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Progress in Chemistry 2021, Vol. 33 Issue (8): 1331-1343 DOI: 10.7536/PC201236 Previous Articles   Next Articles

• Review •

Structural Defects Regulation of Bismuth Molybdate Photocatalyst

Yifan Zhao1, Qiyun Mao1, Xiaoya Zhai1, Guoying Zhang1,2,3()   

  1. 1 Tianjin Key Laboratory of Structure and Performance for Functional Molecules, College of Chemistry, Tianjin Normal University,Tianjin 300387, China
    2 Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University,Jinan 250014, China
    3 Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China
  • Received: Revised: Online: Published:
  • Contact: Guoying Zhang
  • Supported by:
    Open Foundation of Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University(2018KLMNP05); Open Foundation of Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education); College of Chemistry, Nankai University and the Postgraduate and Doctoral Innovation Project of Tianjin(2020YJSS049)
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As a novel type of Bi(Ⅲ)-based semiconductor photocatalyst, bismuth molybdate(Bi2MoO6) possesses the advantages of layered structure, low cost, cleanness and efficiency, narrow band gap and visible light response, etc. Resultantly, it exhibits widely potential applications in various photocatalytic areas such as degradation of water pollutants, air purification, antibacterial, water splitting, carbon dioxide reduction and nitrogen fixation. However, there are still two main bottleneck problems which would restrict the practical applications of Bi2MoO6 and needs to be addressed urgently. One is the low absorption efficiency for solar energy and the other is the fast recombination rate of photogenerated electron-hole pairs. Introduction and regulation of structure defects in Bi2MoO6 have been proved to be effective strategies to resolve the above problems. In the paper, the research progress of Bi2MoO6 defect engineering in recent years is comprehensively reviewed, including elemental doping, oxygen vacancy, synergistic effects, etc. The different methods to construct defects in Bi2MoO6 and the corresponding photocatalytic properties are extensively summarized. Also, the structure-activity relationship and action mechanism of the structural defects in different research fields are in-depth discussed and concluded. Finally, the present shortcomings of defective Bi2MoO6 photocatalyst are analyzed and the development direction and prospects in future are prospected.

