Technical Papers
Feb 1, 2012

Surface Structure and Photocatalytic Activity of Nano-TiO2 Thin Film for Selective Oxidation

Publication: Journal of Environmental Engineering
Volume 138, Issue 9

Abstract

Controlled titanium dioxide (TiO2) thin films were deposited on stainless steel surfaces using the flame-aerosol synthetic technique, which is a one-step coating process that does not require further calcination. Solid state characterization of the coatings was conducted by different techniques, including X-ray diffraction (XRD) spectrum, scanning electron microscope, and atomic force microscope. The coated thin films were used in a gas phase photoreactor for the partial oxidation of hydrocarbons to alcohols and ketones as an alternative production method for the highly sought oxygenates. For this purpose, the oxidation reaction of cyclohexane to form cyclohexanol and cyclohexanone was chosen as a model reaction. The effects of the film thickness, anatase-to-rutile ratio, and particle morphology on the reactivity of the catalyst were studied. Experimental results revealed that there is an optimal film thickness (between 400 and 700 nm) for the photooxidation process that gave a maximum rate of reaction. The yield and selectivity of TiO2 increased with the increase of the film thickness up to 350–400 nm. The activity decreased with a further increase in thickness. The influence of the crystallographic structure of TiO2 on the partial oxidation of cyclohexane showed that the catalyst efficiency increased almost linearly with the increase of the anatase fraction between 20 and 95%. The coating technique that formed highly porous and soft aggregated TiO2 thin films with rough morphology showed lower photoactivity than the technique that formed fine particle and transparent thin film.

Get full access to this article

View all available purchase options and get full access to this article.

