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Design and characterization of N-doped TiO2

coatings for cultural heritage applications
Laura Bergamonti1, Yaron Paz2,
Giovanni Predieri3, Pier Paolo Lottici4, Federica Bondioli1
1

Industrial Engineering Dept., University of Parma, Parco Area delle Scienze

181/a, 43124 Parma (Italy)
2
Chemical Engineering Dept., Technion City, 3200003 Haifa (Israel)
3
Chemistry Dept., University of Parma, Parco Area delle Scienze 17/a, 43124
Parma (Italy)
4
Physics and Earth Sciences Dept., University of Parma, Parco Area delle Scienze
7/a, 43124 Parma (Italy)

The main forms of deterioration on stone buildings and monuments

are related to the accumulation of pollutants and to soiling processes.
Photo-catalyzed oxidation methods can be used for the decomposition of
various environmental pollutants. Photoactive nanocrystalline TiO 2,
obtained by sol-gel process, is a promising de-soiling coating material. To
enhance the absorption of visible light by providing defect states, Ndoped TiO2 nanoparticles were synthesized starting from titanium(IV)
isopropoxide or titanium(IV) oxy-sulfate using urea and nitric acid as
peptizers and have been investigated for self-cleaning photocatalytic
coatings on carbonate stones.
The TiO2 powders were characterized by X-ray diffraction, Raman
spectroscopy and X-ray photoelectron spectroscopy (XPS). Different types
of limestone among the most frequently used in historic buildings were
used as substrates.
Photocatalytic oxidation under solar lamp irradiation of methyl orange
(MeO), Rhodamine B (RhB), Crystal Violet (CV) and methylene blue (MB)
was monitored for the activity efficiency of N-doped TiO 2 sols and TiO2
coatings. XPS measurements indicate that doping by ammonia in the sol
using HNO3 as peptizer leads to the formation of Ti-N chemical interaction
accompanied by some metallic (non-oxidized) Ti. The introduction of
nitrogen by urea is not clearly evidenced by the formation of Ti-N
bonding.
A fast photocatalytic activity is measured for both TiO 2 sols and
coatings. The self-cleaning TiO2-based 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 and wettability tests.

Support from MAECI (project NANO4HER, Nanotechnology at the service

of cultural heritage preservation, Italy-Israel Scientific and Technological
Cooperation) is gratefully acknowledged.