Contents

1 Introduction

2 Elemental doping defect of bismuth molybdate

2.1 Rare earth ion doping

2.2 Transition metal ion doping

2.3 Non-metal ion doping

2.4 Ion co-doping strategy

3 Oxygen vacancy defect of bismuth molybdate

3.1 Ion doping associated oxygen vacancy

3.2 Individual oxygen vacancy

3.3 Oxygen vacancy synergy

4 Conclusion and outlook

Key words: bismuth molybdate, defect modulation, ion doping, oxygen vacancy, synergistic effect, photocatalysis
Fig. 1 (a) Aurivillius structure of BMO[24];(b) Complete and partial DOS diagram of BMO[26]. Copyright 2020, Elsevier; Copyright 2012, Elsevier
Fig. 2 (a) The visible light photocatalytic efficiency of La-BMO for RhB degradation,(b) transition from rod-like to lamellar structure[46];(c) changes in the electronic structure of Sm-BMO with doping content[51]. Copyright 2018, Springer Nature; Copyright 2016, American Chemical Society.
Table 1 Summary of transition metal ions doped BMO
Ion Synthetic method Application Activity Light condition Ref.
Ti4+ Sonochemical MB/MG 90 min 99%/45min 92% 150 W Xe lamp(Visible) 58
Mn2+ Sonochemical MB/MG 90 min 70%/45 min 72% 150 W Xe lamp(Visible) 58
Cu2+ Sonochemical MB/MG 90 min 78%/45 min 90% 150 W Xe lamp(Visible) 58
Zn2+ Sonochemical MB/MG 90 min 80%/45 min 99% 150 W Xe lamp(Visible) 58
Zn2+ Hydrothermal RhB 30 min, 98.9% 240 W Xe lamp(UV-Visible) 59
Fe3+ Solvothermal N2 fixation/Cr(Ⅵ) 106.5 μmol·g-1·h-1/20 min 100% 300 W Xe lamp(Visible) 60
Fe3+ Solvothermal PE of H2O/Na2SO3 0.021%/0.018% AM 1.5(UV-Visible) 61
W6+ Solvothermal PE of H2O/Na2SO3 0.023%/0.021% AM 1.5(UV-Visible) 61
W6+ Hydrothermal RhB 140 min, 100% Xe lamp(Visible) 62
Co2+ Solvothermal RhB 120 min, 99.7% 500 W Xe lamp(Visible) 63
Pd2+ Photo-reduction Phenol 300 min, 22% 300 W halogen tungsten lamp(310~800 nm) 64
Bi3+ Hydrothermal NO removal 40 min, 55% 30 W LEDs(Visible) 65
Ru3+ Theoretical calculation 24
Fig. 3 (a) Comparison of NH3 production capacity,(b) energy band structure change and(c,d) relative work function diagrams of BMO and 0.5% Fe-BMO, respectively[60]. Copyright 2019, Elsevier
Fig. 4 (a) Density of states and(b) EIS Nyquist curves of BOC and Br-BOC[19]; ESR peaks of(c) ·O2-and(d) ·OH in C-BMO[69]. Copyright 2019, Elsevier; Copyright 2017, Wiley
Fig. 5 (a) Schematic diagram of compensated distribution of 4f electrons of Tb/Eu, Dy/Sm and Er/Nd[83];(b) photocatalytic degradation mechanism over Gd/Er/Lu triple-doped BMO[84]. Copyright 2017, Elsevier; Copyright 2019, Elsevier
Fig. 6 (a) Illustration of the possible formation process of crystal defects in Ce-doped BMO structure,(b) the ESR signal of Ce-Vo-defects in Ce-doped BMO structure,(c) visible light photocatalytic degradation of methyl paraoxon, and(d) photocatalytic disinfection efficiency of staphylococcus aureus[99]. Copyright 2016, American Chemical Society
Table 2 Summary of the construction and application of individual Vo-BMO system
Synthetic method Synthetic condition Application Ref.
solvothermal CTAB, 180 ℃,3 h Selective oxidation of BA 101
Br- induction CTAB,140 ℃,72 h,pH=6 NO removal 102
Atmosphere calcination 450 ℃,in air,2 h TC 103
Atmosphere calcination 250 ℃,in air,1 h RhB 104
Atmosphere calcination 250 ℃,in air,2 h Phenol 105
Atmosphere calcination 375 ℃,in air,2 h Phenol/4-NP 106
Chemical reduction NaBH4 + PVP,1 h NO removal 107
Chemical reduction NaBH4,pH=5 RhB/MO/Phenol 108
Reduction-reoxidation CaH2,140 ℃,12 h;250 ℃,5 h Phenol/MB 109
NaOH etching 0.05 M NaOH,20 h SMX/E. coli 110
Template direction BiOBr + Na2MoO4,50 ℃,48 h CO2 reduction/O2 evolution 111
Fig. 7 (a) Diagram of hierarchical Vo-BMO architectures,(b) in situ FTIR spectra of Vo-rich BMO before and after benzyl alcohol adsorption[101],(c) EPR spectra of Vo-BMO ultrathin nanosheets and bulk BMO,(d) atomic resolution STEMI-ADF images[111]. Copyright 2019, Elsevier; Copyright 2019, Elsevier
Fig. 8 (a) UV-vis diffuse reflectance spectra, and(b) transient photocurrent response of BMO-based samples[104];(c) HRTEM image and(d) schematic diagram of photocatalytic degradation mechanism for organic pollutants of Fe(Ⅲ)-Vo-BMO[105]. Copyright 2018, Elsevier; Copyright 2019, Elsevier
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