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Treatment of organic pollutants in water using TiO2 powders: photocatalysis versus sonocatalysis

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Abstract

The scope of this work was to explore the application of different TiO2 powders (P25, PC105, PC500 and their calcined forms) for the photocatalytic and sonocatalytic treatment of model wastewaters containing single pollutants and their mixtures; dyes: C.I. Reactive Violet 2 (RV2), C.I. Mordant Yellow 10 (MY10) and oxalic acid. The influence of the applied catalyst type on the photocatalytic and sonocatalytic efficiency was explored with the emphasis on crystalline form and granulometric properties of powders. Generally, TiO2 powders, which were applied as obtained, demonstrated higher photocatalytic activity (~20 % of organic content oxidized in the mixture of dyes and oxalic acid in 30 min) while their calcined forms were shown to be more prominent as sonocatalysts (up to 13 % of organic contents oxidized in 30 min). The XRD analysis of calcined TiO2 powders confirmed the predominant crystal form of rutile. The degradation and mineralization kinetics of dyes RV2, MY10, oxalic acid and their mixtures was studied. In general, experimental results fitted well (R2 > 0.94) to the half and first order reaction rate model, pointing at the two ongoing mechanisms, i.e. reaction with ·OH radicals and direct electron transfer between adsorbed molecules and catalyst surface. A certain deviation is observed for the model solution containing dye MY10. MY10 serve as a filter for the UV-A irradiation (λmax = 365 nm). A detailed kinetic study confirmed the two simultaneous kinetic pathways and the comparable mechanisms for oxalic acid and dyes photocatalysis. The performed study confirmed the similarity of occurring mechanisms in photocatalysis and sonocatalysis due to sonoluminescence, with the extent of acoustic cavitation in ·OH radical generation.

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Abbreviations

\( d \) :

Particle size (expressed with diameter value) (m)

\( d_{i} \) :

Particle size in size class i (m)

\( \overline{{d_{i} }} \) :

Average particle size in size class i (m)

d 3,2 :

Sauter mean diameter (m)

\( d_{\text{p}} \) :

Pore size (expressed with diameter value) (m)

\( d_{{{\text{p, av}} .}} \) :

Average pore size (expressed with diameter value) (m)

\( {\text{d}}Q_{3} \left( {d_{i} } \right) \) :

Experimental data for volume content of entities in size interval \( i \) (−)

\( q_{3} \left( d \right) \) :

Normalized volume probability density function (m−1)

\( V \) :

Volume of adsorbed nitrogen gas that is pore volume (m3)

V P :

Single point total pore volume (m3 g−1)

\( S_{V} \) :

Estimated external surface area (m2 m−3)

\( S_{\text{BET}} \) :

BET surface area (m2 g−1)

\( \psi_{\text{Wa}} \) :

Wadel shape factor (−)

\( i \) :

Discussed size interval (\( i = 1 \cdots 86 \))

r:

Reaction rate, mol dm−3 s−1

k:

Reaction rate constant, mol1−n dm3n−3 s−1

n:

Reaction order

X:

Extent, %

[.]:

Molar concentration, mol dm−3

ea :

Volumetric rate of photon absorption

θ :

Surface coverage

a :

Coefficient for calculation of surface coverage at t = 0

b :

Coefficient for calculation of changes in surface coverage

a k :

Exponential decay coefficient for reaction rate constants (s−1)

λ:

Wavelength, nm

λmax :

Wavelength of maxima absorption

f :

Ultrasonic frequency, kHz

UV-A:

Ultraviolet irradiation with maximum at 365 nm

UV-C:

Ultraviolet irradiation with maximum at 254 nm

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Acknowledgments

The authors would like to acknowledge the financial support from the COGITO bilateral project Air and water pollutants abatement on mesoporous silicates modified by oxide particles using advanced oxidation technologies (prof. Vesna Tomašić). The authors would also like to thank prof. Anne Davidson, UPMC, France for complementary analyses.

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Authors and Affiliations

  1. Faculty of Chemical Engineering and Technology, University of Zagreb, Marulićev trg 19, HR-10000, Zagreb, Croatia

    Ivana Grčić, Krunoslav Žižek & Natalija Koprivanac

  2. Department of Environmental Engineering, Faculty of Geotechnical Engineering, University of Zagreb, Hallerova aleja 7, HR-42000, Varaždin, Croatia

    Dinko Vujević

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  1. Ivana Grčić
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  2. Dinko Vujević
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  3. Krunoslav Žižek
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  4. Natalija Koprivanac
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Correspondence to Ivana Grčić.

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Grčić, I., Vujević, D., Žižek, K. et al. Treatment of organic pollutants in water using TiO2 powders: photocatalysis versus sonocatalysis. Reac Kinet Mech Cat 109, 335–354 (2013). https://doi.org/10.1007/s11144-013-0562-5

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  • DOI: https://doi.org/10.1007/s11144-013-0562-5

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