Modified TiO2-based Photocatalytic Films and Powders produced by Aqueous and Non-Aqueous Sol-Gel Processes for Water Purification

Doctoral thesis (2013)

Summary Two major research goals have been proposed for this thesis. The first goal concerns the development of photocatalysts in the shape of thin films coated on glass substrates which includes (i) the ... [more ▼]

Summary Two major research goals have been proposed for this thesis. The first goal concerns the development of photocatalysts in the shape of thin films coated on glass substrates which includes (i) the development of a sol-gel chemistry suitable for the production of stable colloidal suspensions of TiO2 particles, (ii) the optimization of the deposition method and (iii) the development of an experimental device to measure the photocatalytic activity of the films. The second objective is the development of innovative non-aqueous and aqueous sol-gel routes, including the development of new methods for the introduction of dopants as well as the photocatalytic testing of the resulting materials. Two original non-aqueous sol-gel processes involving respectively, an in situ production of water and the controlled addition of a small amount of water, have been developed to produce a series of stable colloidal suspensions of TiO2 particles (sols). From those sols, transparent, adherent, homogeneous thin films have been produced using an optimized dip-coating deposition method and have been proven to be photocatalytically active for the degradation of an organic pollutant in aqueous solution. The photocatalytic activity of the films has been improved through an increase of their roughness thanks to the addition of an organic additive into the sol, leading to an increased active surface involved into the photocatalytic reaction. A mathematical model allowing the rigorous evaluation of the kinetic parameters of the photocatalytic reaction taking into account the influence of the variation of the volume inside the batch photoreactor has been developed. The equations have been established in the case of a photocatalytic powder homogeneously dispersed in the pollutant solution, and in the case of a photocatalytic thin film placed at the bottom of the reactor. The particular case of a first order reaction has been treated and the error on the reaction rate constant induced by neglecting the volume variation has been quantified. An environmentally-friendly aqueous sol-gel process for producing undoped and Cu2+, Ni2+, Zn2+, Pb2+, Fe3+, Cr3+, La3+ or Eu3+ single-doped as well as La3+- Fe3+ and Eu3+- Fe3+ co-doped TiO2 bulk photocatalysts composed of nanocrystallites of anatase and exhibiting a remarkably high photocatalytic activity without requiring any calcination step has been developed. Different effects of the metal ion dopant on the photocatalytic activity have been observed and discussed according to the dopant nature and content. A kinetic study of the photocatalytic degradation of a model pollutant (4-nitrophenol) in aqueous solution under UV-Visible light (330 nm < λ < 800 nm) has been performed over a promising TiO2-Zn2+ doped catalyst. Statistical validations have confirmed the suitability of the phenomenological reaction rate model developed to represent the 4-nitrophenol photocatalytic degradation over time. [less ▲]

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Poster (2012, November)

Production of Highly Active Doped Titania Photocatalysts by Aqueous Sol-Gel Processing

Conference (2012, August)

Production of highly active doped titania photocatalysts by aqueous sol-gel processing - Synthesis and characterization of the xerogels

Poster (2012)

Optimized deposition of photocatalytic TiO2 thin films produced by a non-aqueous sol-gel method

Poster (2011, November)

Development by sol-gel process of photocatalytic TiO2 thin films prepared by dip-coating

Poster (2010, July)