Enhanced photocatalytic activity of Eu3+- and Gd3+-doped BiPO4


Novel europium- and gadolinium-doped bismuth phosphate (Eu/BiPO4 and Gd/BiPO4) microcrystals have been synthesized by a hydrothermal route. The morphologies and optical properties of the as-prepared samples were characterized carefully. Their photocatalytic activities were determined by oxidative decomposition of methylene blue (MB) in aqueous solution. The results revealed that europium and gadolinium doping greatly improves the photocatalytic efficiency of BiPO4 microcrystals. Among these as-prepared europium and gadolinium dopant samples, 1% Eu/BiPO4 and 5% Gd/BiPO4 displayed the highest photocatalytic activity, and the degradation rates are 2 and 2.7 times greater than pure BiPO4, respectively. The photodegradation reactions of MB by Eu- and Gd-BiPO4 followed first-order kinetics. The different photocatalytic mechanisms of Eu/BiPO4 and Gd/BiPO4 photocatalysts are discussed.

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  1. 1.

    X.C. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J.M. Carlsson, K. Domen, and M. Antonietti: A metal-free polymeric photocatalyst for hydrogen production. Nat. Mater. 8, 76 (2009).

    CAS  Article  Google Scholar 

  2. 2.

    H. Tong, S.X. Ouyang, Y.P. Bi, N. Umezawa, M. Oshikiri, and J.H. Ye: Nano-photocatalytic materials: Possibilities and challenges. Adv. Mater. 24, 229 (2012).

    CAS  Article  Google Scholar 

  3. 3.

    A. Kubacka, M. Fernández-García, and G. Colón: Advanced nanoarchitectures for solar photocatalytic applications. Chem. Rev. 112, 1555 (2012).

    CAS  Article  Google Scholar 

  4. 4.

    K.K. Akurati, A. Vital, J.P. Dellemann, K. Michalow, T. Graule, D. Fetti, and A. Baiker: Flame-made WO3/TiO2 nanoparticles: Relation between surface acidity, structure and photocatalytic activity. Appl. Catal., B 79, 53 (2008).

    CAS  Article  Google Scholar 

  5. 5.

    H.Q. Wang, M. Miyauchi, Y. Ishikawa, A. Pyatenko, N. Koshizaki, Y. Li, L. Li, X.Y. Li, Y. Bando, and D. Golberg: Single-crystalline rutile TiO2 hollow spheres: Room-temperature synthesis, tailored visible-light-extinction, and effective scattering layer for quantum dot-sensitized solar cells. J. Am. Chem. Soc. 133, 19102 (2011).

    CAS  Article  Google Scholar 

  6. 6.

    N.D. Feng, Q. Wang, A.M. Zheng, Z.F. Zhang, J. Fan, S.B. Liu, J.P. Amoureux, and F. Deng: Understanding the high photocatalytic activity of (B, Ag)-co doped TiO2 under solar-light irradiation with XPS, solid-state NMR, and DFT calculations. J. Am. Chem. Soc. 135, 1607 (2013).

    CAS  Article  Google Scholar 

  7. 7.

    S.B. Rawal, S.D. Sung, and W.I. Lee: Novel Ag3PO4/TiO2 composites for efficient decomposition of gaseous 2-propanol under visible-light irradiation. Catal. Commun. 17, 131 (2012).

    CAS  Article  Google Scholar 

  8. 8.

    W. Choi, A. Termin, and M.R. Hoffmann: The role of metal ion dopants in quantum-sized TiO2: Correlation between photoreactivity and charge carrier recombination dynamics. J. Phys. Chem. 98, 13669 (1994).

    Article  Google Scholar 

  9. 9.

    V. Vamathevan, R. Amal, D. Beydoun, G. Low, and S. McEvoy: Photocatalytic oxidation of organics in water using pure and silver-modified titanium dioxide particles. J. Photochem. Photobiol., A 148, 233 (2002).

    CAS  Article  Google Scholar 

  10. 10.

    C. He, Y. Yu, X.F. Hu, and A. Larbot: Influence of silver doping on the photocatalytic activity of titania films. Appl. Surf. Sci. 200, 239 (2002).

    CAS  Article  Google Scholar 

  11. 11.

