University of Parma - Italy and Technion-Israel Institute of Technology - Israel

Travertine stone: photocatalytic coatings by N-doped TiO2

Laura Bergamonti1, Giovanni Predieri2, Yaron Paz3, Pier Paolo Lottici4, Federica Bondioli1
1

Department of Industrial Engineering, University of Parma, Parco Area delle Scienze 181/a, 43124 Parma, Italy
2 Department of Chemistry, University of Parma, Parco Area delle Scienze 17/a, 43124 Parma, Italy
3 Department of Chemical Engineering, Technion-Israel Institute of Technology, Technion City, 32000 Haifa, Israel
4 Department of Physics and Earth Sciences, University of Parma, Parco Area delle Scienze 7/a, 43124 Parma, Italy

Self cleaning photocatalytic coatings for limestones, based on N-doped TiO2 nanoparticles, obtained by the sol-gel process and dispersed
in aqueous medium, have been studied. The selected test material is Travertine, one of most widely used as building stones, from Roman
period. XRD, XPS and Raman investigations were carried out to characterize the TiO2 nanoparticles. Nanocrystalline anatase and, to a
lesser extent, brookite are obtained. To evaluate the compatibility of the coatings with the substrate, colorimetric changes, static contact
angle test and water absorption by capillarity were performed. Photocatalytic activity of the TiO2 sols and coatings was assessed under
solar lamp (Osram Vitalux) irradiation through degradation tests of methyl orange, crystal violet, rhodamine B and methylene blue dyes.
A simple one-step procedure to synthesize water based N-doped nanosols of anatase is
employed. Two sols, named Ti-N and Ti-U were obtained by hydrolysis of titaniumoxysulfate (TiOSO) and tetraisopropyl orthotitanate (TiPOT), respectively.
Ti-N after hydrolysis of TiOSO was precipitated with ammonia, washed and peptized with
nitric acid; Ti-U sol is obtained by hydrolysis of TiPOT using urea as complexing agent
and as N-source. Each sol was heated at 373 K for three hours. The powders, for the
characterizations, were obtained by drying the sols at room temperature.

Raman

Ti-U

Ti-N

XPS

XRD

Doping by ammonia the powder

obtained by TiOSO leads to the
formation of Ti-N chemical bonds.

Ti-N

In all the titania powders, with respect to

crystalline anatase, the frequency shift observed
and the FWHM of the most intense peak may be
compatible with anatase nanocrystals of 4-10 nm
size as suggested by XRD.

UV/Vis
Reflectance
The crystallite size of anatase nanoparticles,
estimated from the FWHM of A(101) peak, is in the
10-12 nm range for Ti-U and 4-6 nm for Ti-N.
The brookite phase results ~10 % for Ti-N and less
than 4 % for Ti-U.

P25
Ti-N
Ti-U

Photocatalytic
tests
Self-cleaning test on different dyes
with P25, Ti-N and Ti-U coatings.
NT is the untreated stone

Diffuse Reflectance measurements on

TiO2 powders show the red shift of the
optical band-gap due to the nitrogen
doping of TiO2 nanoparticles.
Travertine

Ratio between the pseudo first order

photocatalytic degradation rate constant k of
the dyes measured for different nanosols with
respect to the rate constant k0 of the pure dye.

a
400 m

400 m

Contact angle measurements under solar irradiation (01-3 hrs) of Travertine coated with N-TiU.

(a) SEM image of Travertine coated with Ti-N and

(b) EDS map of Ti distribution.
Capillary absorption curves

NT

E*
( s.d.)
-

P25
Ti-N
Ti-U

2.4 (0.7)
1.5 (0.5)
1.1 (0.4)

RCI
(0.02)
1.00
0.98
0.88
0.75

Color change (E*) and Relative

Capillary Index (RCI) [1] of the coated
and uncoated Travertine stone samples.

CONCLUSIONS: Water-based sols containing N-doped titanium dioxide were

deposited on Travertine, to obtain self-cleaning coatings. The sols were
synthesized by the solgel method, working at low temperatures. The
synthesized N-doped TiO2 nanosols do not change the original appearance of
the stone, according to the colorimetric tests. The coatings, with respect to the
uncoated stone, slightly reduce the capillarity water absorption. The efficiency
of the photodegradation of the N-doped TiO2 sols under solar irradiation is
improved with respect to commercial P25.