Photocatalytic H2 production on TiO2 with tuned phase structure via controlling the phase transformation


A series of TiO2 samples were prepared from the precursor P25 using impregnation method followed by a calcination. The phase compositions of the samples were controlled by addition of various additives, including NaNO3, NaHCO3, Na2SO4, Na3PO4, Na2SiO3, and Na2MoO4. X-ray diffraction patterns demonstrate that the phase transformation from anatase to rutile can be suppressed to a different extent by these additives. Photocatalytic H2 production reactions were performed in methanol aqueous solution. The catalysts, with the addition of NaNO3, NaHCO3, and Na2SO4, show a great improvement in the H2 production activity, while others show a negative effect. This indicates that both the phase structure and the properties of the additives are important for the photocatalytic activity. Infrared spectra of pyridine adsorption on the catalysts reveal that the decreased acidity of the samples may be responsible for the suppressed CO production in the photocatalytic methanol reforming.

This is a preview of subscription content, access via your institution.

FIG. 1.
FIG. 2.
FIG. 3.
FIG. 4.
FIG. 5.


  1. 1.

    H. Balat and E. Kirtay: Hydrogen from biomass - present scenario and future prospects. Int. J. Hydrogen Energy 35, 7416 (2010).

    CAS  Article  Google Scholar 

  2. 2.

    X. Chen and S.S. Mao: Titanium dioxide nanomaterials: Synthesis, properties, modifications, and applications. Chem. Rev. 107, 2891 (2007).

    CAS  Article  Google Scholar 

  3. 3.

    G.L. Chiarello, A. Di Paola, L. Palmisano, and E. Selli: Effect of titanium dioxide crystalline structure on the photocatalytic production of hydrogen. Photochem. Photobiol. Sci. 10, 355 (2011).

    CAS  Article  Google Scholar 

  4. 4.

    T. Tong, J. Zhang, B. Tian, F. Chen, and D. He: Preparation and characterization of anatase TiO2 microspheres with porous frameworks via controlled hydrolysis of titanium alkoxide followed by hydrothermal treatment. Mater. Lett. 62, 2970 (2008).

    CAS  Article  Google Scholar 

  5. 5.

    K. Tanaka, T. Hisanaga, and A.P. Rivera: Effect of crystal form of TiO2 on the photocatalytic degradation of pollutants. Photocatalytic Purif. Treat. Water Air 3, 169 (1993).

    CAS  Google Scholar 

  6. 6.

    K.L. Schulte, P.A. DeSario, and K.A. Gray: Effect of crystal phase composition on the reductive and oxidative abilities of TiO2 nanotubes under UV and visible light. Appl. Catal., B 97, 354 (2010).

    CAS  Article  Google Scholar 

  7. 7.

    Y.Y. Zhang, J.Z. Chen, and X.J. Li: Preparation and photocatalytic performance of anatase/rutile mixed-phase TiO2 nanotubes. Catal. Lett. 139, 129 (2010).

    CAS  Article  Google Scholar 

  8. 8.

    J. Zhang, Q. Xu, Z.C. Feng, M.J. Li, and C. Li: Importance of the relationship between surface phases and photocatalytic activity of TiO2. Angew. Chem. Int. Ed. 47, 1766 (2008).

    CAS  Article  Google Scholar 

  9. 9.

    Q. Xu, Y. Ma, J. Zhang, X.L. Wang, Z.C. Feng, and C. Li: Enhancing hydrogen production activity and suppressing CO formation from photocatalytic biomass reforming on Pt/TiO2 by optimizing anatase-rutile phase structure. J. Catal. 278, 329 (2011).

    CAS  Article  Google Scholar 

  10. 10.

    Y. Ma, Q. Xu, X. Zong, D.G. Wang, G.P. Wu, X. Wang, and C. Li: Photocatalytic H2 production on Pt/TiO2-SO42- with tuned surface-phase structures: Enhancing activity and reducing CO formation. Energy Environ. Sci. 5, 6345 (2012).

    CAS  Article  Google Scholar 

  11. 11.

    J. Zhang, M.J. Li, Z.C. Feng, J. Chen, and C. Li: UV Raman spectroscopic study on TiO2. I. Phase transformation at the surface and in the bulk. J. Phys. Chem. B 110, 927 (2006).

    CAS  Article  Google Scholar 

  12. 12.

    H.Y. Chen, O. Zahraa, and M. Bouchy: Inhibition of the adsorption and photocatalytic degradation of an organic contaminant in an aqueous suspension of TiO2 by inorganic ions. J. Photochem. Photobiol., A 108, 37 (1997).

    CAS  Article  Google Scholar 

  13. 13.

    C. Guillard, H. Lachheb, A. Houas, M. Ksibi, E. Elaloui, and J.M. Herrmann: Influence of chemical structure of dyes, of pH and of inorganic salts on their photocatalytic degradation by TiO2 comparison of the efficiency of powder and supported TiO2. J. Photochem. Photobiol., A 158, 27 (2003).

    CAS  Article  Google Scholar 

  14. 14.

    K.H. Wang, Y.H. Hsieh, C.H. Wu, and C.Y. Chang: The pH and anion effects on the heterogeneous photocatalytic degradation of o-methylbenzoic acid in TiO2 aqueous suspension. Chemosphere 40, 389 (2000).

    CAS  Article  Google Scholar 

  15. 15.

    Y.X. Li, G.X. Lu, and S.B. Li: Photocatalytic hydrogen generation and decomposition of oxalic acid over platinized TiO2. Appl. Catal., A 214, 179 (2001).

    CAS  Article  Google Scholar 

  16. 16.

    J.Z. Zhang, Z.M. Liu, and J.G. Goodwin: The effect of low concentrations of CO on H2 adsorption and activation on Pt/C. Part 1: In the absence of humidity. J. Power Sources 195, 3060 (2010).

    CAS  Article  Google Scholar 

  17. 17.

    R.J. Bellows, E.P. MarucchiSoos, and D.T. Buckley: Analysis of reaction kinetics for carbon monoxide and carbon dioxide on polycrystalline platinum relative to fuel cell operation. Ind. Eng. Chem. Res. 35, 1235 (1996).

    CAS  Article  Google Scholar 

  18. 18.

    P. Mars, J.J.F. Scholten, and P. Zwietering: The catalytic decomposition of formic acid. Adv. Catal. 14, 35 (1963).

    CAS  Google Scholar 

  19. 19.

    Y. Uemura, T. Taniike, M. Tada, Y. Morikawa, and Y. Iwasawa: Switchover of reaction mechanism for the catalytic decomposition of HCOOH on a TiO2(110) surface. J. Phys. Chem. C 111, 16379 (2007).

    CAS  Article  Google Scholar 

Download references


We acknowledge the financial support for this work from the National Natural Science Foundation of China (Grant No. 20673112), the National Basic Research Program of China (Grant No. 2009CB220010), and the Solar Energy Project of Chinese Academy of Sciences (Grant No. KGCX2-YW-391-1).

Author information



Corresponding author

Correspondence to Can Li.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Ma, Y., Xu, Q., Chong, R. et al. Photocatalytic H2 production on TiO2 with tuned phase structure via controlling the phase transformation. Journal of Materials Research 28, 394–399 (2013).

Download citation