Citation: Wang Yimeng, Zhang Shenping, Ge Yu, Wang Chenhui, Hu Jun, Liu Honglai. Highly Efficient Photocatalytic Degradation of Tetracycline Using a Bimetallic Oxide/Carbon Photocatalyst[J]. Acta Physico-Chimica Sinica, ;2020, 36(8): 190508. doi: 10.3866/PKU.WHXB201905083 shu

Highly Efficient Photocatalytic Degradation of Tetracycline Using a Bimetallic Oxide/Carbon Photocatalyst

Wang Yimeng ^1,† ,
Zhang Shenping ^1,† ,
Ge Yu ² ,
Wang Chenhui ¹ ,
Hu Jun ^1,, ,
Liu Honglai ¹

1.
School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China
2.
Shanghai Institute of Quality Inspection and Technical Research, Shanghai 200233, P. R. China

Corresponding author: Hu Jun, junhu@ecust.edu.cn
Received Date: 30 May 2019
Revised Date: 8 July 2019
Accepted Date: 9 July 2019
Available Online: 18 July 2019
Fund Project: The project was supported by the National Natural Science Foundation of China (91834301, 21676080, 21878076)The project was supported by the National Natural Science Foundation of China 21878076The project was supported by the National Natural Science Foundation of China 91834301The project was supported by the National Natural Science Foundation of China 21676080

Recently, MOF-derived metal oxides have been demonstrated as excellent semiconductor materials. Their derivatives can retain the high porosity and high specific surface area of the parent MOFs, effectively improving the adsorption capacity and mass transfer rate of reactive substances. Herein, UiO-67 was selected as the substrate due to its high hydrothermal stability and high specific surface area. Through the in situ growth of TiO₂ nanoparticles, a series of double metal composite catalysts (Zr_xTi/C) were produced after calcination at 400 ℃. The X-ray diffraction (XRD) patterns showed that the UiO-67 crystal structure of collapsed after calcination, forming a Zr-O-C/TiO₂ heterojunction. Energy-dispersive spectrometry (EDS) mapping images showed that Ti, Zr, and O were evenly distributed throughout the materials without obvious aggregation. Compared to conventional inorganic semiconductor materials, Zr_xTi/C heterojunction catalysts provided much higher BET surface area (317 m²·g^-1) for the effective enrichment of contaminants on the catalyst surface. Tetracycline was selected as a representative antibiotic to study photodegradation performance under a 300 W Xenon lamp. Among the obtained catalysts, the Zr_0.3Ti/C heterojunction catalyst exhibited the best photocatalytic efficiency, achieving 98% degradation within 30 min in a 10 mg·L^-1 tetracycline solution. Fluorescence spectra, electrochemical impedance spectroscopy, and transient photocurrent responses showed that the Zr_0.3Ti/C heterojunction catalyst exhibited the fastest charge-hole separation rate and a maximum photocurrent density of 8.75 μA·cm^-2, which was 2.64 and 3.71 times those of UiO-67 and UiO-67_0.3/TiO₂, respectively. The mechanism of tetracycline photodegradation was determined by UV-visible diffuse-reflectance absorption spectroscopy, Mott-Schottky plots, and electron spin resonance technology. A direct Z-scheme charge separation path was formed by the transfer and recombination of photoexcited e^- in the conduction band (CB) of Zr-O-C with h⁺ in the valence band (VB) of TiO₂, which effectively reduced the combination rate of e^- and h⁺ in Zr-O-C and TiO₂. The photodegradation rate constant of Zr_0.3Ti/C was 16 and 3.7 times those of TiO₂ and Zr-O-C, respectively, due to its large specific surface area and excellent tetracycline adsorption performance. Furthermore, the Zr-O-C/TiO₂ heterostructure exhibiting suitable energy level matching and containing highly conductive carbon material improved the separation and migration of electron-hole pairs. Mechanistic studies revealed that the three types of radicals, superoxide radicals (O₂^•-), hydroxyl radicals (•OH), and a small amount of holes (h⁺) simultaneously promoted tetracycline photodegradation. After five recycling tests, Zr_0.3Ti/C heterojunction catalyst maintained 91.2% removal efficiency for tetracycline, indicating good cycle stability. Combining the synergistic effects of adsorption and photodegradation, using bimetallic heterojunction composites with high specific surface area is promising for the photodegradation of environmental pollutants.
