0.2 g/L CFZ, [PMS] = 1 mmol/L, [MO] = 50 mg/L, pH 8, T = 25 ℃) Colorful figures are available on website

Table 1 SBET and pore size analysis data of the prepared zeolite and CFZ

Sample	S_BET/(m²·g^-1)	Pore volume/ (cm³·g^-1)	Pore size/nm
Zeolite	30.13	0.08	15.00
CFZ	107.06	0.33	16.24

Fig. 5 Effects of (a) coexisting anions on MO removal, (b) cyclic experiments and (c) ROS quenching tests (0.2 g/L CFZ, under the conditions of [PMS] = 1 mmol/L, [MO] = [coexisting anions] = 50 mg/L, pH 8, T = 25 ℃, [scavengers] = 100 mmol/L) Colorful figures are available on website

Fig. 6 Schematic of ROS generation and MO degradation The black arrows show the generation route of ROS and the balls with colors correspond to different reactants, intermediates or products Colorful figures are available on website

Fig. S1 Degradation performance on different concentrations of MO (0.2 g/L CFZ, [PMS]=1 mmol/L, pH 8, T=25 ℃)

Fig. S2 Effect of high-concentration coexisting anions ([MO]=50 mg/L, [SO42-]=[CO32-]=[Cl-]=[H2PO42-]=1000 mg/L, 0.2 g/L CFZ, [PMS]=1 mmol/L, pH 7, T=25 ℃)

Fig. S3 XRD patterns of the fresh CFZ and the used CFZ

Fig. S4 SEM image of the CFZ cycled for 5 times

Fig. S5 Effect of initial solution pH on MB removal

Table S1 Removal efficiency of MB under different pH conditions

pH	3	5	7	9	11
Removal efficiency/%	73.96	91.83	94.22	93.99	94.96

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Enhanced Degradation of Methyl Orange with CoFe₂O₄@Zeolite Catalyst as Peroxymonosulfate Activator: Performance and Mechanism

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