Citation: Ying-Xin ZHAO, Hao HU, Xin ZHOU, Shui-Jin YANG, Yun YANG. Preparation and photocatalytic degradation performance of MOF-808/BiOCl composites[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(8): 1553-1563. doi: 10.11862/CJIC.2023.114 shu

Preparation and photocatalytic degradation performance of MOF-808/BiOCl composites

Ying-Xin ZHAO ¹ ,
Hao HU ¹ ,
Xin ZHOU ¹ ,
Shui-Jin YANG ^1,, ,
Yun YANG ^2,,

1.
College of Chemistry and Chemical Engineering, Hubei Key Laboratory of Pollutant Analysis & Reuse Technology, Hubei Normal University, Huangshi, Hubei 435002, China
2.
College of Chemistry and Environmental Engineering, Hanjiang Normal University, Shiyan, Hubei 442000, China

Corresponding author: Shui-Jin YANG, yangshuijin@hbnu.edu.cn Yun YANG, yangyunhub@163.com
Received Date: 10 January 2023
Revised Date: 26 May 2023

Figures(13)

A novel MOF-808/BiOCl composite heterojunction material was prepared by combining highly stable MOF-808 with BiOCl by simple hydrothermal method. The photocatalytic performance of composite MOF-808/BiOCl on ciprofloxacin (CIP) was investigated using CIP as a contaminant. Compared with pure BiOCl, the performance of composite materials has been improved. Among them, composites containing 10% MOF-808 (MOF-808/BiOCl-10%) showed the best photocatalytic activity. Within 20 min of UV light irradiation, the photocatalytic degradation efficiency of CIP by MOF-808/BiOCl-10% was as high as 94.7%. X-ray powder diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), fluorescence spectroscopy, ultraviolet-visible diffuse reflection spectroscopy (UV-Vis DRS), photocurrent, electrochemical impedance, and other characterization techniques were performed to analyze the phase composition, morphology and photoelectrochemical properties of materials. The formation of MOF-808 and BiOCl heterojunctions is beneficial to suppress the compounding efficiency of photogenerated carriers and improving photocatalytic activity. The UV-Vis diffuse reflectance spectroscopy results show that the light absorption range of MOF-808/BiOCl-10% material is improved. At the same time, radical trapping experiments were carried out. It indicates that ·O₂^- and h⁺ are the active species that play a major role in the degradation of CIP by MOF-808/BiOCl-10%. Based on the above experimental data, the possible photocatalytic mechanism of MOF-808/BiOCl composites was proposed.
- Zr-MOF,
- BiOCl,
- photocatalysis,
- antibiotics,
- degradation mechanism
1. [1]
  Saini G, Kalra S, Kaur U. The purification of wastewater on a small scale by using plants and sand filter[J]. Appl. Water Sci., 2021,11(4)68. doi: 10.1007/s13201-021-01406-4
2. [2]
  Russell J N, Yost C K. Alternative, environmentally conscious approaches for removing antibiotics from wastewater treatment systems[J]. Chemosphere, 2021,263128177. doi: 10.1016/j.chemosphere.2020.128177
3. [3]
  ZHOU X, ZHANG Z, CHEN P, YANG S J, YANG Y. Preparation and photocatalytic degradation performance of Br-doped Br₂WO₆ microsphere[J]. Chinese J. Inorg. Chem., 2022,38(9):1716-1728.
4. [4]
  Zewde A, Zhang L, Li Z, Odey E A. A review of the application of sonophotocatalytic process based on advanced oxidation process for degrading organic dye[J]. Rev. Environ. Health, 2019,34(4):365-375. doi: 10.1515/reveh-2019-0024
5. [5]
  Qi K M, Song M X, Xie X Y, Wen Y, Wang Z R, Wei B, Wang Z W. CQDs/biochar from reed straw modified Z-scheme MgIn₂S₄/BiOCl with enhanced visible-light photocatalytic performance for carbamazepine degradation in water[J]. Chemosphere, 2021,287(2)132192.
6. [6]
  XU Q S, SONG Y J, LIU J X, WANG X C, LI C Q, WANG H. Effect of Si to Al ratio of Cu/HZSM-5 catalyst on the catalytic decomposition of N₂O[J]. Chinese Journal of Environmental Engineering, 2020,14(6):1579-1591.