- Photocatalytic degradation,
- Porous catalyst,
- Bimetallic heterojunction,
- Metal organic framework material,
- Tetracycline
1. [1]
  Zhang, Q.; Xin, Q.; Zhu, J. M.; Cheng, J. P. Environ. Chem. 2014, 33, 1075. doi: 10.7524/j.issn.0254-6108.2014.07.001
2. [2]
  Hirsch, R.; Ternes, T.; Haberer, K.; Kratz, K. L. Sci. Total Environ. 1999, 225, 109. doi: 10.1016/S0048-9697(98)00337-4 doi: 10.1016/S0048-9697(98)00337-4
3. [3]
  Li, X. W.; Wang, B.; Yin, W. X.; Di, J.; Xia, J. X.; Zhu, W. S.; Li, H. M. Acta Phys. -Chim. Sin. 2020, 36, 1902001. doi: 10.3866/PKU.WHXB201902001
4. [4]
  Selvam, N. C. S.; Manikandan, A.; Kennedy, L. J.; Vijaya, J. J. J. Colloid Interface Sci. 2013, 389, 91. doi: 10.1016/j.jcis.2012.09.014 doi: 10.1016/j.jcis.2012.09.014
5. [5]
  Tao, J.; Gong, Z.; Yao, G.; Cheng, Y.; Zhang, M.; Lv, J.; Shi, S.; He, G.; Jiang, X.; Chen, X. J. Alloys Compd. 2016, 688, 605. doi: 10.1016/j.jallcom.2016.07.074 doi: 10.1016/j.jallcom.2016.07.074
6. [6]
  Liu, J.; Ke, J.; Li, Y.; Liu, B.; Wang, L.; Xiao, H.; Wang, S. Appl. Catal. B: Environ. 2018, 236, 396. doi: 10.1016/j.apcatb.2018.05.042 doi: 10.1016/j.apcatb.2018.05.042
7. [7]
  Zhang, L.; Qin, M.; Yu, W.; Zhang, Q.; Xie, H.; Sun, Z.; Shao, Q.; Guo, X.; Hao, L.; Zheng, Y.; et al. J. Electrochem. Soc. 2017, 164, H1086. doi: 10.1149/2.0881714jes doi: 10.1149/2.0881714jes
8. [8]
  Yuan, L.; Lu, K. Q.; Zhang, F.; Fu, X.; Xu, Y. J. Appl. Catal. B: Environ. 2018, 237, 424. doi: 10.1016/j.apcatb.2018.06.019 doi: 10.1016/j.apcatb.2018.06.019
9. [9]
  Issarapanacheewin, S.; Wetchakun, K.; Phanichphant, S.; Kangwansupamonkon, W.; Wetchakun, N. Catal. Today 2016, 278, 280. doi: 10.1016/j.cattod.2015.12.028 doi: 10.1016/j.cattod.2015.12.028
10. [10]
  Wang, M.; Hu, Y.; Han, J.; Guo, R.; Xiong, H.; Yin, Y. J. Mater. Chem. A 2015, 3, 20727. doi: 10.1039/C5TA05839B doi: 10.1039/C5TA05839B
11. [11]
  Yang, L.; Luo, S.; Li, Y.; Xiao, Y.; Kang, Q.; Cai, Q. Environ. Sci. Technol. 2010, 44, 7641. doi: 10.1021/es101711k doi: 10.1021/es101711k
12. [12]
  Zhang, N.; Yang, M. Q.; Liu, S.; Sun, Y.; Xu, Y. J. Chem. Rev. 2015, 115, 10307. doi: 10.1021/acs.chemrev.5b00267 doi: 10.1021/acs.chemrev.5b00267
13. [13]
  Zhang, N.; Xu, Y. J. CrystEngComm 2016, 18, 24. doi: 10.1039/C5CE01712B doi: 10.1039/C5CE01712B
14. [14]
  Zhang, N.; Zhang, Y.; Xu, Y. J. Nanoscale 2012, 4, 5792. doi: 10.1039/C2NR31480K doi: 10.1039/C2NR31480K
15. [15]
  Lu, K. Q.; Xin, X.; Zhang, N.; Tang, Z. R.; Xu, Y. J. J. Mater. Chem. A 2018, 6, 4590. doi: 10.1039/C8TA00728D doi: 10.1039/C8TA00728D
