Citation: Fei ZHOU, Xiaolin JIA. Co₃O₄/TiO₂ composite photocatalyst: Preparation and synergistic degradation performance of toluene[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(11): 2232-2240. doi: 10.11862/CJIC.20240236 shu

Co₃O₄/TiO₂ composite photocatalyst: Preparation and synergistic degradation performance of toluene

Fei ZHOU ^1,, ,
Xiaolin JIA ^{1, 2}

1.
Jiangsu Keyida Environmental Technology Co., Ltd., Yancheng, Jiangsu 224051, China
2.
Yancheng Chengnan New Area Development and Construction Investment Co., Ltd., Yancheng, Jiangsu 224008, China

Corresponding author: Fei ZHOU, 422826571@qq.com
Received Date: 24 June 2024
Revised Date: 8 October 2024

Figures(6)

TiO₂ nanobelts and Co₃O₄/TiO₂ catalytic materials were prepared using the hydrothermal method. The catalyst was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray electron spectroscopy, and fluorescence spectroscopy. At room temperature, with a relative humidity of 50.0%, the total gas flow rate of 1.0 L·min^-1, the space velocity of 1.05×10⁴ h^-1, and toluene volume concentration of 25.0 μL·L^-1, two 6 W vacuum ultraviolet lamps were used as light sources to catalyze, degrade, and mineralize toluene. The results show that the prepared catalyst is in the shape of nano-ribbons. The loading of Co₃O₄ inhibits the recombination of photogenerated electrons and holes and can effectively improve the catalytic performance. The Co₃O₄/TiO₂ with a load of 6.0% Co₃O₄ has the best catalytic effect. When N₂ was used as a carrier gas, the degradation rate of toluene was only 34.7%. The toluene degradation is mainly due to the photolysis of vacuum ultraviolet light. When air was used as a carrier gas, O₃ was produced. The Co₃O₄/TiO₂ with a load of 6.0% and vacuum ultraviolet synergistically promote toluene degradation. The highest degradation rate of toluene was 91.7% and the mineralization rate was 74.6%. The degradation rate of toluene was 2.6 times that of nitrogen as a carrier gas.
- vacuum ultraviolet,
- photocatalysis,
- toluene,
- degradation,
- Co₃O₄/TiO₂
1. [1]
  LI S H, LI X Q, HU F T, ZHANG C, YAN X H. Catalytic oxidation of toluene with low loading bimetallic Au@Pt core-shell catalyst[J]. Chinese J. Inorg. Chem., 2019,35(3):553-562.
2. [2]
  Chen G Y, Wang Z, Lin F W, Zhang Z M, Yu H D, Yan B B, Wang Z H. Comparative investigation on catalytic ozonation of VOCs in different types over supported MnOx catalysts[J]. J. Hazard. Mater., 2020,391122218. doi: 10.1016/j.jhazmat.2020.122218
3. [3]
  Wang D S, Zhu X M, Yang X F, Jiao R Y, Zhao S, Song R N, Lü M H, Yang M. VOCs and odors control and development in pharmaceutical fermentation industry[J]. Environ. Sci., 2019,40:1990-1998.
4. [4]
  OU R, LIU M T, LU Y T, WANG X Y, YUAN A H, LI L L, YANG F. Improved catalytic abatement efficiency of VOCs via creating efficient synergy of dispersed Cu-Co oxides in molecular sieve[J]. Chinese J. Inorg. Chem., 2021,37(7):1322-1336.
5. [5]
  LIU J, XIA Y S, BAO D C, ZENG L. Mesoporous Cr₂O₃ with high surface area: Preparation and catalytic activity performance for toluene combustion[J]. Chinese J. Inorg. Chem., 2014,30(2):353-358.
6. [6]
  Liang S M, Shu Y J, Li K, Jian J, Huang H B, Deng J G, Leung D Y C, Wu M Y, Zhang Y G. Mechanistic insights into toluene degradation under VUV irradiation coupled with photocatalytic oxidation[J]. J. Hazard. Mater., 2020,399122967. doi: 10.1016/j.jhazmat.2020.122967
7. [7]
  Huang H B, Huang H L, Zhang L, Hu P, Xu Y, Ye X G, Liang X S, Chen J D, Ji M Y. Photooxidation of gaseous benzene by 185 nm VUV irradiation[J]. Environ. Eng. Sci., 2014,31:481-486. doi: 10.1089/ees.2014.0100
8. [8]
  Huang H B, Huang H L, Feng Q Y, Liu G Y, Zhan Y J, Wu M Y, Lu H X, Shu Y J, Leung D Y C. Catalytic oxidation of benzene over Mn modified TiO₂/ZSM-5 under vacuum UV irradiation[J]. Appl. Catal. B-Environ. Energy, 2017,203:870-878. doi: 10.1016/j.apcatb.2016.10.083
