Abstract
Oxygen vacancies (OVs) defects in metal oxide-based photocatalysts play a crucial role in improving the charge carrier separation efficiencies to enhance the photocatalytic performances. In this work, OVs were introduced in 3D Bi2MoO6 microspheres through a facile and fast microwave-assisted method via the modulation of tetramethylethylenediamine (TMEDA). EPR, Raman and XPS results demonstrated that large amounts of oxygen vacancies were formed on the surface of BMO microspheres. The photocatalytic properties of the samples were studied by degradation of tetracycline (TC) under visible light. The optimal Bi2MoO6 with OVs exhibited optimum photocatalytic activity, and the degradation rate was 7.0 times higher than that of pristine Bi2MoO6. This enhancement can be attributed to the 3D structure furnishing more surface active sites and suitable OVs defects favoring the electron–hole separation. Moreover, the defective Bi2MoO6 microspheres exhibit high stability because the photocatalytic activity remains almost unchanged after 5 cycles, making them favorable for practical applications. Finally, a possible visible light photocatalysis mechanism for the degradation of TC was tentatively proposed.
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A. G. Trovo, R. F. P. Nogueira, A. Agüera, A. R. Fernandez-Alba, and S. Malato, Corrigendum to “Degradation of the antibiotic amoxicillin by photo-Fenton process–Chemical and toxicological assessment”, Water Res., 2011, 45, 1394–1402
X. H. Liu, Y. Liu, S. Y. Lu, X. C. Guo, H. B. Lu, P. Qin, B. Bi, Z. F. Wan, B. D. Xi, and T. T. Zhang, Occurrence of typical antibiotics and source analysis based on PCA-MLR model in the East Dongting Lake, China, Ecotoxicol. Environ. Saf., 2018, 163, 145–152
C. I. Brinzila, N. Monteiro, M. J. Pacheco, L. Ciríaco, I. Siminiceanu, and A. Lopes, Degradation of tetracycline at a boron-doped diamond anode: influence of initial pH, applied current intensity and electrolyte, Environ. Sci. Pollut. Res., 2014, 21, 8457–8465
O. Hanay, B. Yıldız, S. Aslan, and H. Hasar, Removal of tetracycline and oxytetracycline by microscale zerovalent iron and formation of transformation products, Environ. Sci. Pollut. Res., 2014, 21, 3774–3782
T. H. Xu, R. J. Zou, X. F. Lei, X. M. Qi, Q. Wu, W. F. Yao, and Q. J. Xu, New and stable g-C3N4/HAp composites as highly efficient photocatalysts for tetracycline fast degradation, Appl. Catal., B, 2019, 245, 662–671
L. Shao, Z. M. Ren, G. S. Zhang, and L. L. Chen, Facile synthesis, characterization of a MnFe2O4/activated carbon magnetic composite and its effectiveness in tetracycline removal, Mater. Chem. Phys., 2012, 135, 16–24
Z. Y. Lu, J. Y. Peng, M. S. Song, Y. Liu, X. L. Liu, P. W. Huo, H. J. Dong, S. Q. Yuan, Z. F. Ma, and S. Han, Improved recyclability and selectivity of environment-friendly MFA-based heterojunction imprinted photocatalyst for secondary pollution free tetracycline orientation degradation, Chem. Eng. J., 2019, 360, 1262–1276
Q. F. Wu, Z. H. Li, and H. L. Hong, Adsorption of the quinolone antibiotic nalidixic acid onto montmorillonite and kaolinite, Appl. Clay Sci., 2013, 74, 66–73
