Efficient visible light photodegradation of BiVO₄:Yb³⁺/Tm³⁺ with high content of tetragonal phase

Abstract

In photocatalytic studies, tetragonal bismuth vanadate (t-BiVO₄) is not promising due to its wide band gap. However, according to previous studies, the tetragonal phase is inevitable when the monoclinic bismuth vanadate (m-BiVO₄) is modified. Therefore, it is necessary to find ways to improve the photoresponse and photocatalytic ability of t-BiVO₄ under visible light. In this study, Yb³⁺ and Tm³⁺ co-doped BiVO₄ was synthesized by a simple hydrothermal method, and its microstructure, morphology and optical properties were characterized and analyzed by scanning electron microscope, transmission electron microscopy, Brunauer-Emmett-Teller, X-ray diffraction, Raman, X-ray photoelectron spectroscopy, diffuse reflectance spectra, photoluminescence, upconversion luminescence and other means. The results show that BiVO₄:Yb³⁺/Tm³⁺ (BVYT) has a high content of tetragonal phase (about 80%), showing the characteristics of t-BiVO₄. BVYT shows a higher separation efficiency of photogenerated carriers, its transient photocurrent response intensity increased by about 3 times, and the photocatalytic efficiency is significantly improved compare with the undoped m-BiVO₄. Under simulated sunlight, BVYT completely degraded methylene blue (MB) solution and rhodamine B solution in 45 and 90 min, respectively, and the reaction rate was significantly improved. BVYT also shows excellent photocatalytic ability under visible light, about 35% of MB solution was degraded within 45 min under visible light irradiation (> 420 nm), this is because Yb³⁺ effectively promotes the upconversion luminescence of Tm³⁺ in response to visible light, and the energy cycle mechanism of Yb-Tm-Tm is proposed. Consequently, BiVO₄ with high content of tetragonal phase has excellent photoactivity, even exceeding m-BiVO₄. This is a novel discovery in the field of photocatalysis, which provides a broader application prospect for BiVO₄ in photocatalysis.

Key words： photocatalysis; bismuth vanadate; rare earth; upconversion luminescence

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work is financially supported by National Natural Science Foundation of China (Grant No. 51974168), Science and Technology Major Project of Inner Mongolia Autonomous Region in China (Grant Nos. 2019ZD023 and 2021ZD0028) and State Key Laboratory of Silicate Materials for Architectures (Wuhan University of Technology) (Grant No. SYSJJ2020-08).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2473-6 and is accessible for authorized users.

References

1 Zhang J , Wei X , Zhao J , Zhang Y , Wang L , Huang J , She H , Wang Q . Electronegative Cl^– modified BiVO₄ photoanode synergized with nickel hydroxide cocatalyst for high-performance photoelectrochemical water splitting. Chemical Engineering Journal, 2023, 454: 140081

2 Hua C , Liu X , Ren S , Zhang C , Liu W . Preparation of visible light-responsive photocatalytic paper containing BiVO₄@diatomite/MCC/PVBCFs for degradation of organic pollutants. Ecotoxicology and Environmental Safety, 2020, 202: 110897

3 ObregónSColónG. Excellent photocatalytic activity of Yb³⁺, Er³⁺ co-doped BiVO₄ photocatalyst. Applied Catalysis B: Environmental, 2014, 152–153: 328–334

4 Jo W J , Kang H J , Kong K J , Lee Y S , Park H , Lee Y , Buonassisi T , Gleason K K , Lee J S . Phase transition-induced band edge engineering of BiVO₄ to split pure water under visible light. Proceedings of the National Academy of Sciences of the United States of America, 2015, 112(45): 13774–13778

5 Bakhtiarnia S , Sheibani S , Nadi A , Aubry E , Sun H , Briois P , Yazdi M A P . Preparation of sputter-deposited Cu-doped BiVO₄ nanoporous thin films comprised of amorphous/crystalline heterostructure as enhanced visible-light photocatalyst. Applied Surface Science, 2023, 608: 155248

6 Liu J , Qiu L , Chang M J , Yuan B , Sun M , Fan S M , Cui W N , Hui Q , Ni F R , Li M Y . . Fabrication of novel fibrous BiVO₄/CdS heterostructures by electrospinning method for efficient visible light photodegradation. Materials Chemistry and Physics, 2020, 247: 122858

7 LiYXiaoXYeZ. Fabrication of BiVO₄/RGO/Ag₃PO₄ ternary composite photocatalysts with enhanced photocatalytic performance. Applied Surface Science, 2019, 467–468: 902–911

