Citation: Qiang XIA, Xiao-Gang LIAO, Hai-Li SHEN, Lin ZHENG, Gang LI, Tian TIAN. Co₃O₄ with Different Morphologies: Synthesis and Performances in Activating Peroxymonosulfate for Methylene Blue Degradation[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(11): 2191-2201. doi: 10.11862/CJIC.2022.221 shu

Co₃O₄ with Different Morphologies: Synthesis and Performances in Activating Peroxymonosulfate for Methylene Blue Degradation

Qiang XIA ¹ ,
Xiao-Gang LIAO ¹ ,
Hai-Li SHEN ¹ ,
Lin ZHENG ¹ ,
Gang LI ^1,, ,
Tian TIAN ^{1, 2}

1.
College of Chemistry and Chemical Engineering, Chongqing University of Technology, Chongqing 400054, China
2.
52 Institute of China North Industries Group, Baotou, Inner Mongolia 014000, China

Corresponding author: Gang LI, ligang2015@cqut.edu.cn
Received Date: 12 April 2022
Revised Date: 6 September 2022

Figures(10)

Three methods (urea hydrothermal-calcination, chemical bath deposition-calcination, and oxalate pyrolysis) were used to prepare Co₃O₄ powder materials with different morphologies, which were named Co₃O₄-A, Co₃O₄-B, and Co₃O₄-C, respectively. All of them were taken as catalysts to activate peroxymonosulfate (PMS) for the degradation of methylene blue (MB). It is found that these Co₃O₄ materials were quite different in their catalytic performance. Under the assistance of Co₃O₄-A, Co₃O₄-B, and Co₃O₄-C, the PMS decomposition reaction rate constants were measured as 0.047 1, 0.217 4, and 0.003 7 min^-1, while the degradation ratios of MB were 91.25% (reaction time: 50 min), 100.00% (reaction time: 25 min), and 31.55% (reaction time: 50 min), respectively. That is, Co₃O₄-B had the best catalytic performance. To make clear the difference in the catalytic ability of Co₃O₄, a series of characterizations were carried out. It is discovered that these Co₃O₄ materials are different in many ways such as crystallinity, microstructure, specific surface area, surface oxygen vacancy concentration, and surface hydroxyl density. And it is confirmed that the primary factor influencing the catalytic performance of Co₃O₄ is the surface hydroxyl density. In addition, the optimized parameters for MB degradation in the Co₃O₄-B/PMS reaction system were determined as follows: reaction temperature 25 ℃, catalyst dosage 0.02 g·L^-1, and PMS dosage 0.6 mmol·L^-1, where the MB degradation ratio was as high as 98.33%. Moreover, the reactive oxygen species ·SO₄^-, ·OH, ·O₂^- and ¹O₂ were all detected in the Co₃O₄-B/PMS system according to the quenching experiments and electron paramagnetic resonance tests, and sulfate radicals were identified as the primary reactive oxygen species.
- advanced oxidation processes,
- Co₃O₄,
- peroxymonosulfate,
- surface hydroxyl,
- methylene blue
1. [1]
  Oh W D, Chang V W C, Hu Z T, Goei R, Lim T T. Enhancing the Catalytic Activity of g-C₃N₄ through Me Doping (Me=Cu, Co and Fe) for Selective Sulfathiazole Degradation via Redox-Based Advanced Oxidation Process[J]. Chem. Eng. J., 2017,323:260-269. doi: 10.1016/j.cej.2017.04.107
2. [2]
  Hu P D, Long M C. Cobalt-Catalyzed Sulfate Radical-Based Advanced Oxidation: A Review on Heterogeneous Catalysts and Applications[J]. Appl. Catal. B-Environ., 2016,181:103-117. doi: 10.1016/j.apcatb.2015.07.024
3. [3]
  Zhang A Y, He Y Y, Chen Y P, Feng J W, Huang N H, Lian F. Degradation of Organic Pollutants by Co₃O₄ - Mediated Peroxymonosulfate Oxidation: Roles of High-Energy {001}-Exposed TiO₂ Support[J]. Chem. Eng. J., 2018,334:1430-1439. doi: 10.1016/j.cej.2017.11.078