7. [7]
  García-Montaño J, Domènech X, García-Hortal J A, Torrades F, Peral J. The testing of several biological and chemical coupled treatments for Cibacron Red FN-R azo dye removal[J]. J. Hazard Mater., 2008,154(3):484-490.
8. [8]
  Wang J, Wang S. Reactive species in advanced oxidation processes: Formation, identification and reaction mechanism[J]. Chem. Eng. J., 2020,401126158. doi: 10.1016/j.cej.2020.126158
9. [9]
  Yan X, Anguille S, Bendahan M, Moulin P. Ionic liquids combined with membrane separation processes: A review[J]. Sep. Purif. Technol., 2019,222:230-253. doi: 10.1016/j.seppur.2019.03.103
10. [10]
  Sanghamitra P, Mazumder D, Mukherjee S. J. Treatment of wastewater containing oil and grease by biological method—A review. J. Environ. Sci. Health Part A-Toxic/Hazard[J]. Subst. Environ. Eng., 2021,56(4):394-412. doi: 10.1080/10934529.2021.1884468
11. [11]
  LIANG M J, DENG N, XIANG X Y, MEI Y, YANG Z Y, YANG Y, YANG S J. Bi/BiVO₄ & Bi₄V₂O₁₁ Composite catalysts: Preparation and photocatalytic performance[J]. Chinese J. Inorg. Chem., 2019,35(2):263-270.
12. [12]
  Wang Q, Gao Q, Al-Enizi A M, Nafady A, Ma S. Recent advances in MOF-based photocatalysis: Environmental remediation under visible light[J]. Inorg. Chem. Front., 2020,7(2):300-339. doi: 10.1039/C9QI01120J
13. [13]
  ZOU C T, ZHANG Z, LIAO W J, YANG S J. Enhancement of photocatalytic performance of layered Bi₂MoO₆ by ferroelectric polarization[J]. Chinese J. Inorg. Chem., 2020,36(9):1717-1727.
14. [14]
  Byrne C, Subramanian G, Pillai C S. Recent advances in photocatalysis for environmental applications[J]. J. Environ. Chem. Eng., 2018,6(3):3531-3555. doi: 10.1016/j.jece.2017.07.080
15. [15]
  ZHANG Z, ZOU C T, YANG Z Y, YANG S J. One-step preparation and photocatalytic activity of Bi₂MoO₆/CoMoO₄ embroidery ball structure[J]. Chinese J. Inorg. Chem., 2020,36(8):1446-1456.
16. [16]
  Liu C, Ren Y H, Wang Z W, Shi Y Z, Guo B B, Yu Y, Wu L. Flowerlike BiOCl nanospheres fabricated by an in situ self-assembly strategy for efficiently enhancing photocatalysis[J]. J. Colloid Interface Sci., 2022,607(1):423-430.
17. [17]
  Liu M Y, Zhu H Q, Zhu N L, Yu Q L. Vacancy engineering of BiOCl microspheres for efficient removal of multidrug-resistant bacteria and antibiotic-resistant genes in wastewater[J]. Chem. Eng. J., 2021,426130710. doi: 10.1016/j.cej.2021.130710
18. [18]
  Kato D, Hongo K, Maezono R, Higashi M, Kunioku H, Yabuuchi M, Suzuki H, Okajima H, Zhong C, Nakano K, Abe R, Kageyama H. Valence band engineering of layered bismuth oxyhalides toward stable visible-light water splitting: Madelung site potential analysis[J]. J. Am. Chem. Soc., 2017,139(51):18725-18731. doi: 10.1021/jacs.7b11497
19. [19]
  Liang Y, Zhou X H, Li W, Peng H L. Preparation of two-dimensional [Bi₂O₂]^- based layered materials: Progress and prospects[J]. APL Mater., 2021,9(6)060905. doi: 10.1063/5.0052300
20. [20]
  Xiong D Z, Zhao W, Guo J J, Li S B, Ye Y, E L, Yang X F. Highly efficient and reusable BiOCl photocatalyst modulating by hydrogel immobilization and oxygen vacancies engineering[J]. Sep. Purif. Technol., 2021,277119628. doi: 10.1016/j.seppur.2021.119628
21. [21]
  Zhao H, Liu X, Dong Y M, Xia Y M, Wang H J. A special synthesis of BiOCl photocatalyst for efficient pollutants removal: New insight into the band structure regulation and molecular oxygen activation[J]. Appl. Catal. B-Environ., 2019,256117872. doi: 10.1016/j.apcatb.2019.117872
22. [22]
  YANG B Y, LI H, SHANG N Z, FENG C, GAO S T, WANG C. Visible-light responsive photocatalyst g-C₃N₄@BiOCl with hollow flower-like structure: Preparation and photocatalytic performance[J]. Chinese J. Inorg. Chem., 2017,33(3):396-404.