16. [16]
  Han, C.; Zhang, N.; Xu, Y. J. Nano Today 2016, 11, 351. doi: 10.1016/j.nantod.2016.05.008 doi: 10.1016/j.nantod.2016.05.008
17. [17]
  Zhang, T.; Lin, W. Chem. Soc. Rev. 2014, 43, 5982. doi: 10.1039/C4CS00103F doi: 10.1039/C4CS00103F
18. [18]
  Zeng, X.; Huang, L.; Wang, C.; Wang, J.; Li, J.; Luo, X. ACS Appl. Mater. Inter. 2016, 8, 20274. doi: 10.1021/acsami.6b05746 doi: 10.1021/acsami.6b05746
19. [19]
  Li, X.; Pi, Y.; Hou, Q.; Yu, H.; Li, Z.; Li, Y.; Xiao, J. Chem. Commun. 2018, 54, 1917. doi: 10.1039/C7CC09072B doi: 10.1039/C7CC09072B
20. [20]
  Wong-Foy, A. G.; Matzger, A. J.; Yaghi, O. M. J. Am. Chem. Soc. 2006, 128, 3494. doi: 10.1021/ja058213h doi: 10.1021/ja058213h
21. [21]
  Bux, H.; Chmelik, C.; Krishna, R.; Caro, J. J. Membr. Sci. 2011, 369, 284. doi: 10.1016/j.memsci.2010.12.001 doi: 10.1016/j.memsci.2010.12.001
22. [22]
  Montoro, C.; Linares, F.; Quartapelle Procopio, E.; Senkovska, I.; Kaskel, S.; Galli, S.; Masciocchi, N.; Barea, E.; Navarro, J. A. J. Am. Chem. Soc. 2011, 133, 11888. doi: 10.1021/ja2042113 doi: 10.1021/ja2042113
23. [23]
  Chen, Y. Z.; Zhang, R.; Jiao, L.; Jiang, H. L. Coordin. Chem. Rev. 2018, 362, 1. doi: 10.1016/j.ccr.2018.02.008 doi: 10.1016/j.ccr.2018.02.008
24. [24]
  Bala, S.; Mondal, I.; Goswami, A.; Pal, U.; Mondal, R. J. Mater. Chem. A 2015, 3, 20288. doi: 10.1039/C5TA05210F doi: 10.1039/C5TA05210F
25. [25]
  Su, Y.; Ao, D.; Liu, H.; Wang, Y. J. Mater. Chem. A 2017, 5, 8680. doi: 10.1039/C7TA00855D doi: 10.1039/C7TA00855D
26. [26]
  Pan, L.; Muhammad, T.; Ma, L.; Huang, Z. F.; Wang, S.; Wang, L.; Zou, J. J.; Zhang, X. Appl. Catal. B: Environ. 2016, 189, 181. doi: 10.1016/j.apcatb.2016.02.066 doi: 10.1016/j.apcatb.2016.02.066
27. [27]
  Zhang, Y. F.; Qiu, L. G.; Yuan, Y. P.; Zhu, Y. J.; Jiang, X.; Xiao, J. D. Appl. Catal. B: Environ. 2014, 144, 863. doi: 10.1016/j.apcatb.2013.08.019 doi: 10.1016/j.apcatb.2013.08.019
28. [28]
  Guo, Z.; Cheng, J. K.; Hu, Z.; Zhang, M.; Xu, Q.; Kang, Z.; Zhao, D. RSC Adv. 2014, 4, 34221. doi: 10.1039/C4RA05429F doi: 10.1039/C4RA05429F
29. [29]
  Dekrafft, K. E.; Wang, C.; Lin, W. Adv. Mater. 2012, 24, 2014. doi: 10.1002/adma.201200330 doi: 10.1002/adma.201200330
30. [30]
  Nickerl, G.; Leistner, M.; Helten, S.; Bon, V.; Senkovska, I.; Kaskel, S. Inorg. Chem. Front. 2014, 1, 325. doi: 10.1039/C3QI00093A doi: 10.1039/C3QI00093A
31. [31]
  Yan, S.; Ouyang, S.; Xu, H.; Zhao, M.; Zhang, X.; Ye, J. J. Mater. Chem. A 2016, 4, 15126. doi: 10.1039/C6TA04620G doi: 10.1039/C6TA04620G
32. [32]