4. [4]
  Wang Q, Xu Z T, Cao Y T, Chen Y Q, Du X, Yang Y, Wang Z H. Two- Dimensional Ultrathin Perforated Co₃O₄ Nanosheets Enhanced PMS- Activated Selective Oxidation of Organic Micropollutants in Environmental Remediation[J]. Chem. Eng. J., 2022,427131953. doi: 10.1016/j.cej.2021.131953
5. [5]
  Anipsitakis G P, Stathatos E. Heterogeneous Activation of Oxone Using Co₃O₄[J]. J. Phys. Chem. B, 2005,109:13052-13055. doi: 10.1021/jp052166y
6. [6]
  Chen X Y, Chen J W, Qiao X L, Wang D G, Cai X Y. Performance of Nano-Co₃O₄/Peroxymonosulfate System: Kinetics and Mechanism Study Using Acid Orange 7 as a Model Compound[J]. Appl. Catal. B - Environ., 2008,80:116-121. doi: 10.1016/j.apcatb.2007.11.009
7. [7]
  Liang J P, Fu L. Activation of Peroxymonosulfate(PMS) by Co₃O₄ Quantum Dots Decorated Hierarchical C@Co₃O₄ for Degradation of Organic Pollutants: Kinetics and Radical - Nonradical Cooperation Mechanisms[J]. Appl. Surf. Sci., 2021,563150335. doi: 10.1016/j.apsusc.2021.150335
8. [8]
  CHEN T M, CHEN H M, MA H Y, TANG K X, ZHAO Y W. Biochar- Co₃O₄ Composite Activates Peroxymonosulfate to Degrade Atrazine[J]. China Environmental Science, 2020,40(11):4786-4794. doi: 10.3969/j.issn.1000-6923.2020.11.018
9. [9]
  Liu B M, Song W B, Wu H X, Liu Z Y, Teng Y, Sun Y J, Xu Y H, Zheng H L. Degradation of Norfloxacin with Peroxymonosulfate Activated by Nanoconfinement Co₃O₄@CNT Nanocomposite[J]. Chem. Eng. J., 2020,398125498. doi: 10.1016/j.cej.2020.125498
10. [10]
  Xu H D, Zhang Y C, Li J J, Hao Q Q, Li X, Liu F H. Heterogeneous Activation of Peroxymonosulfate by a Biochar-Supported Co₃O₄ Composite for Efficient Degradation of Chloramphenicols[J]. Environ. Pollut., 2020,257113610. doi: 10.1016/j.envpol.2019.113610
11. [11]
  Wang Z M, Wang Z H, Li W, Lan Y Q, Chen C. Performance Comparison and Mechanism Investigation of Co₃O₄ - Modified Different Crystallographic MnO₂ (α, β, γ, and δ) as an Activator of Peroxymonosulfate(PMS) for Sulfisoxazole Degradation[J]. Chem. Eng. J., 2022,427130888. doi: 10.1016/j.cej.2021.130888
12. [12]
  Zhang H X, Wang J N, Zhang X Y, Li B, Cheng X W. Enhanced Removal of Lomefloxacin Based on Peroxymonosulfate Activation by Co₃O₄/δ-FeOOH Composite[J]. Chem. Eng. J., 2019,369:834-844. doi: 10.1016/j.cej.2019.03.132
13. [13]
  LIU M, HU L M, ZHANG G S, WANG P. Activation of Peroxymonosulfate by the Co/Zn Bimetallic Oxide for the Degradation of Bisphenol A[J]. Environmental Chemistry, 2018,37(4):753-760.
14. [14]
  Zhao L L, Zhang J M, Zhang Z P, Wei T, Wang J, Ma J, Ren Y M, Zhang H X. Co₃O₄ Crystal Plane Regulation to Efficiently Activate Peroxymonosulfate in Water: The Role of Oxygen Vacancies[J]. J. Colloid Interface Sci., 2022,623:520-531. doi: 10.1016/j.jcis.2022.05.045
15. [15]
  Li X N, Rykov A I, Zhang B, Zhangc Y J, Wang J H. Graphene Encapsulated FexCoy Nanocages Derived from Metal-Organic Frameworks as Efficient Activators for Peroxymonosulfate[J]. Catal. Sci. Technol., 2016,6:7486-7494. doi: 10.1039/C6CY01479H
16. [16]
  Oh W D, Lua S K, Dong Z L, Lim T K. High Surface Area DPA - Hematite for Efficient Detoxification of Bisphenol A via Peroxymonosulfate Activation[J]. J. Mater. Chem. A, 2014,2:15836-15845. doi: 10.1039/C4TA02758B
17. [17]
  Wacławek S, Grübel K, Černík M. Simple Spectrophotometric Determination of Monopersulfate[J]. Spectroc. Acta Pt. A - Molec. Biomolec. Spectr., 2015,149:928-933. doi: 10.1016/j.saa.2015.05.029
18. [18]