8 Noor M , Sharmin F , Mamun M A A , Hasan S , Hakim M A , Basith M A . Effect of Gd and Y co-doping in BiVO₄ photocatalyst for enhanced degradation of methylene blue dye. Journal of Alloys and Compounds, 2022, 895: 162639

9 Su W , Zheng M , Li L , Wang K , Qiao R , Zhong Y , Hu Y , Li Z . Directly coat TiO₂ on hydrophobic NaYF₄:Yb,Tm nanoplates and regulate their photocatalytic activities with the core size. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2014, 2(33): 13486–13491

10 Li Y , Cheng Z , Yao L , Yang S , Zhang Y . Boosting NIR-driven photocatalytic activity of BiOBr:Yb³⁺/Er³⁺/Ho³⁺ nanosheets by enhanced green upconversion emissions via energy transfer from Er³⁺ to Ho³⁺ ions. ACS Sustainable Chemistry & Engineering, 2019, 7(21): 18185–18196

11 Yang J , Liu J , Shi F , Ran S , Liu S . Tm, Yb co-doped urchin-like Cs_xWO₃ nanoclusters with dual functional properties: transparent heat insulation performance and enhanced photocatalysis. Ceramics International, 2021, 47(6): 8345–8356

12 Cao B , Gong S , Zubairu S M , Liu L , Xu Y , Guo L , Dang R , Zhu G . Fabrication of Er³⁺/Yb³⁺ co-doped Bi₅O₇I microsphere with upconversion luminescence and enhanced photocatalytic activity for bisphenol A degradation. Frontiers in Chemistry, 2020, 8: 773

13 Padhye P , Poddar P . Static and dynamic photoluminescence and photocatalytic properties of uniform, monodispersed up/down-converting, highly luminescent, lanthanide-ion-doped β-NaYF₄ phosphor microcrystals with controlled multiform morphologies. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2014, 2(45): 19189–19200

14 Li X , Li W , Liu X , Geng L , Fan H , Khan A , Ma X , Dong M , Qiu H . The construction of Yb/Er/Pr triple-doped Bi₂WO₆ superior photocatalyst and the regulation of superoxide and hydroxyl radicals. Applied Surface Science, 2022, 592: 153311

15 Liu T , Tan G , Zhao C , Xu C , Su Y , Wang Y , Ren H , Xia A , Shao D , Yan S . Enhanced photocatalytic mechanism of the Nd-Er co-doped tetragonal BiVO₄ photocatalysts. Applied Catalysis B: Environmental, 2017, 213: 87–96

16 Huang H , Wang Z , Huang B , Wang P , Zhang X , Qin X , Dai Y , Zhou G , Whangbo M H . Intense single red emission induced by near-infrared irradiation using a narrow bandgap oxide BiVO₄ as the host for Yb³⁺ and Tm³⁺ ions. Advanced Optical Materials, 2018, 6(15): 1701331

17 Huang S , Zhu N , Lou Z , Gu L , Miao C , Yuan H , Shan A . Near-infrared photocatalysts of BiVO₄/CaF₂:Er³⁺, Tm³⁺, Yb³⁺ with enhanced upconversion properties. Nanoscale, 2014, 6(3): 1362–1368

18 Nie Z , Ke X , Li D , Zhao Y , Zhu L , Qiao R , Zhang X L . NaYF₄:Yb,Er,Nd@NaYF₄: Nd upconversion nanocrystals capped with Mn:TiO₂ for 808 nm NIR-triggered photocatalytic applications. Journal of Physical Chemistry C, 2019, 123(37): 22959–22970

19 Obregón S , Colón G . On the origin of the photocatalytic activity improvement of BiVO₄ through rare earth tridoping. Applied Catalysis A, General, 2015, 501: 56–62

20 Ganguli S , Hazra C , Chatti M , Samanta T , Mahalingam V . A highly efficient UV-Vis-NIR active Ln³⁺-doped BiPO₄/BiVO₄ nanocomposite for photocatalysis application. Langmuir, 2016, 32(1): 247–253

21 Bai S , Li Q , Han N , Zhang K , Tang P , Feng Y , Luo R , Li D , Chen A . Synthesis of novel BiVO₄/Cu₂O heterojunctions for improving BiVO₄ towards NO₂ sensing properties. Journal of Colloid and Interface Science, 2020, 567: 37–44

22 Shan L , Liu Y . Er³⁺, Yb³⁺ doping induced core-shell structured BiVO₄ and near-infrared photocatalytic properties. Journal of Molecular Catalysis A Chemical, 2016, 416: 1–9