  Liu, L.; Zhang, F.; Zhang, J.; Tan, X.; Zhang, B.; Shi, J.; Shao, D.; Tan, D.; Han, B.; Yang, G. Soft Matter 2017, 13, 9174. doi: 10.1039/C7SM02007D doi: 10.1039/C7SM02007D
33. [33]
  Liang, Y.; Cui, Z.; Zhu, S.; Li, Z.; Yang, X.; Chen, Y.; Ma, J. Nanoscale 2013, 5, 10916. doi: 10.1039/C3NR03616B doi: 10.1039/C3NR03616B
34. [34]
  Zhang, H.; Guo, L. H.; Wang, D.; Zhao, L.; Wan, B. ACS Appl. Mater. Inter. 2015, 7, 1816. doi: 10.1021/am507483q doi: 10.1021/am507483q
35. [35]
  Yu, J. H.; Fan, M. G.; Li, B.; Dong, L. H.; Zhang, F. Y. Acta Phys. -Chim. Sin. 2015, 31, 519. doi: 10.3866/PKU.WHXB201412291
36. [36]
  Zheng, D. Y.; Zhou, X. M.; Mutyala, S.; Huang, X. C. Chem.: Eur. J. 2018, 24, 19141. doi: 10.1002/chem.201803900 doi: 10.1002/chem.201803900
37. [37]
  Wang, A.; Zhou, Y.; Wang, Z.; Chen, M.; Sun, L.; Liu, X. RSC Adv. 2016, 6, 3671. doi: 10.1039/C5RA24135A doi: 10.1039/C5RA24135A
38. [38]
  Hong, Y.; Jiang, Y.; Li, C.; Fan, W.; Yan, X.; Yan, M.; Shi, W. Appl. Catal. B: Environ. 2016, 180, 663. doi: 10.1016/j.apcatb.2015.06.057 doi: 10.1016/j.apcatb.2015.06.057
39. [39]
  Di, J.; Xia, J.; Ge, Y.; Li, H.; Ji, H.; Xu, H.; Zhang, Q.; Li, H.; Li, M. Appl. Catal. B: Environ. 2015, 168, 51. doi: 10.1016/j.apcatb.2014.11.057 doi: 10.1016/j.apcatb.2014.11.057
40. [40]
  Du, X. Y.; Li, Y.; Yin, H.; Xiang, Q. J. Acta Phys. -Chim. Sin. 2018, 34, 414. doi: 10.3866/PKU.WHXB201708283
41. [41]
  Fang, W. H.; Zhang, L.; Zhang, J. Acta Phys. -Chim. Sin. 2018, 34, 781. doi: 10.3866/PKU.WHXB201711131
42. [42]
  Ma, X.; Xiang, Q.; Liao, Y.; Wen, T.; Zhang, H. Appl. Surf. Sci. 2018, 457, 846. doi: 10.1016/j.apsusc.2018.07.003 doi: 10.1016/j.apsusc.2018.07.003
43. [43]
  Yan, Y.; Zhou, X.; Lan, J.; Li, Z.; Zheng, T.; Cao, W.; Zhu, N.; Liu, W. J. Photochem. Photobiol. 2018, 367, 355. doi: 10.1016/j.jphotochem.2018.08.045 doi: 10.1016/j.jphotochem.2018.08.045
44. [44]
  Villamena, F. A.; Hadad, C. M.; Zweier, J. L. J. Am. Chem. Soc. 2004, 126, 1816. doi: 10.1021/ja038838k doi: 10.1021/ja038838k
45. [45]
  Clément, J. L.; Ferré, N.; Siri, D.; Karoui, H.; Rockenbauer, A.; Tordo, P. J. Org. Chem. 2005, 70, 1198. doi: 10.1021/jo048518z doi: 10.1021/jo048518z
46. [46]
  Li, H.; Zhai, F.; Gui, D.; Wang, X.; Wu, C.; Zhang, D.; Dai, X.; Deng, H.; Su, X.; Diwu, J.; et al. Appl. Catal. B: Environ. 2019, 254, 47. doi: 10.1016/j.apcatb.2019.04.087 doi: 10.1016/j.apcatb.2019.04.087
47. [47]
  Rawal, S. B.; Kang, H. J.; Won, D. I.; Lee, W. I. Appl. Catal. B: Environ. 2019, 256, 117856. doi: 10.1016/j.apcatb.2019.117856 doi: 10.1016/j.apcatb.2019.117856
