NICOM’2 (Bilbao, 13-16 November 2005)

NANOTECHNOLOGY AND PHOTOCATALYSIS IN CEMENTITIOUS

MATERIALS

L. Cassar

CTG Italcementi Group, Italy

Abstract

A new and innovative approach to the material science has demonstrated that photocatalytic
activity may be conferred to cementitious construction materials such as paints, mortars,
concrete, roads etc.

This has been confirmed by the results obtained in the generalised use of self–cleaning
surfaces which allows buildings to maintain their aesthetic appearance unaltered over time.

In parallel, the capability of photocatalysis in cementitious materials to reduce the levels of

urban pollution has been proved in laboratory, in the field and in an experimental site properly
adjusted (“Canyon Street”).

One of the most important element which permitted obtaining such results is the use of
nanostructured TiO2 dispersed in the cementitious matrix.

Several examples of nanometric TiO2 behaviour in cementitious composition and their

activity are shown in the present work.

Key words: photocatalysis, cement, TiO2

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1. INTRODUCTION

A new and innovative approach to the material science has demonstrated that
photocatalytic activity may be conferred to cementitious construction materials such as paints,
mortars, concrete etc.[1,2].

Among the various semiconductor materials, TiO2 in the form of anatase has attracted
wide interest, due to its strong oxidizing power under near-UV radiation, its chemical stability
when exposed to acidic and basic compounds, its chemical inertness in the absence of UV
light, and its absence of toxicity. TiO2 has proved to be very effective in the reduction of
pollutants such as NOx, aromatics, ammonia, and aldehydes [3,4]. The use of TiO2 in
combination with cementitious materials has shown a favourable synergistic effect in the
reduction of pollutants [5,6].

In the present work we report the activity of nano-structured TiO2 in cementitious matrix
in particular in systems to clean buildings and removing NOx.

The cement/TiO2 system is interesting since in a certain number of cases , contradictory

results are found for the overall photo activity of the resulting materials.

2. CLEAN BUILDINGS

This technology for the photocatalytic degradation of organic pollutants is aimed at

maintaining the aesthetic characteristics of concrete structures, particularly those based on
white cement. The main reason for the discoloration of cementitious materials is the
accumulation of coloured organic compounds on their surfaces.

Suitable amounts of TiO2 have been introduced into cement mixes to render the surface of
the resulting structures photocatalytically active.

Self-cleaning properties were evaluated through the monitoring via colorimetric

measurements of the disappearance of a dye tainted into the surface [7].

This test consisted in monitoring the rate of photocatalytic decomposition of an organic

dye, rhodamine B ,by colorimetric measurements on polluted samples exposed to UV
irradiation during a 30 h period.

Samples were then placed under a UV-light (300 W Ultra-Vitalux lamp from Osram)
which provides an efficient wavelength band as contained in natural sunlight . The distance
between the lamp and samples was 1 m (figure 1), which corresponds to an intensity of 3700
Lux. This intensity has been chosen to limit the direct photolysis of rhodamine B and
simultaneously allows photocatalytic decomposition to continue.

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 1.05 m

samples

Figure 1: UV lamp lighting

Colorimetric measurements were carried out using a tristimulus colorimeter MINOLTA

CR 231. The results are expressed in the CIE LAB system with L*, a* and b* colorimetric
parameters (figure 2). Colour differences are established in terms of the following variations:
+∆L* = lighter -∆L* = darker
+∆a* = redder -∆a* = greener
+∆b* = yellower -∆b* = bluer

Figure 2: L*a*b* colorimetric system

Photocatalytic efficiency is assessed according to the sample ability to recover its initial
coloration more or less rapidly.

