International RILEM Symposium on Photocatalysis, Environment and Construction Materials

8-9 October 2007, Florence, Italy

PHOTOCATALYTIC CEMENT: A NEW APPROACH TO

ENVIRONMENTAL PROTECTION
Luigi Campanella (1), Fabio Borzetti (1, 2) and Luigi Cassar (2)

(1) Università di Roma “La Sapienza”, Dipartimento di Chimica – Roma, Italy

(2) Italcementi S.p.A. – Bergamo, Italia

Abstract
The interest for photocatalytic cement pastes to protect environment has here been
finalized to abate on degradation PM10 concentration considered as the most dangerous
pollutant to citizens of urban centres. The catalytic action of these materials was evaluated on
measuring the respiratory capacity of yeast Saccharomyces cerevisiae cells incubated with
particulate matter samples treated or untreated with them.The cement contained 3% of TiO2
as photoactive catalyst based for its photocatalytic activity on its semiconducting properties.
The experimental time ranged from 24 to 96 hours. The value of abatement was relatively low
(about 30%), but it was possible to double it on enriching the cement by addition of TiO2 or
by using a cement richer in TiO2 since its preparation step. The catalytic activity is also
enhanced by an antimicrobic one.

1. INTRODUCTION
A new and innovative approach contributing to minimize the airborne pollutants in our cities
may be the use of suitable photocatalytic cementitious materials containing TiO2. In general
heterogeneous photocatalysis can be considered as one of the new “advanced oxidation
technologies” used in the recent years as a promising method for the removal of toxic organic
and some inorganic contaminants from the air and the water.
Several bibliographical reviews have been recently devoted to this problem [1-8]. When a
semiconductor catalyst, such as TiO2, absorbs a photon of energy that is equal to or greater
than its band gap (in case of TiO2 amounting to 3.2 eV), an electron (e – ) may be promoted
from the valence band (VB) to the conduction band (CB) thus generating an electron vacancy
‘‘hole ’’(h+) and obviously an electronic site. The electron and the hole can migrate to the
catalyst surface where they participate in redox reactions with different species adsorbed on
catalyst surface. Holes can particularly react with surface-bond H2O or OH– to produce the
hydroxyl radical OH•, whereas electrons during reaction with oxygen can generate superoxide
radical anion O2 • –. The hydroxyl (OH • ) and superoxide radical anions (O2 • – ) are supposed

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8-9 October 2007, Florence, Italy

to be the primary oxidizing species in the photocatalytic oxidation processes. An example of

the described mechanism can be ressumed as follows:

TiO2 + hν (UV) TiO2 (eCB – + hVB+) (1)

TiO2 (hVB+) + H2O TiO2 + H++ OH • (2)
TiO2 (eCB –) + O2 TiO2 + O2 • – (3)
O2 • – + H+ HO2 • (4)
Organic compounds + OH • degradation products (5)

At the end of the process, most organic compounds can be oxidized to carbon dioxide and
water. In a recent patent of Italcementi, also the cementitious materials opportunely prepared
containing titanium dioxide, mainly in the form of anatase, show photocatalytic activity when
irradiated with adequate wavelength light. Therefore, these materials containing a non-toxic
semiconductor catalyst such as titanium dioxide might be a good help and a new way to abate
the airborne pollutants (i.e. particulate matter PM containing many different organic chemical
species adsorbed on it). In the present work, the main objective was aiming to evaluate action
of photocatalytic cementitious materials on PM10 (airborne particulate matter with
aerodynamic diameter less than 10 μm) in a possible decrease of the concentration of this
dangerous environmental pollutant. This evaluation has been realized by suitable
respirometric tests on S. Cerevisiae cells. It’s well known that, in the cellular respiration,
using glucose as a nutrient, the aerobic cells consume oxygen as schematically described in
the following reaction:

yeast cells
C6H6O6 + 6O2 6CO2 + 6H2O + Energy (6)

