CoFe2O4@Zeolite催化剂活化过一硫酸盐对甲基橙的强化降解: 性能与机理

doi:10.15541/jim20220591

无机材料学报 ›› 2023, Vol. 38 ›› Issue (4): 469-476.DOI: 10.15541/jim20220591

• 研究快报 • 上一篇

CoFe₂O₄@Zeolite催化剂活化过一硫酸盐对甲基橙的强化降解: 性能与机理

王磊¹(), 李建军¹^,²(), 宁军³, 胡天玉¹^,², 王洪阳¹, 张占群¹, 武琳馨¹

1.安徽理工大学材料科学与工程学院, 淮南 232001
2.安徽理工大学环境友好材料与职业健康研究院, 芜湖 241000
3.安徽水韵环保股份有限公司, 芜湖 241000

收稿日期:2022-10-09 修回日期:2022-11-27 出版日期:2023-04-20 网络出版日期:2022-12-30
通讯作者: 李建军, 教授. E-mail: ljj.hero@126.com
作者简介:王磊(1998-), 男, 硕士研究生. E-mail: wangleidreamer@126.com

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

WANG Lei¹(), LI Jianjun¹^,²(), NING Jun³, HU Tianyu¹^,², WANG Hongyang¹, ZHANG Zhanqun¹, WU Linxin¹

1. School of Materials Science and Engineering, Anhui University of Science and Technology, Huainan 232001, China
2. Institute of Environment-friendly Materials and Occupational Health, Anhui University of Science and Technology, Wuhu 241000, China
3. Anhui Shuiyun Environmental Protection Co., Ltd., Wuhu 241000, China

Received:2022-10-09 Revised:2022-11-27 Published:2023-04-20 Online:2022-12-30
Contact: LI Jianjun, professor. E-mail: ljj.hero@126.com
About author:WANG Lei (1998-), male, Master candidate. E-mail: wangleidreamer@126.com
Supported by:
Natural Science Foundation of Anhui Province(1908085ME127);Research Foundation of the Institute of Environment-friendly Materials and Occupational Health(Wuhu);Anhui University of Science and Technology(ALW2021YF11)

摘要/Abstract

摘要：

采用共沉淀水热法制备了CoFe₂O₄@Zeolite (CFZ), 并将其用于活化过一硫酸盐(PMS)降解合成染料。综合表征表明, 组成多孔壳层的CoFe₂O₄纳米颗粒均匀地覆盖在Na-A沸石上。CFZ的比表面积为107.06 m²/g, 是原始沸石比表面积的3倍。CFZ的饱和磁化强度为29.0 A·m²·kg^-1, 可以进行有效磁分离。催化降解实验表明, CFZ/PMS体系对甲基橙(MO)的去除率远远高于单独使用CFZ或PMS。在最佳条件([MO]=50 mg/L、[PMS]=1.0 mmol/L、0.2 g/L CFZ、pH 8和T=25 ℃)下, MO去除率可达到97.1%。实验研究了pH、PMS用量、CFZ用量、MO浓度以及共存阴离子等因素对CFZ催化性能的影响。活性氧粒子淬灭实验表明, ¹O₂和O₂^•-在降解过程中起主导作用。CFZ具有良好的回收性能, 5次循环后MO去除效率仅下降2.4%。本文还详细讨论了CFZ/PMS体系的催化降解机理。

关键词: 高级氧化技术, 过一硫酸盐活化, 磁性催化剂, CoFe₂O₄@Zeolite, 活性氧粒子, 降解

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

中图分类号:

TB332

王磊, 李建军, 宁军, 胡天玉, 王洪阳, 张占群, 武琳馨. CoFe₂O₄@Zeolite催化剂活化过一硫酸盐对甲基橙的强化降解: 性能与机理[J]. 无机材料学报, 2023, 38(4): 469-476.

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.

图/表 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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CoFe₂O₄@Zeolite催化剂活化过一硫酸盐对甲基橙的强化降解: 性能与机理

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

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