Nanocrystalline TiO2 by sol–gel: Characterisation and photocatalytic activity on Modica and Comiso stones

Abstract A self-cleaning photocatalytic coating for limestone materials, based on TiO2 nanoparticles obtained by the sol–gel process has been studied. TiO2 sol was applied directly to the surface or after a SiO2 intermediate layer. The selected test materials are the Modica and the Comiso calcarenites, limestones of Ragusa Formation outcropping in the South Eastern Sicily (Italy). SEM–EDS, XRD and Raman investigations were carried out to characterise the TiO2 nanoparticles and coating. Nanocrystalline anatase and, to a lesser extent, brookite forms are obtained. To evaluate the harmlessness of the treatment, colorimetric tests, water absorption by capillarity and crystallisation of salts measurements were performed. Photocatalytic activity of the TiO2 colloidal suspension and of the coatings (TiO2 and SiO2/TiO2) was assessed under UV irradiation through methyl orange dye degradation tests. The results show good photodegradation activity and satisfactory compatibility between the sol and the surface of the investigated limestones.

[1]  A. Robertson,et al.  Colorimetry: Fundamentals and Applications , 2005 .

[2]  P. Mazzoleni,et al.  The Cathedral of S. Giorgio in Ragusa Ibla (Italy): characterization of construction materials and their chromatic alteration , 2008 .

[3]  V. Polshettiwar,et al.  Synthesis of hierarchical anatase TiO2 nanostructures with tunable morphology and enhanced photocatalytic activity , 2012 .

[4]  A. Alivisatos Perspectives on the Physical Chemistry of Semiconductor Nanocrystals , 1996 .

[5]  Farid Elhaddad,et al.  A novel TiO2–SiO2 nanocomposite converts a very friable stone into a self-cleaning building material , 2013 .

[6]  R. J. Dunham Classification of Carbonate Rocks According to Depositional Textures , 1962 .

[7]  P. V. Ashrit,et al.  Study of Anatase to Rutile Phase Transition in Nanocrystalline Titania Films , 2002 .

[8]  I. Kiricsi,et al.  Synthesis and characterization of titania photocatalysts: The influence of pretreatment on the activity , 2006 .

[9]  Gino Mirocle Crisci,et al.  Multifunctional TiO2 coatings for Cultural Heritage , 2012 .

[10]  B. Ohtani,et al.  Photocatalytic Activity of Amorphous−Anatase Mixture of Titanium(IV) Oxide Particles Suspended in Aqueous Solutions , 1997 .

[11]  A. Bard,et al.  An Improved Photocatalyst of TiO2/SiO2 Prepared by a Sol-Gel Synthesis , 1995 .

[12]  Tarek A. Kandiel,et al.  Brookite versus anatase TiO_2 photocatalysts: phase transformations and photocatalytic activities , 2013, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[13]  Claudio Oleari,et al.  Spectrophotometric Scanner for Imaging of Paintings and Other Works of Art , 2004, CGIV.

[14]  P. P. Lottici,et al.  Raman study of nanosized titania prepared by sol–gel route , 1998 .

[15]  A. K. Vasudevan,et al.  Phase transformation in sol–gel titania containing silica , 1999 .

[16]  T. Akita,et al.  Low-temperature synthesis of anatase-brookite composite nanocrystals: the junction effect on photocatalytic activity. , 2005, Journal of colloid and interface science.

[17]  Angela Calia,et al.  Photocatalytic TiO2 coatings on limestone , 2011 .

[18]  Juan L. Vivero-Escoto,et al.  Recent progress in mesoporous titania materials: adjusting morphology for innovative applications , 2012, Science and technology of advanced materials.

[19]  Enrico Quagliarini,et al.  Self-cleaning materials on Architectural Heritage: Compatibility of photo-induced hydrophilicity of TiO2 coatings on stone surfaces , 2013 .

[20]  E. W. Washburn The Dynamics of Capillary Flow , 1921 .

[21]  P. P. Lottici,et al.  Phonon confinement effects in the Raman scattering by TiO2 nanocrystals , 1998 .

[22]  E. Sebastian,et al.  Laboratory simulation showing the influence of salt efflorescence on the weathering of composite building materials , 2008 .

[23]  Enrico Quagliarini,et al.  Smart surfaces for architectural heritage: Preliminary results about the application of TiO2-based coatings on travertine , 2012 .

[24]  Y. Konishi,et al.  A patterned TiO(2)(anatase)/TiO(2)(rutile) bilayer-type photocatalyst: effect of the anatase/rutile junction on the photocatalytic activity. , 2002, Angewandte Chemie.

[25]  J. Banfield,et al.  UNDERSTANDING POLYMORPHIC PHASE TRANSFORMATION BEHAVIOR DURING GROWTH OF NANOCRYSTALLINE AGGREGATES: INSIGHTS FROM TIO2 , 2000 .

[26]  A. Morawski,et al.  Photocatalytic degradation of reactive Black 5. A comparison between Ti02-Tytanpol All and TiO2-Degussa P25 photocatalysts , 2001 .

[27]  Enrico Quagliarini,et al.  Self-cleaning and de-polluting stone surfaces: TiO2 nanoparticles for limestone , 2012 .

[28]  S. Gialanella,et al.  Tailored Anatase/Brookite Nanocrystalline TiO2. The Optimal Particle Features for Liquid- and Gas-Phase Photocatalytic Reactions , 2007 .

[29]  L. Anania,et al.  The stones in monumental masonry buildings of the “Val di Noto” area: New data on the relationships between petrographic characters and physical–mechanical properties , 2012 .

[30]  M. L. Curri,et al.  Nanocrystalline TiO2 based films onto fibers for photocatalytic degradation of organic dye in aqueous solution , 2012 .

[31]  Z. Dohcevic-Mitrovic,et al.  Raman study of the variation in anatase structure of TiO2 nanopowders due to the changes of sol–gel synthesis conditions , 2009 .