  Zhou X Q, Luo C G, Luo M Y, Wang Q L, Wang J, Liao Z W, Chen Z L, Chen Z Q. Understanding the Synergetic Effect from Foreign Metals in Bimetallic Oxides for PMS Activation: A Common Strategy to Increase the Stoichiometric Efficiency of Oxidants[J]. Chem. Eng. J., 2020,381122587. doi: 10.1016/j.cej.2019.122587
19. [19]
  Zhang T, Li C J, Ma J, Tian H, Qiang Z M. Surface Hydroxyl Groups of Synthetic α-FeOOH in Promoting ·OH Generation from Aqueous Ozone: Property and Activity Relationship[J]. Appl. Catal. B-Environ., 2008,82:131-137. doi: 10.1016/j.apcatb.2008.01.008
20. [20]
  Wang Z, Wang W Z, Zhang L, Dong J. Surface Oxygen Vacancies on Co 3O₄ Mediated Catalytic Formaldehyde Oxidation at Room Temperature[J]. Catal. Sci. Technol., 2016,6:3845-3853. doi: 10.1039/C5CY01709B
21. [21]
  Wang Z, Shen G L, Li J Q, Liu H D, Wang Q, Chen Y F. Catalytic Removal of Benzene over CeO₂ - MnO_x Composite Oxides Prepared by Hydrothermal Method[J]. Appl. Catal. B - Environ., 2013,138 - 139:253-259. doi: 10.1016/j.apcatb.2013.02.030
22. [22]
  Du J K, Bao J G, Liu Y, Kim S H, Dionysiou D D. Facile Preparation of Porous Mn/Fe₃O₄ Cubes as Peroxymonosulfate Activating Catalyst for Effective Bisphenol A Degradation[J]. Chem. Eng. J., 2019,376119193. doi: 10.1016/j.cej.2018.05.177
23. [23]
  Wang F F, Xiao M L, Ma X Y, Wu S J, Ge M F, Yu X L. Insights into the Transformations of Mn Species for Peroxymonosulfate Activation by Tuning the Mn₃O₄ Shapes[J]. Chem. Eng. J., 2021,404127097. doi: 10.1016/j.cej.2020.127097
24. [24]
  Khan A, Wang H B, Liu Y, Jawad A, Ifthikar J, Liao Z W, Wang T, Chen Z Q. Highly Efficient α-Mn₂O₃@α-MnO₂-500 Nanocomposite for Peroxymonosulfate Activation: Comprehensive Investigation of Manganese Oxides[J]. J. Mater. Chem. A, 2018,6:1590-1600. doi: 10.1039/C7TA07942G
25. [25]
  Dong Z Y, Zhang Q, Chen B Y, Hong J M. Oxidation of Bisphenol A by Persulfate via Fe₃O₄-α-MnO₂ Nanoflower-like Catalyst: Mechanism and Efficiency[J]. Chem. Eng. J., 2019,357:337-347. doi: 10.1016/j.cej.2018.09.179
26. [26]
  Gong Y, Zhao X, Zhang H, Yang B, Xiao K, Guo T, Zhang J J, Shao H X, Wang Y B, Yu G. MOF-Derived Nitrogen Doped Carbon Modified g-C₃N₄ Heterostructure Composite with Enhanced Photocatalytic Activity for Bisphenol A Degradation with Peroxymonosulfate under Visible Light Irradiation[J]. Appl. Catal. B-Environ., 2018,233:35-45. doi: 10.1016/j.apcatb.2018.03.077
27. [27]
  Yao Y J, Cai Y M, Wu G D, Wei F Y, Li X Y, Chen H, Wang S B. Sulfate Radicals Induced from Peroxymonosulfate by Cobalt Manganese Oxides (CoxMn₃-xO₄) for Fenton - like Reaction In Water[J]. J. Hazard. Mater., 2015,296:128-137. doi: 10.1016/j.jhazmat.2015.04.014
28. [28]
  Gao H Y, Huang C H, Mao L, Shao B, Shao J, Yan Z Y, Tang M, Zhu B Z. First Direct and Unequivocal Electron Spin Resonance Spin - Trapping Evidence for pH-Dependent Production of Hydroxyl Radicals from Sulfate Radicals[J]. Environ. Sci. Technol., 2020,54:14046-14056. doi: 10.1021/acs.est.0c04410
29. [29]
  Shao S, Li X S, Gong Z M, Fan B, Hu J H, Peng J B, Lu K, Gao S X. A New Insight into the Mechanism in Fe₃O₄@CuO/PMS System with Low Oxidant Dosage[J]. Chem. Eng. J., 2022,438135474. doi: 10.1016/j.cej.2022.135474
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Co3O4 with Different Morphologies: Synthesis and Performances in Activating Peroxymonosulfate for Methylene Blue Degradation

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通讯作者: 陈斌, bchen63@163.com

Co₃O₄ with Different Morphologies: Synthesis and Performances in Activating Peroxymonosulfate for Methylene Blue Degradation