References

An, W. J., Thimsen, E., and Biswas, P. (2010). “Aerosol-chemical vapor deposition method for synthesis of nanostructured metal oxide thin films with controlled morphology.” J. Phys. Chem. Lett., 1(1), 249–253.
Badini, G. E., Grattan, K. T. V., and Tseung, A. C. C. (1995). “Sol-gels with fiberoptic chemical sensor potential—Effects of preparation, aging, and long-term storage.” Rev. Sci. Instrum., 66(8), 4034–4040.
Chang, H. T., Wu, N. M., and Zhu, F. Q. (2000). “A kinetic model for photocatalytic degradation of organic contaminants in a thin-film TiO2 catalyst.” Water Res., 34(2), 407–416.
Cheng, D. L., Lin, C. Y., Liu, C. S., Kao, K. S., and Wang, C. M. (2010). “Fabrication of nanocrystalline TiO 518 2 films by aerosol deposition method for dye-sensitized solar cells.” Materials Science Forum: PRICM 7, Vol. 654–656, Nie, J. F., and Morton, A., 2807–2810.
Dagan, G., and Tomkiewicz, M. (1993). “TiO2 aerogels for photocatalytic decontamination of aquatic environments.” J. Phys. Chem., 97(49), 12651–12655.
Einaga, H., Futamura, S., and Ibusuk, I. T. (2002). “Heterogeneous photocatalytic oxidation of benzene, toluene, cyclohexene and cyclohexane in humidified air: Comparison of decomposition behavior on photoirradiated TiO2 catalyst.” Appl. Catalysts B: Environ., 38(3), 215–225.
Fox, M. A., Chen, C. C., Park, K. H., and Younathan, J. N. (1985). “Controlled organic redox reactivity on irradiated semiconductor Surfaces.” ACS Symp. Ser., 278, 69–78.
Gwyddion 2.12 [Computer software]. (2009). 〈http://gwyddion.net/download-old.php〉 (Jul. 10, 2012).
Hoffmann, M. R., Martin, S. T., Choi, W. Y., and Bahnemann, D. W. (1995). “Environmental applications of semiconductor photocatalysis.” Chem. Rev., 95(1), 69–96.
Karakitsou, K. E., and Verykios, X. E. (1993). “Effects of altervalent cation doping of TiO2 on its performance as a photocatalyst for water cleavage.” J. Phys. Chem., 97(6), 1184–1189.
Kim, D. H., and Anderson, M. A. (1996). “Solution factors affecting the photocatalytic and photoelectrocatalytic degradation of formic acid using supported TiO2 thin films.” J. Photochem. Photobiol., A, 94(2–3), 221–229.
Koval, C. A., and Howard, J. N. (1992). “Electron-transfer at semiconductor electrode liquid electrolyte interfaces.” Chem. Rev., 92(3), 411–433.
Low, G. K. C., and Matthews, R. W. (1990). “Flow-injection determination of organic contaminants in water using an ultraviolet-mediated titanium-dioxide film reactor.” Anal. Chim. Acta, 231(1), 13–20.
Mahanta, D., Manna, U., Madras, G., and Patil, S. (2011). “Multi layer self-assembly of TiO2 nanoparticles and polyaniline-grafted-chitosan copolymer (CPANI) for photocatalysis.” ACS Appl. Mater. Interfaces, 3(1), 84–92.
Matthews, R. W. (1987). “Photooxidation of organic impurities in water using thin-films of titanium-dioxide.” J. Phys. Chem., 91(12), 3328–3333.
Matthews, R. W., Abdullah, M., and Low, G. K. C. (1990). “Photocatalytic oxidation for total organic-carbon analysis.” Anal. Chim. Acta, 233(2), 171–179.
Mihaylov, B. V., Hendrix, J. L., and Nelson, J. H. (1993). “Comparative catalytic activity of selected metal-oxides and sulfides for the photooxidation of cyanide.” J. Photochem. Photobiol., A, 72(2), 173–177.
Mills, A., Davies, R. H., and Worsley, D. (1993). “Water-purification by semiconductor photocatalysis.” Chem. Soc. Rev., 22(6), 417–425.
Mills, A., and Eaton, K. (2000). “Optical sensors for carbon dioxide: An overview of sensing strategies past and present.” Quim. Anal., 19, 75–86.
Mills, A., Hill, G., Bhopal, S., Parkin, I. P., and O’Neill, S. A. (2003). “Thick titanium dioxide films for semiconductor photocatalysis.” J. Photochem. Photobiol., A, 160(3), 185–194.
Mills, A., and LeHunte, S. (1997). “An overview of semiconductor photocatalysis.” J. Photochem. Photobiol., A, 108(1), 1–35.
Nishimoto, S., Ohtani, B., Kajiwara, H., and Kagiya, T. (1985). “Correlation of the crystal-structure of titanium-dioxide prepared from titanium tetra-2-propoxide with the photocatalytic activity for redox reactions in aqueous propan-2-ol and silver salt solutions.” J. Chem. Soc., Faraday Trans., 81, 61–68.
Ohtani, B., and Nishimoto, S. (1993). “Effect of surface adsorptions of aliphatic-alcohols and silver ion on the photocatalytic activity of TiO2 suspended in aqueous solutions.” J. Phys. Chem., 97(4), 920–926.
Ollis, D. F., Pelizzetti, E., and Serpone, N. (1989). Photocatalysis-fundamentals and application, Wiley, New York.
O’Regan, B., Lenzmann, F., Muis, R., and Wienke, J. (2002). “A solid-state dye-sensitized solar cell fabricated with pressure-treated P25-TiO2 and CuSCN: Analysis of pore filling and IV characteristics.” Chem. Mater., 14(12), 5023–5029.
Peral, J., and Ollis, D. F. (1992). “Heterogeneous photocatalytic oxidation of gas-phase organics for air purification—acetone, 1-butanol, butyraldehyde, formaldehyde, and meta-xylene oxidation.” J. Catal., 136(2), 554–565.
Rao, M. V., Rajeshwar, K., Paiverneker, V. R., and Dubow, J. (1980). “Photosynthetic production of H2 and H2O2 on semiconducting oxide grains in aqueous-solutions.” J. Phys. Chem., 84(15), 1987–1991.
Rathousky, J., Slabova, M., and Zukal, A. (2003). “Mesostructured TiO2 films as effective photocatalysts for the degradation of organic pollutants.” Nanotechnol. Mesostruct. Mater., Vol. 146, Elsevier, Amsterdam, Netherlands, 601–604.
Ryu, J.,et al. (2009). “Photocatalytic nanocomposite thin films of TiO2-beta-calcium phosphate by aerosol-deposition.” Catal. Commun., 10(5), 596–599.
Sahle-Demessie, E., Gonzalez, M., Wang, Z. M., and Biswas, P. (1999). “Synthesizing alcohols and ketones by photoinduced catalytic partial oxidation of hydrocarbons in TiO2 film reactors prepared by three different methods.” Ind. Eng. Chem. Res., 38(9), 3276–3284.
Serpone, N., Lawless, D., and Khairutdinov, R. (1995). “Size effects on the photophysical properties of colloidal anatase TiO2 particles: Size quantization versus direct transitions in this indirect semiconductor?” J. Phys. Chem., 99(45), 16646–16654.
Tennakone, K., Tilakaratne, C. T. K., and Kottegoda, I. R. M. (1997). “Photomineralization of carbofuran by TiO2-supported catalyst.” Water Res., 31(8), 1909–1912.
Tunesi, S., and Anderson, M. (1991). “Influence of chemisorption on the photodecomposition of salicylic-acid and related-compounds using suspended TiO2 ceramic membranes.” J. Phys. Chem., 95(8), 3399–3405.
Wang, Z. M., and Biswas, P. (2000). “Nickel speciation and aerosol formation during combustion of kerosene doped with nickel nitrate aerosol in a premixed burner.” Aerosol Sci. Technol., 33(6), 525–535.
Wang, Z. M., Sahle-Demessie, E., and Hassan, A. A. (2011). “Selective oxidation using flame aerosol synthesized iron and vanadium-doped nano-TiO2.” J. Nanotechnol., 2011, 209150.
Wang, Z. M., Yang, G. X., Biswas, P., Bresser, W., and Boolchand, P. (2001). “Processing of iron-doped titania powders in flame aerosol reactors.” Powder Technol., 114(1–3), 197–204.