D. L. Jiang, X. Peng, L. Q. Shao, L. Di, and C. Min, RGO-promoted all-solid-state g-C3N4/BiVO4 Z-scheme heterostructure with enhanced photocatalytic activity toward the degradation of antibiotics, Ind. Eng. Chem. Res., 2017, 56, 8823–8832
X. Yan, X. Y. Wang, W. Gu, M. M. Wu, Y. Yan, B. Hu, G. B. Che, D. L. Han, J. H. Yang, and W. Q. Fan, Single-crystalline AgIn(MoO4)2 nanosheets grafted Ag/AgBr composites with enhanced plasmonic photocatalytic activity for degradation of tetracycline under visible light, Appl. Catal., B, 2015, 164, 297–304
H. Zhou, K. Kalware, M. Shen, S. T. Zhong, and Y. F. Yao, Formamide-assisted one-step synthesis of BiOCOOH and Bi/BiOCOOH micro-/nanostructures with tunable morphologies and composition and their photocatalytic activities, CrystEngComm, 2020, 22, 1368–1380
F. Guo, M. Y. Li, H. J. Ren, X. L. Huang, W. X. Hou, C. Wang, W. L. Shi, and C. Y. Lu, Fabrication of pn CuBi2O4/MoS2 heterojunction with nanosheets-on-microrods structure for enhanced photocatalytic activity towards tetracycline degradation, Appl. Surf. Sci., 2019, 491, 88–94
S. Kumar, A. Baruah, S. Tonda, B. Kumar, V. Shanker, and B. Sreedhar, Cost-effective and eco-friendly synthesis of novel and stable N-doped ZnO/g-C3N4 core–shell nanoplates with excellent visible-light responsive photocatalysis, Nanoscale, 2014, 6, 4830–4842
F. Guo, M. Y. Li, H. J. Ren, X. L. Huang, K. K. Shu, W. L. Shi, and C. Y. Lu, Facile bottom-up preparation of Cl-doped porous g-C3N4 nanosheets for enhanced photocatalytic degradation of tetracycline under visible light, Sep. Purif. Technol., 2019, 228, 115770
L. Y. Zhang, T. G. Xu, X. Zhao, and Y. F. Zhu, Controllable synthesis of Bi2MoO6 and effect of morphology and variation in local structure on photocatalytic activities, Appl. Catal., B, 2010, 98, 138–146
S. Y. Wang, X. Ding, N. Yang, G. M. Zhan, X. H. Zhang, G. H. Dong, L. Z. Zhang, and H. Chen, Insight into the effect of bromine on facet-dependent surface oxygen vacancies construction and stabilization of Bi2MoO6 for efficient photocatalytic NO removal, Appl. Catal., B, 2020, 265, 118585
Z. Dai, F. Qin, H. P. Zhao, J. Ding, Y. L. Liu, and R. Chen, Crystal defect engineering of aurivillius Bi2MoO6 by Ce doping for increased reactive species production in photocatalysis, ACS Catal., 2016, 6, 3180–3192
L. Guo, Q. Zhao, H. D. Shen, X. X. Han, K. L. Zhang, D. J. Wang, F. Fu, and B. Xu, Ultrafine Au nanoparticles anchored on Bi2MoO6 with abundant surface oxygen vacancies for efficient oxygen molecule activation, Catal. Sci. Technol., 2019, 9, 3193–3202
J. J. Zhang, T. Wang, X. X. Chang, A. Li, and J. L. Gong, Fabrication of porous nanoflake BiMOx (M = W, V, and Mo) photoanodes via hydrothermal anion exchange, Chem. Sci., 2016, 7, 6381–6386
Z. W. Zhao, W. D. Zhang, Y. X. Sun, J. Y. Yu, Y. X. Zhang, H. Wang, F. Dong, and Z. B. Wu, Bi cocatalyst/Bi2MoO6 microspheres nanohybrid with SPR-promoted visible-light photocatalysis, J. Phys. Chem. C, 2016, 120, 11889–11898
J. L. Long, S. C. Wang, H. J. Chang, B. Z. Zhao, B. T. Liu, Y. G. Zhou, W. Wei, X. X. Wang, L. Huang, and W. Huang, Bi2MoO6 nanobelts for crystal facet-enhanced photocatalysis, Small, 2014, 10, 2791–2795
