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Energy Procedia
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00 (2017)
(2017) 000–000
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Energy
EnergyProcedia
Procedia119 (2017) 000–000
00 (2017) 332–345
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International
International Conference
Conference on
on Technologies
Technologies and
and Materials
Materials for
for Renewable
Renewable Energy,
Energy, Environment
Environment
and Sustainability, TMREES17, 21-24 April 2017, Beirut Lebanon
and Sustainability, TMREES17, 21-24 April 2017, Beirut Lebanon

Exploring potential
The 15th Environmental
International applications
Symposium on District of TiO2
Heating and Cooling
Nanoparticles
Assessing the feasibility of using the heat demand-outdoor
Adawiya
Adawiya J.
temperatureJ. Haider
Haidera*, Riyad Hassan AL- Anbarib, Ghadah Rasim Kadhimb,
function for
, Riyad a long-term
Hassan
a*
district
AL- Anbari heat
, Ghadah demand
Rasim Kadhimforecast
,
b b
Chafic Touma Salamecc
Chafic Touma Salame
a,b,caa Applied scienceadepartment, University
a of Technology,bBaghdad (10066), Iraq c c
I. Andrić *, A. Pina
Applied , P. Ferrão
science department, , J. ofFournier
University ., B. Lacarrière
Technology, Baghdad (10066), Iraq , O. Le Corre
Department of Building and Construction Engineering, University of Technology, Baghdad (10066), Iraq
b
b
Department of Building and Construction Engineering, University of Technology, Baghdad (10066), Iraq
c Lebanon University, Beirut, Lebanon
c
a Lebanon
IN+ Center for Innovation, Technology and Policy University,
Research Beirut,
- Instituto Lebanon
Superior Técnico, Av. Rovisco Pais 1, 1049-001 Lisbon, Portugal
b
Veolia Recherche & Innovation, 291 Avenue Dreyfous Daniel, 78520 Limay, France
c
Département Systèmes Énergétiques et Environnement - IMT Atlantique, 4 rue Alfred Kastler, 44300 Nantes, France
Abstract
Abstract