9. [9]
  Yuan J, Huang X, Chen M X, Shi J W, Shangguan W F. Ozone-assisted photocatalytic degradation of gaseous acetaldehyde on TiO₂/M-ZSM-5 (M=Zn, Cu, Mn)[J]. Catal. Today, 2013,201:182-188. doi: 10.1016/j.cattod.2012.06.003
10. [10]
  CHEN D B, DING J Y, ZHANG G L, FAN L, SUN L, CHENG F, LIU Y L, CHEN Y K, XU Q. Manganese supported nitrogen-doped graphene and performance of catalytic decomposition high-humidity ozone[J]. Chinese J. Inorg. Chem., 2022,38(10):2072-2082. doi: 10.11862/CJIC.2022.203
11. [11]
  Zhang J J, Hu Y J, Zheng H, Zhang P Y. Hierarchical Z-scheme 1D/2D architecture with TiO₂ nanowires decorated by MnO₂ nanosheets for efficient adsorption and full spectrum photocatalytic degradation of organic pollutants[J]. Catal Sci Technol., 2020,10:3603-3612. doi: 10.1039/D0CY00419G
12. [12]
  LIU F Q, WANG L M, FAN D, XU L H, PAN H. Preparation and photocatalytic properties of TiO₂/Cu₂O/Pt composite hollow microspheres[J]. Chinese J. Inorg. Chem., 2023,39(2):300-308.
13. [13]
  Zhang Z Q, Bai L L, Li Z J, Qu Y, Jing L Q. Review of strategies for the fabrication of heterojunctional nanocomposites as efficient visible-light catalysts by modulating excited electrons with appropriate thermodynamic energy[J]. J. Mater. Chem. A, 2019,7:10879-10897. doi: 10.1039/C9TA02373A
14. [14]
  Chen D J, Cheng Y L, Zhou N, Chen P, Wang Y P, Li K, Huo S H, Cheng P F, Peng P, Zhang R C, Wang L, Liu H, Liu Y H, Ruan R. Photocatalytic degradation of organic pollutants using TiO₂-based photocatalysts: A review[J]. J. Clean. Prod., 2020,268121725. doi: 10.1016/j.jclepro.2020.121725
15. [15]
  Zhao X R, Cao Y Q, Chen J, Zhu L, Qian X, Li A D, Wu D. Photocatalytic properties of Co₃O₄-coated TiO₂ powders prepared by plasma-enhanced atomic layer deposition[J]. Nano. Res. Lett., 2017,12497. doi: 10.1186/s11671-017-2269-4
16. [16]
  Liu J, Ke J, Li Y, Liu B J, Wang L D, Xiao H N, Wang S B. Co₃O₄ quantum dots/TiO₂ nanobelt hybrids for highly efficient photocatalytic overall water splitting[J]. Appl. Catal. B-Environ., 2018,236:396-403. doi: 10.1016/j.apcatb.2018.05.042
17. [17]
  Huang B, Yang W J, Wen Y W, Shan B, Chen R. Co₃O₄-modified TiO₂ nanotube arrays via atomic layer deposition for improved visible-light photoelectrochemical performance[J]. ACS Appl. Mater. Interfaces, 2015,7:422-431. doi: 10.1021/am506392y
18. [18]
  Bala S, Mondal I, Goswami A, Pal U, Mondal R. Co-MOF as a sacrificial template: Manifesting a new Co₃O₄/TiO₂ system with a p-n heterojunction for photocatalytic hydrogen evolution[J]. J. Mater. Chem. A, 2015,3:20288-20296. doi: 10.1039/C5TA05210F
19. [19]
  Shi Z K, Lan L, Li Y Z, Yang Y, Zhang Q, Wu J C, Zhang G Q, Zhao X J. Co₃O₄/TiO₂ nanocomposite formation leads to a tremendous improvement in UV-Vis-IR driven thermocatalytic activity due to novel photoactivation and photocatalysis-thermocatalysis synergetic effect[J]. ACS Sustain. Chem. Eng., 2018,6:16503-16514. doi: 10.1021/acssuschemeng.8b03602
20. [20]
  Dai J, Yang J, Wang X H, Zhang L, Li Y J. Enhanced visible-light photocatalytic activity for selective oxidation of amines into imines over TiO₂(B)/anatase mixed-phase nanowires[J]. Appl. Surf. Sci., 2015,349:343-352. doi: 10.1016/j.apsusc.2015.04.232
21. [21]
  Yu B, Meng F M, Khan M W, Qin R, Liu X B. Synthesis of hollow TiO₂@g-C₃N₄/Co₃O₄ core-shell microspheres for effective photooxidation degradation of tetracycline and MO[J]. Ceram. Int., 2020,46:13133-13143. doi: 10.1016/j.ceramint.2020.02.087
22. [22]
  Liu J, Li Y, Ke J, Wang S B, Wang L D, Xiao H N. Black NiO-TiO₂ nanorods for solar photocatalysis: Recognition of electronic structure and reaction mechanism[J]. Appl. Catal. B-Environ., 2018,224:705-714. doi: 10.1016/j.apcatb.2017.11.028
23. [23]