    R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, and Y. Taga: Visible-light photocatalysis in nitrogen-doped titanium oxides. Science 293, 269 (2001).

    CAS  Article  Google Scholar 

  12. 12.

    S. Livraghi, M.C. Paganini, E. Giamello, A. Selloni, C. Di Valentin, and G. Pacchioni: Origin of photoactivity of nitrogen-doped titanium dioxide under visible light. J. Am. Chem. Soc. 128, 15666 (2006).

    CAS  Article  Google Scholar 

  13. 13.

    N. Feng, A. Zheng, Q. Wang, P. Ren, X. Gao, S.B. Liu, Z. Shen, T. Chen, and F. Deng: Boron environments in b-doped and (B, N)-codoped TiO2 photocatalysts: A combined solid-state NMR and theoretical calculation study. J. Phys. Chem. C 115, 2709 (2011).

    CAS  Article  Google Scholar 

  14. 14.

    D.M. Chen, Q. Zhu, Z.J. Lv, X.T. Deng, F.S. Zhou, and Y.X. Deng: Microstructural and photocatatlytic properties of Eu-doped mesporous titanium dioxide nanoparticles by sol-gel method. Mater. Res. Bull. 47, 3129 (2012).

    CAS  Article  Google Scholar 

  15. 15.

    Y. Tian, L.D. Zhang, and J.X. Zhang: A superior visible light-driven photocatalyst: Europium-doped bismuth tungstate hierarchical microspheres. J. Alloys Compd. 537, 24 (2012).

    CAS  Article  Google Scholar 

  16. 16.

    R.R. Guo, L. Fang, W. Dong, F.G. Zheng, and M.R. Shen: Enhanced photocatalytic activity and ferromagnetism in Gd doped BiFeO3 nanoparticles. J. Phys. Chem. C 114, 21390 (2010).

    CAS  Article  Google Scholar 

  17. 17.

    C.S. Pan and Y.F. Zhu: New type of BiPO4 oxy-acid salt photocatalyst with high photocatalytic activity on degradation of dye. Environ. Sci. Technol. 44, 5570 (2010).

    CAS  Article  Google Scholar 

  18. 18.

    M.L. Zhao, G.S. Li, L.P. Li, L.S. Yang, and J. Zheng: Structures and polymorph-sensitive luminescence properties of BiPO4/Eu grown in hydrothermal conditions. Cryst. Growth Des. 12, 3983 (2012).

    CAS  Article  Google Scholar 

  19. 19.

    G. Colon, S.M. Lopez, M.C. Hidalgo, and J.A. Navio, Sunlight highly photoactive Bi2WO6–TiO2 heterostructures for rhodamineB degradation. Chem. Commun. 46, 4809 (2010).

    CAS  Article  Google Scholar 

  20. 20.

    S.W. Liu, J.G. Yu, and M. Jaroniec: Anatase TiO2 with dominant high-energy {001} facets: Synthesis, properties, and applications. Chem. Mater. 23, 4085 (2011).

    CAS  Article  Google Scholar 

  21. 21.

    Y.B. Zhao, W.H. Ma, Y. Li, H.W. Ji, C.C. Chen, H.Y. Zhu, and J.C. Zhao: The surface-structure sensitivity of dioxygen activation in the anatase-photocatalyzed oxidation reaction. Angew. Chem. Int. Ed. 51, 3188 (2012).

    CAS  Article  Google Scholar 

  22. 22.

    A.W. Xu, Y. Gao, and H.Q. Liu: The preparation, characterization, and their photocatalytic activities of rare-earth-doped TiO2 nanoparticles. J. Catal. 207, 151 (2002).

    CAS  Article  Google Scholar 

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This work was supported by the Fundamental Research Funds for the Central Universities (Grant No. 2652013052) and the special co-construction project of Beijing city education committee, Key Project of Chinese Ministry of Education (Grant No. 107023).

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Correspondence to Hongwei Huang.

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Huang, H., Qi, H., He, Y. et al. Enhanced photocatalytic activity of Eu3+- and Gd3+-doped BiPO4. Journal of Materials Research 28, 2977–2984 (2013). https://doi.org/10.1557/jmr.2013.296

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  • optical properties
  • scanning electron microscopy (SEM)
  • x-ray diffraction (XRD)