This
This study
study aims
aims at at preparing
preparing thinthin layers
layers ofof (TiO2)
(TiO2) with
with aa high
high photocatalytic
photocatalytic activity
activity and
and antibacterial
antibacterial properties
properties for
for use
use
as a self-
Abstract cleaning transparent coatings for windows in outdoors
as a self- cleaning transparent coatings for windows in outdoors applications. applications.
Titanium dioxide
Titanium dioxide (TiO2)
(TiO2) nanoparticles
nanoparticles were were prepared
prepared by by sol-gel
sol-gel process
process using
using Titanium
Titanium Tetrachloride
Tetrachloride (TiCl4)
(TiCl4) asas aa
precursor,
precursor, and
and calcined
District heating networks
calcined at
at different
are commonly
different calcination temperatures
addressed
calcination (400,
(400, 600,
in the literature
temperatures 600,as 800,
one of
800, and
andthe1000)
mostᵒC.
1000) The
The synthesized
effective
ᵒC. solutions for
synthesized nanoparticles
decreasing the
nanoparticles
were
were characterized
greenhouse
characterized by
by X-ray
gas emissions X-ray fromdiffraction
diffraction (XRD),
the building
(XRD), Scanning
sector. Electron
These systems
Scanning Microscopy
Electronrequire (SEM),
(SEM), Ultraviolet
high investments
Microscopy which are
Ultraviolet spectroscopy (Uv-Vis),
returned through
spectroscopy the heat
(Uv-Vis),
Atomic
Atomic Force Microscopy (AFM). Self-cleaning properties were studies through two important tests; hydrophilicity by
sales. Force
Due to Microscopy
the changed (AFM).
climate Self-cleaning
conditions andproperties
building were studies
renovation through
policies, two
heat important
demand in tests;
the hydrophilicity
future could decrease,
by
measuring
prolongingthe
measuring theWater
the investment
Water Contact
Contact Angle
return (WCA)
(WCA) and
period.
Angle and photocatalytic
photocatalytic activity
activity by
by using
using potassium
potassium permanganate
permanganate (KMnO4)
(KMnO4) as as aa
model
model organic
The main scope
organic pollutant. Secondly,
of this paper
pollutant. aa thin
thin film
is to assess
Secondly, coating
coating of
the feasibility
film ofofTiO2
using
TiO2 nanoparticles was
was deposited
the heat demand
nanoparticles – outdoorby
deposited spin
spin coating.
temperature
by The
The antimicrobial
function
coating. for heat demand
antimicrobial
activity
activity of TiO2 nanoparticles was assessed quantitatively against two types of bacteria, (Pseudomonas aeruginosa),
forecast.of TiO2
The nanoparticles
district of was
Alvalade, assessed
located inquantitatively
Lisbon against
(Portugal), two
was types
used of
as a bacteria,
case (Pseudomonas
study. The district is consisted and
aeruginosa), of 665
and
(Staphylococcus
buildings that
(Staphylococcus aurous).aurous).
vary in both construction period and typology. Three weather scenarios (low, medium, high) and three district
© 2017
2017 The
The Authors.
©renovation scenariosPublished
Authors. by
by Elsevier
were developed
Published Elsevier Ltd.
(shallow,
Ltd. intermediate, deep). To estimate the error, obtained heat demand values were
© 2017 Thewith
Peer-review
compared Authors.
under resultsPublished
responsibility by
of
from a dynamic Elsevier
the heatLtd.
Euro-Mediterranean
demand model, Institute for
previously Sustainable Development
validated by(EUMISD).
Peer-review
Peer-review under
under responsibility
responsibility of the
of the Euro-Mediterranean
Euro-Mediterranean Institute
Institute fordeveloped
for Sustainable
Sustainable
andDevelopment
Development
the authors.
(EUMISD).
(EUMISD).
The results showed that when only weather change is considered, the margin of error could be acceptable for some applications
(the errorTitanium
Keywords:
Keywords: in annual
Titanium dioxide;
demand
dioxide; Antibacterial
was lower
Antibacterial activity;
than Bacteria;
activity; 20% forPhotocatalysis;
Bacteria; Self-cleaning
all weather scenarios
Photocatalysis; Nanocoating
considered).
Self-cleaning Nanocoating However, after introducing renovation
scenarios, the error value increased up to 59.5% (depending on the weather and renovation scenarios combination considered).
The value of slope coefficient increased on average within the range of 3.8% up to 8% per decade, that corresponds to the
decrease in the number of heating hours of 22-139h during the heating season (depending on the combination of weather and
*
* Corresponding
Corresponding Author
Author Email
Email address:
address: adawiyajumaa96@gmail.com
adawiyajumaa96@gmail.com
renovation scenarios considered). On the other hand, function intercept increased for 7.8-12.7% per decade (depending on the
coupled scenarios). The values suggested could be used to modify the function parameters for the scenarios considered, and
1.
1. Introduction
improve Introduction
the accuracy of heat demand estimations.

© 2017A major
AThe
major problem
problem
Authors. that
thatbyfacing
Published facing the modern
theLtd.
Elsevier societies and
modern societies and threatening
threatening humankind
humankind health
health is
is air
air and
and water
water
pollution
pollution [1]. On
On aaresponsibility
[1].under
Peer-review daily
daily basis,
basis,ofcivil,
civil, industrial
industrial
the Scientific and
and military
military
Committee activities
activities
of The create
create an enormous
anSymposium
15th International enormous onamount
Districtof
amount organic
ofHeating andand
organic and
inorganic
Cooling. pollutants
inorganic pollutants that
that unavoidably
unavoidably end end upup in
in our
our atmosphere,
atmosphere, rivers,
rivers, seas
seas and
and soil.
soil. Furthermore,
Furthermore, microbes
microbes
Keywords:©Heat
1876-6102 demand; Forecast; Climatebychange
1876-6102 © 2017
2017 The
The Authors.
Authors. Published
Published by Elsevier
Elsevier Ltd.
Ltd.
Peer-review
Peer-review under responsibility of
under responsibility of the
the Euro-Mediterranean
Euro-Mediterranean Institute
Institute for
for Sustainable
Sustainable Development
Development (EUMISD).
(EUMISD).

1876-6102 © 2017 The Authors. Published by Elsevier Ltd.

Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and Cooling.
1876-6102 © 2017 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility of the Euro-Mediterranean Institute for Sustainable Development (EUMISD).
10.1016/j.egypro.2017.07.117
 Adawiya J. Haider et al. / Energy Procedia 119 (2017) 332–345 333
2 Adawiya J. Haider et al. / Energy Procedia 00 (2017) 000–000

growth and deposition on surfaces such as walls, windows and tables pose a substantial threat to human health.
Continual exposure to these pollutants can lead to varied health troubles such as irritations and toxic effects, and
other various respiratory or skin diseases [2]. Thus, Science was interested in searching for new alternatives and
ecologically sustainable, renewable and environmentally friendly methods for cleaning up environmental
contamination. Antimicrobial Photocatalytic coatings, including TiO2 nanoparticles, could be a way to prevent
microbial proliferation or significantly reduce the amount of microorganisms that grow on surfaces of building
materials [3].
The research on photocatalysts shows that it is a promising technique for the decomposition of organic
contaminant using clean solar energy without yielding any harmful by-products [4]. This technique can be
envisaged as one of the most promising Advanced Oxidation Process (AOPs) due to its specific advantages, such
as bland reaction conditions, the possibility of using molecular oxygen as oxidant species, the total mineralization
of pollutants into substances innocuous to the environment [5]. Photocatalysis is based on the interaction between
semiconductor materials and light by considering that ‘free’ light from the sun, the idea of using solar light energy
as resource to clean up the environment is an ideal and promising approach.
The efficiency of photocatalytic materials, such as titanium dioxide (TiO2), to degrade organic
contaminants in the air and water has been studied for more than 30 years [6]. Titanium dioxide (TiO2) has been
widely used as a photocatalyst for solar energy conversion [7][8][9][10] and environmental applications and
building materials such as tiles, concrete, paints and glasses due to its interesting properties that include chemical
stability, good optical transparency, high refractive index, low cost, and non-toxicity [11][12][13][14].
The photocatalytic disinfection efficiency is attributed to the oxidative damage mainly induced by reactive
oxygen species (ROS), like O2•−, H2O2 and HO•. These reactive oxygen species are produced on the surface of
TiO2 when illuminated by photons with energy greater than its band gap, so electron will excited from valance
band to the conduction band thus creating an electron-hole pair. With holes (h+) and hydroxyl radicals (OH•)
generated in the valence band, and electrons and superoxide anions (O2 •-) generated in the conduction band,
irradiated TiO2 photocatalysts can decompose and mineralize organic compounds by a series of oxidation
reactions leading to carbon dioxide [15]. The mechanism of radical’s generation (•OH and •O2¯) is presented as
follows [16] :
TiO2 + hν →TiO2 (e‾+h+) (1)
H2O + TiO2 (h+) →TiO2+•OH+H+ (2)
O2+ TiO2 (e‾) →TiO2+•O2¯ (3)

Antimicrobial coatings have been developed for a variety of different applications to reduce the
proliferation of bacteria, fungi, and viruses on surfaces. Two significant effects related to photoactive TiO2
coatings nature had been by this time discovered:
i. The effect of self-cleaning due to redox reactions on the photocatalyst surface when excited by sunlight
(or in general, weak U.V. light);
ii. The photo-induced hydrophilicity [17] of the surface of the catalyst, which enhances the self-cleaning
effect, dirt and stains on surfaces that caused by inorganics can be easily removed due to soaking the
rainwater between the adsorbed substance and the surface of TiO2.

Photocatalytic glasses give an example of self-cleaning and anti-fogging (wetting) properties [18].
The aim of this study was the evaluation of the photoactivated antibacterial activity of TiO2-coated
surfaces. Different bacterial strains that represent common contaminants of environment and healthcare facilities,
were used as model organisms (Staphylococcus aureus, Pseudomonas aeruginosa). Initially bacterial inactivation
ability was evaluated using photocatalytic TiO2 powder deposited as a thin layer on glass substrate. The
photocatalytic activity of TiO2-coated surfaces was verified by measuring the potassium permanganate (KMnO4)
degradation rate in water under sunlight exposure, and the relationship with antibacterial activity was evaluated.
 
334 Adawiya J. Haider et al. / Energy Procedia 119 (2017) 332–345
Adawiya J. Haider et al. / Energy Procedia 00 (2017) 000–000 3

2. Experimental section

2.1 Synthesis of tio2 nanoparticles

All of the chemicals were analytical grade. 20 ml Titanium Tetrachloride TiCl4 (99.99%, BDH, England)
was slowly added dropwise into 200 ml absolute ethanol CH3CH2OH (99.99%, GCC, U.K) at room temperature.
The reaction was performed in a fume hood due to the large amount of Cl2 and HCl that was exhausted during the
mixing process. A light yellow solution was obtained and gelatinized to form sol- gel. The pH of the solution was
in the range of (1-2). Then, the sol-gel solution was vaporized at 80 ᵒC until a dry-gel was obtained. The dry-gel
precursor was calcined for one and a half hour in the box furnace at different calcination temperatures (400, 600,
800 and 1000) ᵒC, to form TiO2 Nano powders.