X. Ding, K. Zhao, and L. Z. Zhang, Enhanced photocatalytic removal of sodium pentachlorophenate with self-doped Bi2WO6 under visible light by generating more superoxide ions, Environ. Sci. Technol., 2014, 48, 5823–5831
Y. C. Hao, X. L. Dong, X. Y. Wang, S. R. Zhai, H. C. Ma, and X. F. Zhang, Controllable, electrostatic self-assembly of sub-3 nm graphene quantum dots incorporated into mesoporous Bi2MoO6 frameworks: efficient physical and chemical simultaneous co-catalysis for photocatalytic oxidation, J. Mater. Chem. A, 2016, 4, 8298–8307
J. G. Hou, S. Y. Cao, Y. Z. Wu, F. Liang, Y. F. Sun, Z. S. Lin, and L. C. Sun, Simultaneously efficient light absorption and charge transport of phosphate and oxygen-vacancy confined in bismuth tungstate atomic layers triggering robust solar CO2 reduction, Nano Energy, 2017, 32, 359–366
X. Xu, X. Ding, X. L. Yang, P. Wang, S. Li, Z. X. Lu, and H. Chen, Oxygen vacancy boosted photocatalytic decomposition of ciprofloxacin over Bi2MoO6: Oxygen vacancy engineering, biotoxicity evaluation and mechanism study, J. Hazard. Mater., 2019, 364, 691–699
Y. Chen, W. Y. Yang, S. Gao, C. X. Sun, and Q. Li, Synthesis of Bi2MoO6 nanosheets with rich oxygen vacancies by postsynthesis etching treatment for enhanced photocatalytic performance, ACS Appl. Nano Mater., 2018, 1, 3565–3578
W. T. Bi, C. M. Ye, C. Xiao, W. Tong, X. D. Zhang, W. Shao, and Y. Xie, Spatial location engineering of oxygen vacancies for optimized photocatalytic H2 evolution activity, Small, 2014, 10, 2820–2825
Y. H. Lv, Y. F. Liu, Y. Y. Zhu, and Y. F. Zhu, Surface oxygen vacancy induced photocatalytic performance enhancement of a BiPO4 nanorod, J. Mater. Chem. A, 2014, 2, 1174–1182
Y. S. Li, Z. L. Tang, J. Y. Zhang, and Z. T. Zhang, Defect engineering of air-treated WO3 and its enhanced visible-light-driven photocatalytic and electrochemical performance, J. Phys. Chem. C, 2016, 120, 9750–9763
Y. H. Lv, C. S. Pan, X. G. Ma, R. L. Zong, X. J. Bai, and Y. F. Zhu, Production of visible activity and UV performance enhancement of ZnO photocatalyst via vacuum deoxidation, Appl. Catal., B, 2013, 138, 26–32
X. Y. Pan, M. Q. Yang, X. Z. Fu, N. Zhang, and Y. J. Xu, Defective TiO2 with oxygen vacancies: synthesis, properties and photocatalytic applications, Nanoscale, 2013, 5, 3601–3614
F. C. Lei, Y. F. Sun, K. T. Liu, S. Gao, L. Liang, B. C. Pan, and Y. Xie, Oxygen vacancies confined in ultrathin indium oxide porous sheets for promoted visible-light water splitting, J. Am. Chem. Soc., 2014, 136, 6826–6829
D. J. Wang, H. D. Shen, L. Guo, C. Wang, F. Fu, and Y. C. Liang, Ag/Bi2MoO6-x with enhanced visible-light-responsive photocatalytic activities via the synergistic effect of surface oxygen vacancies and surface plasmon, Appl. Surf. Sci., 2018, 436, 536–547
Y. J. Sun, H. Wang, Q. Xing, W. Cui, J. Y. Li, S. J. Wu, and L. D. Sun, The pivotal effects of oxygen vacancy on Bi2MoO6: Promoted visible light photocatalytic activity and reaction mechanism, Chin. J. Catal., 2019, 40, 647–655