However, in the presence of any chemical perturbation (i.e. PM10 containing many toxic
substances for one or more of the metabolic processes in the cell respiration), it’s possible to
observe a variation of oxygen consumed by the yeast cells. As larger is this variation, as
higher has to be considered the concentration of toxic substances to which yeast cells have
been exposed. Therefore, the toxicity can be expressed as inhibition percentage of yeast cells
respiration and estimated by appropriate respirometric curves consisting in the measure of the
oxygen consumed by the yeasts with the time. From the experimental point of view, the
catalytic action of photocatalytic cementitious materials has been realized using two halves of
each PM10 filter sample (PM10 fibre glass filters exposed to urban air were provided by ISS
in Rome - Italy) to estimate the PM10 toxicity itself with the first half and with the second
one the toxicity of photoexposed PM10 to UV light in presence of an Italcementi
photocatalytic material for 48, 72, and 96 hours. The photoexposure has been performed in
controlled conditions by a veterometer photodegradator QUV Weathering Tester and
Italcementi photocatalytic cementitious paint containing 3% of titanium dioxide was used as
catalyst. In particular two half filters sampling treated-untreated PM 10 were incubated with
the yeasts and toxicity tests were subsequently carried out. In conclusion, the comparison

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8-9 October 2007, Florence, Italy

between the obtained results has permitted to evaluate the photocatalytic cementitious
material action on the toxicity abatement of treated PM10 samples. Some other preliminary
tests indicated that the photocatalytic materials richer (up to 7%) in TiO2 than those
containing 3% of dioxide titanium might be more active in PM10 abatement.

2. EXPERIMENTAL

2.1 Materials and instruments

The following reagents and materials were used: D-glucose for microbiology, a buffer
solution prepared at pH about 5,6 by suitable phosphate salts, as catalyst material it has been
used a photocatalytic cementitious paint containing 3% of TiO2 made available by
Italcementi. The cells used in the toxicity tests belonged to a wild diploid strain of
Saccharomyces cerevisiae. Such tests will be described in a next paragraph. The following
apparatus was used: veterometer, photodegradator QUV Weathering Tester-Model
QUV/spray Q-Panel LAB-Products for the photoexposures (UV - λ = 310 nm, irradiance 0,6
W/m2, humidity 58%) of the PM10 samples in presence of photocatalytic cementitious paint;
Amel Instruments, Dissolved oxygen meter, model 360 and amperometric oxygen gas
diffusion sensor (Clark electrode). A computer was used to record as function of time the
oxygen consumed by the yeast cells in respiration.

2.2 Samples
The PM 10 samples have been provided by the I.S.S. in Rome – Italy. Such samples of PM 10
have been collected on fibre glass filters (Schleicher & Schuell, d= 47 mm) in urban area of
Rome.

2.3 Preparation of samples

At the beginning of the preparation of PM10 samples, each filter has been divided in two
identical halves and three petri dishes have been prepared. Subsequently in the first dish we
have exactly injected 1500 μl of a Saccharomyces cerevisiae yeast solution (this was
previously prepared by hydration of yeasts in distilled water) and 10 ml of phosphate buffer
solution (pH =5,6). In the second petri dish containing the same quantity of yeast cells and
buffer solution, the first half of PM10 filter has been added. In the last petri dish we have
exactly added 1500 μl of the Saccharomyces cerevisiae yeast solution, the another half of
PM10 filter previously exposed to UV light with photocatalytic paint, and 10 ml (final
volume) of buffer solution which had been used in the photocatalysis. The three petri dishes
(respectively, blank/control, untread PM10 sample, treated PM10 sample) containing the
yeasts have been subjected to incubation time of 24 hours under magnetic stirring. After
incubation period, the content of the three petri dishes has been poured off one by one in three
suitable tubes to which their washing water was also added. Then such tubes have been
centrifugated to 3000 rpm for 20 min. At the end, the pellet of yeast in the bottom of each
tubes was recovered without the solution which was above. The pellets of yeast were again
suspended in each tube by 1500 μl of distilled water. The solutions of yeast in the three tubes
have been later used for respirometric tests. The photoexposures of PM10 half filters have
been carried out in veterometer by opened dishes to which it was applied the photocatalytic
paint. In each modified dish there was the PM10 sample and 5 ml of the buffer solution.