2.2 Preparation of TiO2 coating

A thin layer of photocatalytic TiO2 nanoparticles was deposited on glass substrate. Before coating, glass
slids (75 × 25mm) were ultrasonically cleaned in acetone and then dipped in absolute ethanol for 5 min, after
which a thorough wash was carried out. TiO2 powder suspended in water (1 mg cm-2) was deposited by a spin
coating method then dried at room temperature. Then incubated for 1h at 100°C to fix the TiO2 particles.

2.3 Characterization

The prepared nanoparticles were characterized for the crystalline phase by X-ray diffraction using (XRD-
6000 2kw type), at room temperature, operating at 40 kV and 30 mA, Cu (1.54060 A). The morphological
changes of prepared TiO2 nanoparticles at different calcination temperatures were analyzed using Scanning
Electron Microscopy (SEM, Tescan VEGA3 SB). Atomic Force Microscopy (AFM) was used to visualize the
surface topography and surface roughness of the prepared samples using AFM/SPM Scanning Probe Microscope
in intermittent.

3. Results and discussions

3.1 X-Ray Diffraction (XRD) analysis

Figure 1 present the XRD pattern of TiO2 nanoparticles obtained by sol gel method and calcined at
different temperatures. Crystallite size was obtained by Scherrer’s formula given by equation:
D=Kλ/ (βcosθ) (1)
where k is a constant that depends on the crystallite shape (0.9, with the assumption of spherical particles)
[13][19], λ is the X-ray wavelength, β is the full width at half maximum of the selected peak and θ is the Bragg’s
angle of diffraction for the peak. The rutile to anatase ratio was determined from the relation [20]:

Where WR is the rutile weight fraction in percent, IA and IR are integrated diffraction peak intensity from
anatase (101) and rutile (110), respectively. Io is the total integrated (101) and (110) peak intensity.
The XRD patterns results indicate that the structure of TiO2 was anatase at calcination temperatures at 400
ᵒC, and 600 ᵒC, rutile at 1000 ᵒC and mixed phase at calcination temperature of 800 ᵒC. The anatase phase was
identified at 2θ values of 25.4ᵒ, 38.1ᵒ, 48.2ᵒ, 53.9ᵒ and 55.1 , corresponds to the crystal planes of (101), (004),
(200), and (105) respectively, agreement with the standard XRD pattern (JCPDS files No. 21-1272). Rutile phase
was also identified at 2θ values of 27.5ᵒ, 36.1ᵒ, 41.3ᵒ, 44.2ᵒ and 55.5ᵒ corresponds to the crystal planes of (110),
(101), (200), (111), (210), (211), and (220) respectively, agreement with the standard XRD pattern (JCPDS files
No. 21-1276). At 800 ᵒC, the rutile phase is very prominent with high intensity, which meant high crystallinity.
Additionally, phase components of this catalyst at 800 ᵒC are 13.9% for rutile and 86.1% for anatase. It was
observed that when the crystallite size increases with increasing of calcination temperature due to agglomeration
 Adawiya J. Haider et al. / Energy Procedia 119 (2017) 332–345 335
4 Adawiya J. Haider et al. / Energy Procedia 00 (2017) 000–000

of particles, the diffraction peak becomes narrower as in the case of TiO2 calcined at 1000 ᵒC. Table.1 illustrates
the effect of calcination temperature on the crystalline sizes of TiO2 nanoparticles calculated according to
Scherer’s equation.
Table 1 Effect of calcination temperatures on the crystallite sizes and phase content of TiO2 nanoparticles

CALCINATION  PHASEA 2 (DEG.) (FWHM)  (FWHM) GRAIN  WR

TEMP. (ₒC)  (DEG.)  (RAD.)  SIZEDB (NM)  %
400  A  25.4335 0.7037 0.0123 11.55  0
48.1383 0.7870 0.0137 11.06 
37.9668 0.9371 0.0164 8.97 
600  A  25.3968 0.61070 0.0107 13.35  0
48.1216 0.62480 0.0109 13.94 
37.9092 0.70080 0.0122 11.98 
800  A  25.4201 0.48020 0.0084 16.97  24.
R  48.1525 0.50860 0.0089 17.12  48 