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 A convenient criteria to express and compare activity levels obtained for different
materials is the dye destruction velocity, calculated between 0 and 3 h according to the
following formula (identically for all parameters L*, a*, b*):

∂a * (t)
Va* = ∫tt ==03h .dt
∂t

With:

a * (t) = A × e−B×t + C + a * unp

t +D

A, B, C and D are parameters which are determined by fitting experimental curves.

a*unp corresponds to sample colour before pollution with rhodamine. The velocity is
calculated between 0 and 3 h so as to say in a first order reaction stage. Figure 3 shows the
activity of the samples due to the photo-destruction of the rhodamine dye for a 10 mm-thick
rendering. In particular it was evaluated the colour change rate. The kinetic curve of the
photo-catalytic effect due to the anatase addition shows an exponential form, which is typical
of a first order reaction.

Figure 3: Evolution of colour change (chrominant a*) vs. time for the cement-based materials.

These results open the way to the widespread development of self-cleaning concrete and
mortar-coated walls. TiO2/cement composites are expected to maintain their aesthetic
characteristics unchanged over time, in particular the colour, even in the presence of
aggressive urban environments. In fact, a white cement containing TiO2 (BiancoTX
Millennium) has already been used for the construction of the Cité de la Musique in
Chambéry, France (completed in 2000), the Dives in Misericordia Church in Rome

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(completed in 2003), and for other several applications in Italy and in France.

3. REMOVING NOX

TiO2-loaded cementitious materials are interesting not only for their self-cleaning
properties. Research under way shows that they also have good potential in urban pollution
control. Examples of pollutants that can be eliminated by the photocatalytic TiO2/cement
system are NOx, SOx, NH3, CO, volatile organic carbons such as benzene and toluene, or-
ganic chlorides, aldehydes, and polycondensated aromatics. The mechanism of nitrogen oxide
removal by photocatalysis is not simple. It is assumed that NO in the air is oxidized when the
catalyst is exposed to light. Through the intermediate step of nitrogen dioxide (NO2), it is then
converted to nitrate. When NO2 is formed, part of the gas may escape from the photocatalytic
surface, but in the presence of the cement matrix, the gas may be effectively trapped, together
with the nitrate salt formed [8].

In an experiment the efficiency rate was determined for the cement-based materials, using
a concentration of 200 ppb of NO (Fig 4). Tests were conducted at the Research Centre of EU
in Ispra (VA) in a30-m3 Indoortron room in the framework of the funded project PICADA.

120

100

80 Room loss or cement based

material without TiO2
NO percentage
percentage

60

Cement
40
based
material with
TiO2
20
Time (min)

0
0 50 100 150 200 250 300 350 400 450 500

time (min)

Figure 4 : Photocatalytic activity of the cement-based materials using a concentration of

200 ppb

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4. TIO2 NANOPARTICLES IN CEMENTITIOUS MATRIX

The photocatalytic activity of TiO2 depends on different parameters such as, among others:
crystalline phase, morphology and, indeed, specific surface area. The last parameter is often
reported to play a fundamental role.

While it is well known that, in general, an increase of surface area gives an increase of
photoactivity for TiO2 it cannot be said the same for a system cement/TiO2 [9].
By using the colorimetric method described above we have tested a system cement /TiO2
wherein TiO2 in the anatase form has different surface areas as can be seen in the table 1
below.

Table 1 : Different types of TiO2 in anatase form having different Mean Surface Area

TiO2 Particle size Mean Surface Area

(nm) B.E.T. (m2g-1)
A 150 11
B 150 10
C 15-25 85

In a first test we selected two different dyes (Rhodamine b and Green Bromocresol.) and a
content of TiO2 with respect to cement of 2%. We have taken the TiO2 indicated as C as
reference (Va*=100). The results are reported in table 2.

Table 2 : Different photocatalytic activity

Va* TiO2 A TiO2 B TiO2 C

Rhodamine b 120 118 100
Green 112 111 100
Bromocresol

As can be noted by decreasing the mean surface area the activity (rapid mixing 1 minute)
increases of about 10%.
In a second test we mixed different percentages of different TiO2 and surprisingly we
obtained a synergistic effect as reported in tables 3 and 4.