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8-9 October 2007, Florence, Italy

At the end of photoexposures (48, 72, 96 hours), the treated PM10 samples have been used as
said above, that is evaluated for their respirometric toxicity.

2.4 Method
The principle of method consists in measuring with oxygen electrode the change in O2
concentration which is due to yeast cellular respiratory activity (DppmO2) [9].
In particular the measurement is performed comparing, for each measure, the obtained value
of DppmO2 (2-3) from the cells exposed to PM 10 (treated or untreated with UV light in
presence of photocatalitic paint) with the DppmO2 (1) one deriving from cells (blank) that
have been subjected to same incubation time and same experimental protocol in absence of
exposure to PM10. The inhibition percentage of respirometric activity has been related as to
toxicity. It can be calculed as follows:

Toxicity % = [ DppmO2 (1) – DppmO2(2-3) ] 100 / DppmO2 (1) (a)

From the experimental point of view, for the measurement of dissolved oxygen, the electrode
has been immersed in a glass beaker containing a standard glucose solution, concentration
1 M, under costant magnetic stirring. After stabilisation of the signal, 1000 μl of yeast
solution contained in one of the tubes (see paragraph 2.3) were added to the glucose solution.
The variation of dissolved oxygen concentration, caused by yeast cells in respiration, has been
recorded as fuction of time. In this way we obtained the “respirometric curves” and from
these it has been possible to calculate the toxicity of the coupled half filters of treated-
untreated PM10.

3. RESULTS AND CONCLUSION

The respirometric tests data on the treated PM10 half filters for 48, 72 and 96 hours by
photocatalytic paint under UV light are shown in fig. 1, 2 and 3. In these graphics also the
data of respirometric tests of the blanks and untreated PM10 half filters are plotted.

FIG. 1 - Respirometric tests data (treated PM10 for 48h by UV light and
photocatalytic cementitious paint containing TiO2 3%)
FIG - 1

D1 (ppmO2) BLANK
4
3.5
Delta (ppmO2)

3 D2(ppmO2) - YEAST EXPOSED TO

TREATED PM 10 BY UV LIGHT AND
2.5 PHOTOCATALYTIC CEMENTITIOUS
PAINT FOR 48h
2
D3(ppmO2) -YEAST EXPOSED TO
1.5 UNTREATED PM 10

0 2 4 6 8 10
TEST NUMBER

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8-9 October 2007, Florence, Italy

FIG. 2 - Respirometric tests data (treated PM10 for 72h by UV light and
photocatalytic cementitious paint
FIG. 2

4 D1 (ppmO2) BLANK

3.5
Delta (ppmO2)

3
D2(ppmO2) - YEAST EXPOSED TO
2.5 TREATED PM10 BY UV LIGHT
AND PHOTOCATYTIC
2 CEMENTITIOUS PAINT FOR 72 h
D3(ppmO2) - YEAST EXPOSED TO
1.5 UNTREATED PM10
10 12 14 16 18 20
TEST NUMBER

FIG. 3 - Respirometric tests data (treated PM10 for 96h by UV light and
photocatalytic cementitious paint
FIG. 3

D1 (ppmO2) - BLANK

4.0
Delta (ppmO2)

3.5
D2(ppmO2) - YEAST EXPOPSED
3.0 TO TREATED PM10 BY UV
2.5 LIGHTAND PHOTOCATALYTIC
PAINT FOR 96h
2.0
D3(ppmO2) - YEAST EXPOSED
1.5 TO UNTREATED PM10
20 22 24 26 28 30
TEST NUMBER

In tab.1 we have summarized the obtained results on treated-untreated PM10 samples:

Tab. 1

Treatment time Toxicity % of treated Toxicity % of Toxicity Toxicity

of PM10 by UV PM10 untreated reduction reduction
and PM10
photocatalytic Treatment by UV and % (absolute value)
paint photocatalytic cementitious
(hours) paint containing TiO2