54.1737 0.82330 0.0144 10.85 

1000  R  27.5531 0.50620 0.0088 16.51  100
54.4349 0.50910 0.0089 17.54 
36.1993 0.48250 0.0084 17.32 
a
A stands for anatase and R stands for rutile. b The crystallite size was calculated by using Sherrer’ s equation.

a b

c d

Figure 1 The XRD patterns of TiO2 nanoparticles with different calcination temperatures: (a) 400◦C, (b) 600◦C, (c) 800◦C, and (d) 1000◦C.
Note: (A): anatase phase, ®: rutile phase

3.2 Scanning Electron Microscope (SEM) characteristics

The morphological changes of the prepared TiO2 nanoparticles at different calcination temperatures were
analyzed using Scanning Electron Microscopy (SEM, Tescan VEGA3 SB). SEM can characterize the shape and
336 Adawiya J. Haider et al. / Energy Procedia 119 (2017) 332–345
Adawiya J. Haider et al. / Energy Procedia 00 (2017) 000–000 5

size of TiO2 nanoparticles. The micrographs SEM images of TiO2 nanoparticles were prepared at different
calcination temperatures as shown in Figure 2.
Figure 2a shows TiO2 nanoparticles calcined at 400ᵒC have roughly spherical spongy shape with small
size nanoparticles around the range of less than 20 nm. When the temperature increases up to 600oC, the sizes
become bigger and the agglomeration becomes significant, as shown in Figure 2b. Further increase in temperature
up to 800ᵒC, and 1000ᵒC, TiO2 nanoparticles exhibited non-uniform of particles shape due to the agglomeration
of initial particles with increase in crystalline size. These results are in agreement with XRD results that showed
the particles size of the anatase phase smaller than rutile phase due to aggregation of nanoparticles with increased
calcination temperature.

a b

c d

 
Figure 2 SEM images of TiO2 nanoparticles at: a) 400ᵒC, b) 600ᵒC, c) 800ᵒC, and d) 1000ᵒC, at different magnification 

3.3 Atomic force microscopy (AFM)

The surface morphology was studied by means of AFM (Atomic force microscopy). Figure 3 shows two-
and three-dimensional AFM images of the TiO2 coatings calcined at 400, 600, 800, and 1000 °C, respectively. It
observed that, at different calcination treatment temperature, the surface morphologies and roughness of the TiO2
surface are obviously different. As can be seen from Figure 3a (coating treated at 400 °C), a granular
microstructure and a flat texture, with the lowest surface roughness, and is composed of about 70–80 nm in
diameter of spherical particles. According to previous XRD results, these 70–80 nm particles on the surface of
TiO2 coating are aggregates of many small TiO2 crystallites [21]
 Adawiya J. Haider et al. / Energy Procedia 119 (2017) 332–345 337
6 Adawiya J. Haider et al. / Energy Procedia 00 (2017) 000–000

Figure 3 Two- and three-dimensional AFM image of TiO2 nanoparticles calcined at: (a) 400ᵒC, (b) 600ᵒC, (c) 800ᵒC (d) 1000ᵒC

AFM image analysis also gives the values for the surface roughness, as shows in Table 2. The root mean
square roughness (Rq) of the surface is less than (1 nm) and increases with the increasing calcination temperature,
which indicates the grains of regular shapes develop on the surface. With increase temperature, the surface
morphology and roughness of TiO2 coatings are changed significantly due to phase transformation of anatase to
rutile and growth of TiO2 crystallites [22] [23] [24]. Table 1 shows that the roughness values increase with
increasing calcination temperature.
After calcined up to 1000 °C, a significant increase of the grain size is observed and Rq increases to 1.22
nm. It is because the transformation of anatase into rutile went through the aggregate of smallest particles and
338 Adawiya J. Haider et al. / Energy Procedia 119 (2017) 332–345
Adawiya J. Haider et al. / Energy Procedia 00 (2017) 000–000 7

formation of bigger particles [25], which then increase its grain size. This result is agreement with Jimmy, et al.
[25] and Jiaguo Yu, et al. [26] reports.

Table 2 Shows that the roughness values increase with increasing calcination temperature.