23. [23]
  Nafradi M, Hernadi K, Konya Z, Alapi T. Investigation of the efficiency of BiOI/BiOCl composite photocatalysts using UV, cool and warm white LED light sources—Photon efficiency, toxicity, reusability, matrix effect, and energy consumption[J]. Chemosphere, 2021,280130636. doi: 10.1016/j.chemosphere.2021.130636
24. [24]
  Long Z Q, Wang H L, Huang K W, Zhang G M, Xie H J. Di-functional Cu²⁺-doped BiOCl photocatalyst for degradation of organic pollutant and inhibition of cyanobacterial growth[J]. J. Hazard. Mater., 2021,424127554.
25. [25]
  Liu M Y, Lin G L, Liu Y M, Lin X Y, Wang L J, Xu Y F, Song X C. Ternary heterojunction Ag/AgIO₃/BiOCl(CMC) by a biomass template for photodegradation of tetracycline hydrochloride and gaseous formaldehyde[J]. Solid State Sci., 2021,112106517. doi: 10.1016/j.solidstatesciences.2020.106517
26. [26]
  Wang H X, Liao B, Lu T, Ai Y L, Liu G. Enhanced visible-light photocatalytic degradation of tetracycline by a novel hollow BiOCl@CeO₂ heterostructured microspheres: Structural characterization and reaction mechanism[J]. J. Hazard. Mater., 2020,385121552. doi: 10.1016/j.jhazmat.2019.121552
27. [27]
  Jiang D N, Chen M, Wang H, Zeng G M, Huang D L, Cheng M, Liu Y, Xue W J, Wang Z W. The application of different typological and structural MOFs-based materials for the dyes adsorption[J]. Coord. Chem. Rev., 2018,380:471-483.
28. [28]
  NIU B T, XIA W N, LAI Z Q, GUO H X, CHEN Z X. Metal organic skeleton Ni-BTC and Ni-BDC solvent effect morphology control and supercapacitor performance[J]. Chinese J. Inorg. Chem., 2022,38(8):1643-1654.
29. [29]
  Safaei M, Foroughi M M, Ebrahimpoor N, Jahani S, Omidi A, Khatamia M. A review on metal-organic frameworks: Synthesis and applications[J]. Trac-Trends Anal. Chem., 2019,118:401-425. doi: 10.1016/j.trac.2019.06.007
30. [30]
  Voorde B, Bueken B, Denayer J, Vos D. Adsorptive separation on metal-organic frameworks in the liquid phase[J]. Chem. Soc. Rev., 2014,43:5766-5788. doi: 10.1039/C4CS00006D
31. [31]
  Arora C, Soni S, Sahu S, Mittal J, Kumar P, Bajpaid P. Iron based metal organic framework for efficient removal of methylene blue dye from industrial waste[J]. J. Mol. Liq., 2019,284:343-352. doi: 10.1016/j.molliq.2019.04.012
32. [32]
  Shanahan J, Kissel D S, Sullivan E. PANI@UiO-66 and PANI@UiO-66-NH₂ polymer-MOF hybrid composites as tunable semiconducting materials[J]. ACS Omega, 2020,5(12):6395-6404. doi: 10.1021/acsomega.9b03834
33. [33]
  Rodríguez N A, Parra R, Grela M A. Structural characterization, optical properties and photocatalytic activity of MOF-5 and its hydrolysis products: Implications on their excitation mechanism[J]. RSC Adv., 2015,5(89):73112-73118. doi: 10.1039/C5RA11182J
34. [34]
  Pattappan D, Kavya K V, Vargheese S, Rajendra Kumar R T, Haldorai Y. Graphitic carbon nitride/NH₂-MIL-101(Fe) composite for environmental remediation: Visible-light-assisted photocatalytic degradation of acetaminophen and reduction of hexavalent chromium[J]. Chemosphere, 2022,286(3)131875.