48 (9 + 2) (15 + 2) (34 + 12) (6 + 4)

72 (9 + 3) (19 + 5) (44 + 20) (10 + 4)
96 (12 + 2) (20 + 3) (39 + 13) (8 + 3)

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The confidential intervals shown in tab.1 have been calculated with 80% probability level by
following mathematic equation:

X = X mean + t ST. DEV. / N 0.5

N = 10 number of tests
t = 1,38 for (N-1) freedom degrees and 80 % confidence level

In details after exposing PM10 samples to UV (48, 72, 96 houres) with Italcementi
photocatalytic paint, the toxicity values of PM 10 decreased respectively from (15 + 2)% to
(9 + 2)%, from (19 + 5)% to (9 + 3)%, and from (20 + 3)% to (12 + 2)%. It’s also necessary
to consider that the wide variability of obtained data reflects the variegated composition of the
PM10. In regard to the results of toxicity reduction percentage the following mean values
were respectively obtained (34 + 12)%, (44 + 20)%, and (39 + 13)% for exposure time of 48,
72, 96 hours. As the toxicity abatement value was relatively low, we have supposed that
photocatalytic cementitious materials containing a larger concentration of TiO2 may be more
active than those ones containing 3% TiO2. For this reason two screening measures were
carried out in abating PM10 toxicity by photocatalytic cementitious materials enriched in
TiO2 concentration (7%). The results are shown in tab. 2

Tab. 2

Treatment time Photocatalytic Toxicity % of Toxicity % Toxicity Toxicity

of PM10 by UV cementitious treated PM10 of untreated reduction reduction
and material PM10
photocatalytic containing Treatment by UV % (absolute
cementitious TiO2 - 7% and photocatalytic value)
material cementitious
(hours) material

24 blank paint 32 50 37 18
24 blank cement 28 71 61 43

Last data show that the photocatalytic cementitious materials enriched in TiO2 have a higher
action in abating PM10 toxicity than others containing 3% in TiO2. However, further
measures will be necessary to confirm such results. Some results on the antimicrobic activity
of photocatalytic cementitious materials show that during the first 130 minutes of
photoexposure they have more active than ones not containing photocatalyst (tab. 3).

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8-9 October 2007, Florence, Italy

Tab.3
Treatment time DA (ppmO2) DB (ppmO2) DC (ppmO2)

(min.) oxygen consumption oxygen consumption from oxygen consumption from the
from the respiration the respiration of yeasts respiration of yeasts after their
of yeasts after their after their treatment by treatment by artificial solar light
treatment in dark in artificial solar light in in presence of blank cement
presence of blank presence simply of blank containing TiO2
cement containing cement
TiO2
10 2,0 1,8 1,8
30 1,7 1,2 1,0
60 1,8 0,9 0,8
90 2,0 1,3 0,7
130 1,7 0,5 0,2

In conclusion the tested photocatalytic cementitious materials behave as abating toxicity of

PM even if at relatively low rate. But on the basis of our results their performances can be
improved on increasing TiO2 concentration at higher value than 3%.

REFERENCES
[1] L.Cassar, Photocatalysis of cementitious materials clean buildings and clean air, MRS Bulletin,
May 2004, 328-331
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Res. Vol. 34, No. 5, pp. 1638-1644, 2000
[3] Akira Fujishima, Tata N. Rao, Donald A. Tryk, Titanium dioxide photocatalysis, Journal of
Photochemistry and Photobiology C: Photochemistry Reviews 1 (2000) 1–21
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mediated photocatalytic degradation of gaseous trichloroethylene and dimethyl sulfide on
modified titanium dioxide, Applied Catalysis B: Environmental 61 (2005) 140–149
[4] J.R. Dominguez , J. Beltran, O. Rodriguez, Vis and UV photocatalytic detoxification (usingTiO2,
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[5] M. Anpo and M. Takeuchi, The design and development of highly reactive titanium oxide
photocatalysts operating under visible light irradiation, Journal of Catalysis 216 (2003) 505–516
[6] D.M. Blake, Bibliography of Work on Photocatalytic
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