Information & Authors

Information

Published In

Go to Journal of Environmental Engineering
Journal of Environmental Engineering
Volume 138Issue 9September 2012
Pages: 923 - 931

History

Received: Apr 20, 2011
Accepted: Jan 30, 2012
Published online: Feb 1, 2012
Published in print: Sep 1, 2012

Permissions

Request permissions for this article.

Authors

Affiliations

Zhong-Min Wang, Ph.D. [email protected]
Research Scientist, Environmental Health Laboratory, California Dept. of Public Health, 850 Marina Bay Parkway, EHLB/G365, Richmond, CA 94804 (corresponding author). E-mail: [email protected]
Endalkachew Sahle-Demessie, Ph.D. [email protected]
U.S. Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory, Cincinnati, OH 45268. E-mail: [email protected]
Ashraf Aly Hassan, Ph.D. [email protected]
U.S. Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory, Cincinnati, OH 45268. E-mail: [email protected]
Christopher Perrett [email protected]
Environmental Technician, U.S. Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory, Cincinnati, OH 45268. E-mail: [email protected]

Metrics & Citations

Metrics

Citations

Download citation

If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.

Cited by

View Options

Get Access

Access content

Please select your options to get access

Log in/Register Log in via your institution (Shibboleth)
ASCE Members: Please log in to see member pricing

Purchase

Save for later Information on ASCE Library Cards
ASCE Library Cards let you download journal articles, proceedings papers, and available book chapters across the entire ASCE Library platform. ASCE Library Cards remain active for 24 months or until all downloads are used. Note: This content will be debited as one download at time of checkout.

Terms of Use: ASCE Library Cards are for individual, personal use only. Reselling, republishing, or forwarding the materials to libraries or reading rooms is prohibited.
ASCE Library Card (5 downloads)
$105.00
Add to cart
ASCE Library Card (20 downloads)
$280.00
Add to cart
Buy Single Article
$35.00
Add to cart

Get Access

Access content

Please select your options to get access

Log in/Register Log in via your institution (Shibboleth)
ASCE Members: Please log in to see member pricing

Purchase

Save for later Information on ASCE Library Cards
ASCE Library Cards let you download journal articles, proceedings papers, and available book chapters across the entire ASCE Library platform. ASCE Library Cards remain active for 24 months or until all downloads are used. Note: This content will be debited as one download at time of checkout.

Terms of Use: ASCE Library Cards are for individual, personal use only. Reselling, republishing, or forwarding the materials to libraries or reading rooms is prohibited.
ASCE Library Card (5 downloads)
$105.00
Add to cart
ASCE Library Card (20 downloads)
$280.00
Add to cart
Buy Single Article
$35.00
Add to cart

Media

Figures

Other

Tables

Share

Share

Copy the content Link

Share with email

Email a colleague

Share