23 Tian H , Wu H , Fang Y , Li R , Huang Y . Hydrothermal synthesis of m-BiVO₄/t-BiVO₄ heterostructure for organic pollutants degradation: insight into the photocatalytic mechanism of exposed facets from crystalline phase controlling. Journal of Hazardous Materials, 2020, 399: 123159

24 Regmi C , Kshetri Y K , Ray S K , Pandey R P , Lee S W . Utilization of visible to NIR light energy by Yb³⁺, Er³⁺ and Tm³⁺ doped BiVO₄ for the photocatalytic degradation of methylene blue. Applied Surface Science, 2017, 392: 61–70

25 Huang J , Tan G , Zhang L , Ren H , Xia A , Zhao C . Enhanced photocatalytic activity of tetragonal BiVO₄: influenced by rare earth ion Yb³⁺. Materials Letters, 2014, 133: 20–23

26 Guo M , Xiang H , Tang S , Guo X , Yang Y , Zhang X . Effect of pyrolysis temperature on structure and photocatalytic properties of biochar-coupled BiVO₄. Journal of Environmental Chemical Engineering, 2022, 10(2): 107255

27 Fang S , Xue S , Wang C , Wang G , Wang X , Liang Q , Li Z , Xu S . Fabrication and characterization of CdS/BiVO₄ nanocomposites with efficient visible light driven photocatalytic activities. Ceramics International, 2016, 42(3): 4421–4428

28 Ullah S , Ferreira Neto E P , Hazra C , Parveen R , Rojas Mantilla H D , Calegaro M L , Serge Correales Y E , Rodrigues Filho U P , Ribeiro S J L . Broad spectrum photocatalytic system based on BiVO₄ and NaYbF₄:Tm³⁺ upconversion particles for environmental remediation under UV-Vis-NIR illumination. Applied Catalysis B: Environmental, 2019, 243: 121–135

29 Dong Q , Yang F , Liang F , Zhang Y , Xia D , Zhao W , Wu L , Liu X , Jiang Z , Sun C . Silver particle on BiVO₄ nanosheet plasmonic photocatalyst with enhanced photocatalytic oxidation activity of sulfadiazine. Journal of Molecular Liquids, 2021, 331: 115751

30 Ye S , Xu Y , Huang L , Lai W , Deng L , Lin Z , Peng H , Zhou X , Xie G . MWCNT/BiVO₄ photocatalyst for inactivation performance and mechanism of Shigella flexneri HL, antibiotic-resistant pathogen. Chemical Engineering Journal, 2021, 424: 130415

31 She H , Jiang M , Yue P , Huang J , Wang L , Li J , Zhu G , Wang Q . Metal (Ni²⁺/Co²⁺) sulfides modified BiVO₄ for effective improvement in photoelectrochemical water splitting. Journal of Colloid and Interface Science, 2019, 549: 80–88

32 Wang Q , Li J , Xiao L , Wang Y , Du H . Constructing Z-scheme Fe₃N/BiVO₄ heterojunction via electrostatic self-assembly toward high visible-light photocatalytic hydrogen evolution. Journal of Alloys and Compounds, 2023, 935: 168062

33 Liu F , Zhang S , Xu D , Sun F , Wang W , Li X , Yu W , Dong X , Liu G , Yu H . Columnar cactus-like 2D/1D BiOBr/BiVO₄:Yb³⁺, Er³⁺ heterostructure photocatalyst with ultraviolet-visible-near infrared response for photocatalytic degrading dyes, endocrine disruptors and antibiotics. Journal of Alloys and Compounds, 2022, 929: 167330

34 Fan J , Chen Y , Long Z , Tong L , He G , Hu Z . Giant dielectric response and relaxation behavior in (Tm + Ta) co-doped TiO₂ ceramics. Physical Chemistry Chemical Physics, 2022, 24(8): 4759–4768

35 Kim J H , Kim S J , Lee C I , Jung M A , Oh H J , Rhyee J S , Jo Y , Mitani H , Miyazaki H , Kimura S . . Kondo-like behaviors in magnetic and thermal properties of single crystal Tm₅Si₂Ge₂. Physical Review B: Condensed Matter and Materials Physics, 2010, 81(10): 104401

36 Yu Z , Liang R , Zhou M , Yang K , Mu P , Lu K , Huang W , Ouyang S , Li Z , Yu C . Steering oxygen vacancies for the enhanced photocatalytic degradations of dyes and tetracycline over Cu, Yb co-doped SnO₂ with efficient charge separation and transfer. Journal of the Taiwan Institute of Chemical Engineers, 2022, 133: 104249

