Topics in Catalysis

, Volume 58, Issue 2–3, pp 85–102 | Cite as

Effect of the TiO2 Crystallite Size, TiO2 Polymorph and Test Conditions on the Photo-Oxidation Rate of Aqueous Methylene Blue

  • Wan-Ting Chen
  • Andrew Chan
  • Vedran Jovic
  • Dongxiao Sun-Waterhouse
  • Kei-ichiro Murai
  • Hicham Idriss
  • Geoffrey I. N. Waterhouse
Original Paper
First Online:

Abstract

This study systematically re-examines the titania-catalysed photo-oxidation of methylene blue (MB) in aqueous solution at 20 °C, placing particular emphasis on the effects of TiO2 crystallite size, TiO2 polymorph (anatase, brookite, rutile and combinations thereof) and experimental test conditions on the rate of MB photo-oxidation. For all TiO2 samples tested, the highest rate of MB photo-oxidation was observed at pH 6, slightly above the isoelectric point of TiO2 (~5.8 for P25 TiO2). Increasing the ionic strength at pH 6 induced MB dimer formation in solution, and lowered the rate of MB photo-oxidation by TiO2. For all TiO2 polymorphs, the surface area normalised rate increased with crystallite size reflecting the corresponding reduction in surface and bulk defects (electron–hole pair recombination sites). The optimum crystallite sizes were ~20–25 nm for anatase and ~50 nm for brookite. The photocatalytic activity of the different TiO2 powders followed the general order P25 > anatase > brookite ≫ rutile, with the high activity of P25 TiO2 providing strong evidence that anatase–rutile heterojunctions act as “hotspots” for MB photo-oxidation. Mixed phase anatase–rutile or brookite–rutile powders, each containing ~5 wt% rutile, demonstrated superior area normalized photocatalytic activities for MB photo-oxidation compared to pure phase anatase or brookite powders of comparable crystallite size. Finally, deposition of Pd, Pt or Au nanoparticles decreased the activity of P25 TiO2 for MB photo-oxidation. This paper clarifies long-standing confusion in the scientific literature about the photo-oxidation of aqueous MB over TiO2 and M/TiO2 (M = Pd, Pt and Au) photocatalysts.

Keywords

Photocatalysis Anatase Rutile Brookite P25 Methylene blue 
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Notes

Acknowledgments

Wan-Ting Chen acknowledges the Energy Education Trust of New Zealand for the award of a doctoral scholarship. The authors acknowledge funding support the MacDiarmid Institute for Advance Materials and Nanotechnology and the Australian Institute of Nuclear Science and Engineering (ALNGRA11126). Geoff Waterhouse thanks the Japan Society for the Promotion of Science (JSPS) for award of a JSPS Fellowship to work in Japan (S13179). The authors thank Dr. Peter Swedlund of the University of Auckland for useful insight regarding the competitive adsorption of MB and phosphate on TiO2 surfaces.

Supplementary material

11244_2014_348_MOESM1_ESM.docx (2.5 mb)
Supplementary material 1 (DOCX 2565 kb)

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Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  • Wan-Ting Chen
    • 1
  • Andrew Chan
    • 1
  • Vedran Jovic
    • 1
  • Dongxiao Sun-Waterhouse
    • 1
  • Kei-ichiro Murai
    • 2
  • Hicham Idriss
    • 3
  • Geoffrey I. N. Waterhouse
    • 1
    • 4
  1. 1.School of Chemical SciencesThe University of AucklandAucklandNew Zealand
  2. 2.Graduate School of Advanced Technology and ScienceThe University of TokushimaTokushimaJapan
  3. 3.SABIC, Corporate Research and Innovation (CRI), KAUSTThuwalSaudi Arabia
  4. 4.The MacDiarmid Institute for Advanced Materials and NanotechnologyWellingtonNew Zealand

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