Date of Award

8-2009

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Legacy Department

Materials Science and Engineering

Advisor

Goodwin, James G.

Committee Member

Luo , Jian

Committee Member

Luzinov , Igor

Committee Member

Richardson , Kathleen

Committee Member

Tzeng , Tzuen-Rong J.

Abstract

Titania (TiO2) is useful for many applications in photocatalysis, antimicrobials, pigment, deodorization, and decomposition of harmful organics and undesirable compounds in the air and waste water under UV irradiation. Among the three phases of TiO2, Rutile, Anatase, and Brookite, studies have been more focused on the anatase and rutile phases.
Pure brookite is the most difficult phase to prepare, even under hydrothermal conditions. Predominantly brookite phase TiO2 nanoparticles were prepared by the Water-based Ambient Condition Sol (WACS) process in our laboratory. The objectives of this research were to enhance visible light active (VLA) photocatalytic properties of polymorphic brookite TiO2 by minimizing the lattice defects and narrowing band gap of titania by nitrogen and/or carbon chromophone, and to investigate the deactivation, reusability, and regeneration of the VLA titania in order to design better titania catalysts for organic compound degradation applications.
In order to study the influence of hydroxyl content on photocatalytic activities (PCAs) of polymorphic titania nanoparticles, the WACS samples were post-treated by a Solvent-based Ambient Condition Sol (SACS) process in sec-butanol (sec-BuOH). All samples were characterized for phase composition, surface area, hydroxyl contamination, and particle morphology by x-ray diffraction, N2 physisorption, FT-IR, solid state 1H NMR and scanning electron microscopy, and then compared to a commercial titania, Degussa P25. Evaluation of methyl orange (MO) degradation under UV irradiation results showed that the lower lattice hydroxyl content in SACS titania enhanced the PCA. As-prepared titania and SACS samples, which have similar surface areas and crystallinity, were compared in order to prove that the superior PCA came from the reduction in the lattice hydroxyl content.
To enhance PCA and VLA properties of WACS, an alternative high boiling point polar solvent, N-methylpyrrolidone (NMP), was utilized in the SACS process at a higher treatment temperature to modify polymorphic titania nanoparticles. This SACS sample was called 'SACS-NMP'. SACS, using NMP as the solvent, could also extract lattice hydroxyls, and decorate nitrogen on the titania surface. The PCA of SACS-NMP was superior to that of SACS-sec-BuOH. Nitrogen incorporation of SACS-NMP titania was investigated by CHN analysis and x-ray photoelectron spectroscopy (XPS). VL absorbance for all samples was characterized by UV-Vis absorption spectrophotometry. PCA of MO degradation under UV and VL showed that SACS-NMP is a powerful treatment to enhance PCA by minimizing lattice hydroxyls and doping the titania surface with nitrogen. The effect of calcination conditions on SACS-NMP samples was also studied. The calcination conditions, especially the temperature and calcination atmosphere, have an influence on the BET surface area, crystallite size, titania phase content, and PCA under VL irradiation. SACS-NMP samples calcined in air at 200oC for 2 hours showed the best VL activated photocatalytic performance in this research. Additionally, the SACS-NMP sample exhibited superior VL properties to several available reference anatase titania samples. This could be explained as the effective charge separation by the intercrystalline electron transport from brookite to anatase grains complemented by strong VL absorption by the nitrogen species in NMP.
The deactivation and regeneration of the VLA titania were investigated and compared to a commercial titania, Kronos VLP7000. PCA of the titania under VL for MO decolorization gradually decreased with increasing testing time and the number of runs. The cause of the deactivation was identified as the deposition of the decomposed MO or the carbonaceous deposit. Among the possible regeneration procedures for used SACS-NMP samples, methanol washing was shown to be the most effective up to ~80% of the PCA recovery. Accordingly, the SACS-NMP samples could not be completely recovered since a regeneration process would possibly remove some of nitrogen species responsible for the VL properties.

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