37 Zhao W , Liu Y , Wei Z , Yang S , He H , Sun C . Fabrication of a novel p-n heterojunction photocatalyst n-BiVO₄@p-MoS₂ with core-shell structure and its excellent visible-light photocatalytic reduction and oxidation activities. Applied Catalysis B: Environmental, 2016, 185: 242–252

38 Ma C , Din S T U , Seo W C , Lee J , Kim Y , Jung H , Yang W . BiVO₄ ternary photocatalyst co-modified with N-doped graphene nanodots and Ag nanoparticles for improved photocatalytic oxidation: a significant enhancement in photoinduced carrier separation and broad-spectrum light absorption. Separation and Purification Technology, 2021, 264: 118423

39 Zhang W , Zhang H , Huang W , Lu X , Gao S , Wang J , Zhang D , Zhang X , Wang M . Structure, morphology and photocatalytic performance of europium-doped bismuth vanadate. Inorganic Chemistry Frontiers, 2022, 9(5): 977–986

40 Wang J R , Shen L F , Yan S , Pun E Y B , Lin H . A novel multifunctional BVO-T₁Y₈ porous nanofibers for multi-selective gas sensing and real-time temperature monitoring. Chemical Engineering Journal, 2022, 431: 134175

41 Ren H , Huang F , Jiang J , Wang L , Zhang J . Development of photocatalyst based on NaYF₄:Yb, Tm@NaYF₄:Yb, Ce/NH₂-MIL-101 (Cr): doping Ce³⁺ ions to promote the efficient energy transfer between core and shell. Chemical Engineering Journal, 2022, 427: 132023

42 Zhao K , Liu X , He Q , Zhou W , Yang K , Tao L , Li F , Yu C . Preparation and characterization of Sm³⁺/Tm³⁺ co-doped BiVO₄ micro-squares and their photocatalytic performance for CO₂ reduction. Journal of the Taiwan Institute of Chemical Engineers, 2023, 144: 104737

43 Yuan S , Wang J , Zhao C , Yue L , Ren X , Zeng Z , Hu X , Wu Y , He Y . S-scheme Bi₂O₃/CdMoO₄ hybrid with highly efficient charge separation for photocatalytic N₂ fixation and tetracycline degradation: fabrication, catalytic optimization, physicochemical studies. Separation and Purification Technology, 2023, 325: 124665

44 Zhao C , Li X , Yue L , Yuan S , Ren X , Zeng Z , Hu X , Wu Y , He Y . One-step preparation of novel Bi-Bi₂O₃/CdWO₄ Z-scheme heterojunctions with enhanced performance in photocatalytic NH₃ synthesis. Journal of Alloys and Compounds, 2023, 968: 171956

45 Zhao C , Li X , Yue L , Ren X , Yuan S , Zeng Z , Hu X , Wu Y , He Y . Bi₄O₅Br₂ nanoflower and CdWO₄ nanorod heterojunctions for photocatalytic synthesis of ammonia. ACS Applied Nano Materials, 2023, 6(17): 15709–15720

46 Xie H , Zhang W , Gao S , Wang J , Zhang D , Wang M . Structure, morphology and photocatalytic performance of europium and fluorine co-doped bismuth vanadate. New Journal of Chemistry, 2022, 46(42): 20269–20278

47 Zhou B , Zhao X , Liu H , Qu J , Huang C P . Visible-light sensitive cobalt-doped BiVO₄ (Co-BiVO₄) photocatalytic composites for the degradation of methylene blue dye in dilute aqueous solutions. Applied Catalysis B: Environmental, 2010, 99(1–2): 214–221

48 Obregón S , Colón G . Improved O₂ evolution from a water splitting reaction over Er³⁺ and Y³⁺ co-doped tetragonal BiVO₄. Catalysis Science & Technology, 2014, 4(7): 2042–2050

49 DongSFengJLiYHuLLiuMWangYPiYSunJSunJ. Shape-controlled synthesis of BiVO₄ hierarchical structures with unique natural-sunlight-driven photocatalytic activity. Applied Catalysis B: Environmental, 2014, 152–153: 413–424

50 Zhao C , Li X , Yue L , Ren X , Yuan S , Zeng Z , He Y . Fabrication of novel BiPO₄/Bi₄O₅Br₂ heterojunctions for improving photoactivity in N₂ fixation and dye degradation. Materials Research Bulletin, 2023, 167: 112377