  Wang Y, Li H H, Wang S K, Wa ng, X , He Z, Hu J J. Investigation of sulphated CuCl₂/TiO₂ catalyst for simultaneous removal of Hg⁰ and NO in SCR process[J]. Fuel Process. Technol., 2019,188:179-189. doi: 10.1016/j.fuproc.2019.02.009
24. [24]
  Wu Z B, Sheng Z Y, Liu Y, Wang H Q, Mo J S. Deactivation mechanism of PtOx/TiO₂ photocatalyst towards the oxidation of NO in gas phase[J]. J. Hazard. Mater., 2011,185:1053-1058. doi: 10.1016/j.jhazmat.2010.10.013
25. [25]
  Guo Y, Dai Y X, Zhao W, Li H, Xu B, Sun C. Highly efficient photocatalytic degradation of naphthalene by Co₃O₄/Bi₂O₂CO₃ under visible light: A novel p-n heterojunction nanocomposite with nanocrystals/lotus-leaf-like nanosheets structure[J]. Appl. Catal. B-Environ., 2018,237:273-287. doi: 10.1016/j.apcatb.2018.05.089
26. [26]
  Wang Y T, Zhu C Z, Zuo G C, Guo Y, Xiao W, Dai Y X, Kong J J, Xu X M, Zhou Y X, Xie A M, Sun C, Xian Q M. 0D/2D Co₃O₄/TiO₂ Z-Scheme heterojunction for boosted photocatalytic degradation and mechanism investigation[J]. Appl. Catal. B-Environ., 2020,278119298. doi: 10.1016/j.apcatb.2020.119298
27. [27]
  Wang J K, Gao R, Zhou D, Chen Z J, Wu Z H, Schumacher G, Hu Z B, Liu X F. Boosting the electrocatalytic activity of Co₃O₄ nanosheets for a Li-O₂ battery through modulating inner oxygen vacancy and exterior Co³⁺/Co²⁺ ratio[J]. ACS Catal., 2017,7:6533-6541. doi: 10.1021/acscatal.7b02313
28. [28]
  Wu M Y, Zhang Y G, Szeto W, Pan W D, Huang H B, Leung D Y C. Vacuum ultraviolet (VUV)-based photocatalytic oxidation for toluene degradation over pure CeO₂[J]. Chem. Eng. Sci., 2019,200:203-213. doi: 10.1016/j.ces.2019.01.056
29. [29]
  Zoschke K, Börnick H, Worch E. Vacuum-UV radiation at 185 nm in water treatment-a review[J]. Water Res., 2014,52:131-145. doi: 10.1016/j.watres.2013.12.034
30. [30]
  Li M K, Qiang Z M, Pulgarin C, Kiwi J. Accelerated methylene blue (MB) degradation by Fenton reagent exposed to UV or VUV/UV light in an innovative micro photo-reactor[J]. Appl. Catal. B-Environ., 2016,187:83-89. doi: 10.1016/j.apcatb.2016.01.014
31. [31]
  Hashem T, Zirlewagen M, Braun A. Simultaneous photochemical generation of ozone in the gas phase and photolysis of aqueous reaction systems using one VUV light source[J]. Water Sci. Technol., 1997,35(4):41-48. doi: 10.2166/wst.1997.0081
32. [32]
  Shu Y J, Xu Y, Huang H B, Ji J, Liang S M, Wu M Y, Leung D Y C. Catalytic oxidation of VOCs over Mn/TiO₂/activated carbon under 185 nm VUV irradiation[J]. Chemosphere, 2018,208:550-558. doi: 10.1016/j.chemosphere.2018.06.011
33. [33]
  Liu Y, Yang W J, Zhang P Y, Zhang J Y. Nitric acid-treated birnessite-type MnO₂: An efficient and hydrophobic material for humid ozone decomposition[J]. Appl. Surf. Sci., 2018,442:640-649. doi: 10.1016/j.apsusc.2018.02.204
34. [34]
  Suzuki H, Araki S, Yamamoto H. Evaluation of advanced oxidation processes (AOP) using O₃, UV, and TiO₂ for the degradation of phenol in water[J]. J. Water Process. Eng., 2015,7:54-60. doi: 10.1016/j.jwpe.2015.04.011
35. [35]
  Liu Y, Zhang P Y. Catalytic decomposition of gaseous ozone over todorokite-type manganese dioxides at room temperature: Effects of cerium modification[J]. Appl. Catal. A-Gen., 2017,530:102-110. doi: 10.1016/j.apcata.2016.11.028
36. [36]
  Ochiai T, Masuko K, Tago S, Nakano R, Niitsu Y, Kobayashi G, Horio K, Nakata K, Murakami T, Hara M, Nojima Y, Kurano M, Serizawa I, Suzuki T, Ikekita M, Morito Y, Fujishima A. Development of a hybrid environmental purification unit by using of excimer VUV lamps with TiO₂ coated titanium mesh filter[J]. Chem. Eng. J., 2013,218:327-332. doi: 10.1016/j.cej.2012.12.048
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沈阳化工大学材料科学与工程学院沈阳 110142

Co3O4/TiO2 composite photocatalyst: Preparation and synergistic degradation performance of toluene

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通讯作者: 陈斌, bchen63@163.com

Co₃O₄/TiO₂ composite photocatalyst: Preparation and synergistic degradation performance of toluene