1. [1]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
2. [2]
  Ping ZHANG , Chenchen ZHAO , Xiaoyun CUI , Bing XIE , Yihan LIU , Haiyu LIN , Jiale ZHANG , Yu'nan CHEN . Preparation and adsorption-photocatalytic performance of ZnAl@layered double oxides. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1965-1974. doi: 10.11862/CJIC.20240014
3. [3]
  Qiang ZHAO , Zhinan GUO , Shuying LI , Junli WANG , Zuopeng LI , Zhifang JIA , Kewei WANG , Yong GUO . Cu₂O/Bi₂MoO₆ Z-type heterojunction: Construction and photocatalytic degradation properties. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 885-894. doi: 10.11862/CJIC.20230435
4. [4]
  Shengbiao Zheng , Liang Li , Nini Zhang , Ruimin Bao , Ruizhang Hu , Jing Tang . Metal-Organic Framework-Derived Materials Modified Electrode for Electrochemical Sensing of Tert-Butylhydroquinone: A Recommended Comprehensive Chemistry Experiment for Translating Research Results. University Chemistry, 2024, 39(7): 345-353. doi: 10.3866/PKU.DXHX202310096
5. [5]
  Hongbo Zhang , Yihong Tang , Suxia Zhang , Yuanting Li . Electrochemical Monitoring of Photocatalytic Degradation of Phenol Pollutants: A Recommended Comprehensive Analytical Chemistry Experiment. University Chemistry, 2024, 39(6): 326-333. doi: 10.3866/PKU.DXHX202310013
6. [6]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
7. [7]
  Wenxiu Yang , Jinfeng Zhang , Quanlong Xu , Yun Yang , Lijie Zhang . Bimetallic AuCu Alloy Decorated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312014-. doi: 10.3866/PKU.WHXB202312014
8. [8]
  Zhengyu Zhou , Huiqin Yao , Youlin Wu , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Synergistic Effect of Cu-Graphdiyne/Transition Bimetallic Tungstate Formed S-Scheme Heterojunction for Enhanced Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(10): 2312010-. doi: 10.3866/PKU.WHXB202312010
9. [9]
  Shijie Li , Ke Rong , Xiaoqin Wang , Chuqi Shen , Fang Yang , Qinghong Zhang . Design of Carbon Quantum Dots/CdS/Ta₃N₅ S-Scheme Heterojunction Nanofibers for Efficient Photocatalytic Antibiotic Removal. Acta Physico-Chimica Sinica, 2024, 40(12): 2403005-. doi: 10.3866/PKU.WHXB202403005
10. [10]
  Jianjun LI , Mingjie REN , Lili ZHANG , Lingling ZENG , Huiling WANG , Xiangwu MENG . UV-assisted degradation of tetracycline hydrochloride by MnFe₂O₄@activated carbon activated persulfate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1869-1880. doi: 10.11862/CJIC.20240187
11. [11]
