PHOTOCATALYTIC SELF-CLEANING COATINGS OF LIMESTONES

BY TiO2 BASIC SOLS

Giovanni Predieri1, Ilaria Alfieri1, Laura Bergamonti2, Andrea Lorenzi1, Federica Bondioli2,
Pier Paolo Lottici3
1

Department of Chemistry, University of Parma, Parco Area delle Scienze 17/A, 43124 Parma
Department of Industrial Engineering, University of Parma, Parco Area delle Scienze, 181/A, 43124 Parma, Italy
3
Physics and Earth Sciences Department, University of Parma, Parco Area delle Scienze 7/A, 43124 Parma, Italy

During the last century the increasing environmental pollution in synergistic action with the natural
weathering agents, has caused a rapid worsening of the conditions of the monuments exposed in
urban areas. The main forms of deterioration on the stone facades are related to the accumulation of
pollutants and to soiling processes, with the development of black crusts and other decay forms.
Photocatalysis is an oxidation process that can be used for the decomposition of various
environmental pollutants in both gaseous and liquid phases in a simple and efficient way. Among
the photocatalytic materials, titanium dioxide is the most widely studied and the photoactive
nanocrystalline titania obtained by sol-gel process is a promising de-soiling coating material.
In this paper we report on the results of a study on a new self-cleaning coating for carbonatic stones
based on TiO2 nanoparticles obtained by sol-gel in a basic environment.
Different types of limestone among the most frequently used in historic buildings were used as
substrates. The water based TiO2 sol was easily applied by brushing directly on the stone. The
compatibility of the coatings with the substrate was examined according to the UNI-Normal
protocols by measuring the water absorption by capillarity and colorimetric parameters.
The characterization of the powders obtained by drying the sol at room temperature was made by Raman spectroscopy and XRD. The penetration depth and surface distribution of the sol were
evaluated with SEM-EDS.
Photocatalytic oxidation of methyl orange (MeO) and methylene blue (MB) under fluorescent lamp
irradiation ( = 366 nm) was used as indicator of the catalytic activity of nano-TiO 2 sol and TiO2
coatings.
XRD and Raman measurements confirm the crystalline nature of titania in anatase form with
negligible brookite. The Raman peak positions and FWHM suggest anatase nanocrystals with 5-10
nm size. SEM-EDS shows a penetration depth of a few microns and surface distribution fairly
homogeneous. A fast photocatalytic activity was measured for both TiO2 sol and coatings.
The self-cleaning TiO2-based basic treatment does not introduce colorimetric changes compared to
the untreated limestone and does not alter the properties of the stone as determined by
measurements of the water capillarity absorption
The basic nanocrystalline TiO2 by sol-gel processes is an easy way to obtain photocatalytic desoiling coatings without modifying the morphology and the chemical-physical properties of
limestone and is promising for applications in the field of cultural heritage.
Support from MAECI (project NANO4HER, Nanotechnology at the service of cultural heritage
preservation, Italy-Israel Scientific and Technological Cooperation) is gratefully acknowledged.