35. [35]
  Alvaro M, Carbonell E, Ferrer B, Llabrés F X, Xamena I, Garcia H. Semiconductor behavior of a metal-organic framework (MOF)[J]. Chem. Eur. J., 2007,13(18):5106-5112. doi: 10.1002/chem.200601003
36. [36]
  HU H. Construction of zirconium-based metal-organic framework composites and study on adsorption and degradation of ciprofloxacin. Huangshi: Hubei Normal University. 2022: 1-70
37. [37]
  Ding J, Yang Z Q, He C, Tong X W, Li Y, Niu X J, Zhang H G. UiO-66(Zr) coupled with Bi₂MoO₆ as photocatalyst for visible-light promoted dye degradation[J]. J. Colloid Interface Sci., 2017,497:126-133. doi: 10.1016/j.jcis.2017.02.060
38. [38]
  Sun J Y, Li D Y, Li Y R, Cai Y J, Sun L, Yuan X J, Cao G, Xu H M, Xia D S. CMC/BiOCl 3D hierarchical nanostructures with exposed {001} facets and its enhanced photocatalytic activity[J]. ChemistrySelect, 2018,3(16):4463-4470. doi: 10.1002/slct.201703167
39. [39]
  Chen X Y, Chen D Y, Li N J, Xu Q F, Li H, He J H, Lu J M. Modified-MOF-808-loaded polyacrylonitrile membrane for highly efficient, simultaneous emulsion separation and heavy metal ion removal[J]. ACS Appl. Mater. Interfaces, 2020,12(35):39227-39235. doi: 10.1021/acsami.0c10290
40. [40]
  Dai S, Simms C, Dovgaliuk I, Patriarche G, Tissot A, Parac-Vogt T N, Serre C. Monodispersed MOF-808 nanocrystals synthesized via a scalable room-temperature approach for efficient heterogeneous peptide bond hydrolysis[J]. Chem. Mater., 2021,33(17):7057-7066. doi: 10.1021/acs.chemmater.1c02174
41. [41]
  Yu Z M, Lv Y K, Zhang F, Shi Q, An K, Huang F, Fan T T, Li G, Wang J. Catalytic degradation of organic pollutants in water under visible light by BiOCl@NH₂-MIL-125(Ti-Zr) composite photocatalyst[J]. J. Mater. Sci.-Mater. Electron., 2021,33:19599-19611.
42. [42]
  Xu J, Liu J, Li Z, Wang X B, Wang Z. Synthesis, structure and properties of Pd@ MOF-808[J]. J. Mater. Sci., 2019,54(19):12911-12924. doi: 10.1007/s10853-019-03786-0
43. [43]
  Qin H L, Zhang Y S, He S J, Guan Z Y, Shi Y T, Xie X Y, Xia D S, Li D Y, Xu H M. Increasing the migration and separation efficiencies of photogenerated carriers in CQDs/BiOCl through the point discharge effect[J]. Appl. Surf. Sci., 2021,562150214. doi: 10.1016/j.apsusc.2021.150214
44. [44]
  Hou J H, Tu X Y, Wu X G, Shen M, Wang X Z, Wang C Y, Cao C B, Peng H, Wang G X. Remarkable cycling durability of lithium-sulfur batteries with interconnected mesoporous hollow carbon nanospheres as high sulfur content host[J]. Chem. Eng. J., 2020,401126141. doi: 10.1016/j.cej.2020.126141
45. [45]
  Kong L C, Wang Y, Andrews C B, Zheng C M. One-step construction of hierarchical porous channels on electrospun MOF/polymer/graphene oxide composite nanofibers for effective arsenate removal from water[J]. Chem. Eng. J., 2022,435(1)134830.
46. [46]
  Tong X W, Yang Z Q, Feng J N, Li Y, Zhang H G. BiOCl/UiO-66 composite with enhanced performance for photo-assisted degradation of dye from water[J]. Appl. Organometal. Chem., 2017,32(2)e4049.
47. [47]
  Xu C, Wang J, Gao B R, Dou M M, Chen R. Synergistic adsorption and visible-light catalytic degradation of RhB from recyclable 3D mesoporous graphitic carbon nitride/reduced graphene oxide aerogels[J]. J. Mater. Sci., 2019,54(12):8892-8906. doi: 10.1007/s10853-019-03531-7
48. [48]
  Tang X L, Liu H H, Yang C, Jin X Y, Zhong J B, Li J Z. In-situ fabrication of Z-scheme CdS/BiOCl heterojunctions with largely improved photocatalytic performance[J]. Colloid Surf. A-Physicochem. Eng. Asp., 2020,599124880. doi: 10.1016/j.colsurfa.2020.124880
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