  Kexin Dong , Chuqi Shen , Ruyu Yan , Yanping Liu , Chunqiang Zhuang , Shijie Li . Integration of Plasmonic Effect and S-Scheme Heterojunction into Ag/Ag₃PO₄/C₃N₅ Photocatalyst for Boosted Photocatalytic Levofloxacin Degradation. Acta Physico-Chimica Sinica, 2024, 40(10): 2310013-. doi: 10.3866/PKU.WHXB202310013
12. [12]
  Juntao Yan , Liang Wei . 2D S-Scheme Heterojunction Photocatalyst. Acta Physico-Chimica Sinica, 2024, 40(10): 2312024-. doi: 10.3866/PKU.WHXB202312024
13. [13]
  Jiaming Xu , Yu Xiang , Weisheng Lin , Zhiwei Miao . Research Progress in the Synthesis of Cyclic Organic Compounds Using Bimetallic Relay Catalytic Strategies. University Chemistry, 2024, 39(3): 239-257. doi: 10.3866/PKU.DXHX202309093
14. [14]
  Ke Li , Chuang Liu , Jingping Li , Guohong Wang , Kai Wang . 钛酸铋/氮化碳无机有机复合S型异质结纯水光催化产过氧化氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2403009-. doi: 10.3866/PKU.WHXB202403009
15. [15]
  Asif Hassan Raza , Shumail Farhan , Zhixian Yu , Yan Wu . 用于高效制氢的双S型ZnS/ZnO/CdS异质结构光催化剂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406020-. doi: 10.3866/PKU.WHXB202406020
16. [16]
  Ruolin CHENG , Haoran WANG , Jing REN , Yingying MA , Huagen LIANG . Efficient photocatalytic CO₂ cycloaddition over W₁₈O₄₉/NH₂-UiO-66 composite catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 523-532. doi: 10.11862/CJIC.20230349
17. [17]
  Aiai WANG , Lu ZHAO , Yunfeng BAI , Feng FENG . Research progress of bimetallic organic framework in tumor diagnosis and treatment. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1825-1839. doi: 10.11862/CJIC.20240225
18. [18]
  Kaihui Huang , Dejun Chen , Xin Zhang , Rongchen Shen , Peng Zhang , Difa Xu , Xin Li . Constructing Covalent Triazine Frameworks/N-Doped Carbon-Coated Cu₂O S-Scheme Heterojunctions for Boosting Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(12): 2407020-. doi: 10.3866/PKU.WHXB202407020
19. [19]
  Guimin ZHANG , Wenjuan MA , Wenqiang DING , Zhengyi FU . Synthesis and catalytic properties of hollow AgPd bimetallic nanospheres. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 963-971. doi: 10.11862/CJIC.20230293
20. [20]
  Youlin SI , Shuquan SUN , Junsong YANG , Zijun BIE , Yan CHEN , Li LUO . Synthesis and adsorption properties of Zn(Ⅱ) metal-organic framework based on 3, 3', 5, 5'-tetraimidazolyl biphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1755-1762. doi: 10.11862/CJIC.20240061

Get Citation

PDF

XML

Metrics

PDF Downloads(15)
Abstract views(1874)
HTML views(508)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142