H. D. Li, W. J. Li, S. N. Gu, F. Z. Wang, X. T. Liu, and C. J. Ren, Forming oxygen vacancies inside in lutetium-doped Bi2MoO6 nanosheets for enhanced visible-light photocatalytic activity, Mol. Catal., 2017, 433, 301–312
J. H. Guo, L. Shi, J. Y. Zhao, Y. Wang, K. B. Tang, W. Q. Zhang, C. Z. Xie, and X. Y. Yuan, Enhanced visible-light photocatalytic activity of Bi2MoO6 nanoplates with heterogeneous Bi2MoO6-x@ Bi2MoO6 core-shell structure, Appl. Catal., B, 2018, 224, 692–704
I. Nakamura, N. Negishi, S. Kutsuna, T. Ihara, S. Sugihara, and K. Takeuchi, Role of oxygen vacancy in the plasma-treated TiO2 photocatalyst with visible light activity for NO removal, J. Mol. Catal. A: Chem., 2000, 161, 205–212
Y. H. Lv, W. Q. Yao, R. L. Zong, and Y. F. Zhu, Fabrication of wide-range-visible photocatalyst Bi2WO6−x nanoplates via surface oxygen vacancies, Sci. Rep., 2016, 6, 19347
M. Y. Zhang, C. L. Shao, J. B. Mu, X. M. Huang, Z. Y. Zhang, Z. C. Guo, P. Zhang, and Y. C. Liu, Hierarchical heterostructures of Bi2MoO6 on carbon nanofibers: controllable solvothermal fabrication and enhanced visible photocatalytic properties, J. Mater. Chem., 2012, 22, 577–584
H. W. Du, T. Wan, B. Qu, J. Scott, X. Lin, A. Younis, and D. W. Chu, Tailoring the multi-functionalities of one-dimensional ceria nanostructures via oxygen vacancy modulation, J. Colloid Interface Sci., 2017, 504, 305–314
H. D. Shen, W. W. Xue, F. Fu, J. F. Sun, Y. Z. Zhen, D. J. Wang, B. Shao, and J. W. Tang, Efficient Degradation of Phenol and 4-Nitrophenol by Surface Oxygen Vacancies and Plasmonic Silver Co-Modified Bi2MoO6 Photocatalysts, Chem.–Eur. J., 2018, 24, 18463–18478
J. F. Zhang, Y. F. Hu, X. L. Jiang, S. F. Chen, S. G. Meng, and X. L. Fu, Design of a direct Z-scheme photocatalyst: preparation and characterization of Bi2O3/g-C3N4 with high visible light activity, J. Hazard. Mater., 2014, 280, 713–722
J. N. Zhang, D. Y. Leng, L. Z. Zhang, G. Li, F. Ma, J. Z. Gao, H. B. Lu, and B. P. Zhu, Porosity and oxygen vacancy engineering of mesoporous WO3 nanofibers for fast and sensitive low-temperature NO2 sensing, J. Alloys Compd., 2021, 853, 157339
Y. J. Cai, D. Y. Li, J. Y. Sun, M. D. Chen, Y. R. Li, Z. W. Zou, H. Zhang, H. M. Xu, and D. S. Xia, Synthesis of BiOCl nanosheets with oxygen vacancies for the improved photocatalytic properties, Appl. Surf. Sci., 2018, 439, 697–704
Y. J. Lin, S. Zhou, X. H. Liu, S. Sheehan, and D. W. Wang, TiO2/TiSi2 heterostructures for high-efficiency photoelectrochemical H2O splitting, J. Am. Chem. Soc., 2009, 131, 2772–2773
Y. L. Feng, Z. S. Zhang, K. Zhao, S. L. Lin, H. Li, and X. Gao, Photocatalytic nitrogen fixation: Oxygen vacancy modified novel micro-nanosheet structure Bi2O2CO3 with band gap engineering, J. Colloid Interface Sci., 2021, 583, 499–509
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Huang, C., Ma, S., Zong, Y. et al. Microwave-assisted synthesis of 3D Bi2MoO6 microspheres with oxygen vacancies for enhanced visible-light photocatalytic activity. Photochem Photobiol Sci 19, 1697–1706 (2020). https://doi.org/10.1039/d0pp00247j
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DOI: https://doi.org/10.1039/d0pp00247j