Table 3 : Synergistic effect between A and C

Va* 100% A 75% A /25% C 50% A /50% C 75% A /25% C 100%C

Rhodamine b 120 129 165 157 100
Green 112 155 149 142 100
Bromocresol

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Table 4 : Synergistic effect between B and C

Va* 100% B 75% B /25% C 50% B /50% C 75% B /25% C 100%C

Rhodamine b 118 152 194 157 100
Green 111 158 121 136 100
Bromocresol

It is not easy to find an explanation for such a behaviour, but it is evident that the system
TiO2/cement shows some peculiarities with respect the activity of the TiO2 alone.

In literature [10], Fujishima and coworkers discuss still another factor that is connected to
particle size and surface area, i.e., the state of hydration of particles. On highly hydrated
(hydroxylated) particles, illumination leads to formation of a high number of hydroxy-
radicals that can initiate oxidations.

Moreover water content (%) was shown to markedly influence the surface charge and,
consequently, the movement of illuminated TiO2 particles (Photoelectrorheological Effect)
[11 ]. These phenomena can be important in a system where TiO2 particles, in principle, can
move within channels of the porous cement matrix whose walls are reasonably negatively
charged.
Specific surface area but also particle size and their hydration state are then important
parameters that contribute to establishing the photocatalytic activity of this particular system.

REFERENCES

[1] Cassar, L., Pepe, C., Pimpinelli, N., Amadelli, R. and T. Bonato, “Cementitious materials and
photocatalysis”, Seminario FAST—Materiali: Ricerca e Prospettive Tecnologiche alle Soglie del 2000
(Federazione delle Associazioni Scientifiche e Tecniche, Milano, Italy, 1997) p. 591.

[2] Cassar, L., Pepe, C., Pimpinelli, N., Amadelli, R. and L. Antolini, “New Cement-Based Materials and
Photocatalysis,” presented at Rebuilding the City of Tomorrow, 3rd Eur. Conf. REBUILD (Barcelona, Spain,
1999).

[3] Kaneko, M. and Okura, I., Photocatalysis: Science and Technology (Springer, Berlin, 2002).

[4] Fujishima, A., “Nanotechnology and Photocatalysis: Important Science and Technology for Comfortable
Atmosphere,” presented at the Shanghai International Nanotechnology Cooperation Symposium (SINCS 2002),
Shanghai, China, July 30–Aug 1, 2002.

[5] Cassar, L. and Pepe, C., “Use of organic additives for the preparation of cementitious compositions with
improved properties of constancy of color,” U.S. Patent No. 6,117,229 (September 12, 2000).

[6] Cassar, L., Pepe, C., Tognon, G.P., Guerrini, G.L. and Amadelli, R., “White cement for architectural
concrete, possessing photocatalytic properties, Proc. 11th Int. Congress on the Chemistry of Cement (ICCC),
Vol. IV (Durban, South Africa, 2003) p. 2012.

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[7] Vallée, F., Ruot, B., Bonafous, L., Guillot, L., Pimpinelli, N., Cassar, L., Strini, A., Mapelli, E., Schiavi, L.,
Gobin, C., André, H., Moussiopoulos, H., Papadopoulos, A., Bartzis, J., Maggos, T., McIntyre, R., Lehaut-
Burnouf, C., Henrichsen, A., Laugesen, P., Amadelli, R., Kotzias, D. and Pichat, P. “Innovative Self-Cleaning
and De-Polluting Facade Surfaces,” CIB World Building Congress 2004, May 2–7, 2004, Toronto, Canada.

[8] Cassar, L., “Photocatalysis of cementitious materials: clean buildings and clean air”, MRS Bulletin, May
2004

[9] Colombet, P., Guillot, L., Cassat, P., Bonafous, L. and Cassar, L., “Mélange granulaire photocatalytique
pour mortier et béton et son utilisation”, Patent No. FR 2 845 375 (26.11.2004)

[10] Sakai, N., Komoda, Y., Rao, T.N., Tryk, D.A. and Fujishima, A., J. Electroanal.Chem., 445 (1998) 1

[11] Rao, T.N., Komoda, Y., Sakai, N. and Fujishima, A., Chem.Lett., 1997, 307

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