1. Calcination temp. (ₒC) 2. Sq. (Root mean square) (nm)

3. 400 4. 0.206
5. 600  6. 0.422
7. 800  8. 0.732
9. 1000 10. 2.87

3.4 UV-Visible spectroscopy

The optical band gap of TiO2 nanoparticles prepared by sol-gel method was measured by UV-Visible
spectrophotometer in the range from 190 nm to 1100 nm at different calcination temperatures, 400, 600, 800, and
1000 ᵒC. figure 4 illustrate the optical band gap (Eg) which derived assuming a direct transition between the edge
of the valence band and conduction.

a b
b

c d
b

Figure 4 Plots of (αhυ)2 verses photon energy (hυ) of TiO2 nanoparticles calcined at, a) 400˚C, b) 600˚C, c) 800ᵒC, d) 10000ᵒC
 Adawiya J. Haider et al. / Energy Procedia 119 (2017) 332–345 339
8 Adawiya J. Haider et al. / Energy Procedia 00 (2017) 000–000

3.5 Contact angle measurement

Figure 5 illustrates the relationship between contact angle values measured in degrees and the exposure
time. The water contact angles on the coated samples were measured before and after exposure to sunlight.

Figure 5 The relationship between water contact angle and various exposure times to UV light

From the results above, it is shown that the water contact angle of samples calcined at 400ᵒC, 600ᵒC, and
800ᵒC reached zero. This means that the samples' surfaces are completely wetting, since that occurs just when the
contact angle equals (0º), and that these samples reached super- hydrophobicity property [27]. These results
showing that the prepared coatings are efficient to give superhydrophilic property to the glass as a self- cleaning
effect. In the case of samples calcined at 1000ᵒC, WCA decreased to 16.23, respectively. This means that the
coatings also show good hydrophilicity.
These results show that the water contact angle decreased with increasing exposure time to UV light.
Moreover, the contact angle for anatase phase decreased with UV exposure time more than rutile phase due to the
difference in energy band gap for anatase than rutile, so it needs less energy for transition. Also, the wettability of
solid surfaces with water is governed by its geometry. This supports the conclusion of [28] that the particles size
is still a parameter in retaining wetting behavior. In addition, the analysis of the water contact angle on films with
different RMS shows the influence of the film roughness by contact angles. The obtained results from this study
are in agreement with Tamai and Aratani [29], who reported that the increase of average roughness increases the
contact angle. This result also agreed with [25].
In conclusion, the wetting phenomenon of TiO2 films is affect by physical parameters, such as surface
morphology, roughness, and agglomerate size.

3.6 Photocatalysis activity characterization

The photocatalytic activity was evaluated by photocatalytic oxidation of Potassium permanganate

(KMnO4) under direct sunlight irradiation, by measuring the degradation of Potassium permanganate (KMnO4)
under direct sunlight irradiation. UV-Visible Spectrophotometry demonstrated the absorbance value for different
films samples with Potassium permanganate after exposure to UV- irradiation from sunlight. Figure 6 shows that
the color of Potassium permanganate dye gradually reduces, and finally completely disappears which means the
dye is completely degraded. Spectrum shown in Figure 7 demonstrates the relationship between the absorbance
values and exposure time to irradiation in (hr.).
The results illustrate calcination temperature effect on the degradation of the dye [30]. It demonstrates that
TiO2 with pure anatase phase exhibit higher photocatalytic activity compared with TiO2 with pure rutile that need
340 Adawiya J. Haider et al. / Energy Procedia 119 (2017) 332–345
Adawiya J. Haider et al. / Energy Procedia 00 (2017) 000–000 9

more time to degrade the dye. This perhaps is due to the higher adsorptive affinity of anatase surface and lower
recombination rate of electron–hole pairs as compared to rutile [31][32]. At high calcination temperatures 1000ᵒC,
the rutile crystallite size increased due to aggregation under direct sunlight irradiation. The electron generated was
permanently trapped in the larger rutile crystallites aggregates, which results in increasing electron–hole
recombination rate and decreasing the photocatalytic activity. In addition, the growth of TiO2 crystallites at
higher calcination temperature, results in a significant decrease in the surface area. TiO2 calcined at 800ᵒC show
the highest photocatalytic activity. This is because its' composed of both anatase and rutile phases. The photo-
generated electrons transfered from the anatase to the rutile phase may have reduced the rate of electron–hole
combination and thus enhanced the photoactivity.

a b c d

Figure 6 (a) Potassium permanganate (KMnO4) with TiO2 naoparticles befor irradation, immediately after preparing, (b) after 30min
irradation, (c)After 60min irradation, (d)After 120min irradation
Note: samples in (b), (c) and (d) standing from left to right from 400 to 1000 ᵒ

b
a

c d

Figure 7 Illustrates the relationship between absorbance and wavelength for TiO2 nanoparticle calcined at a) 400˚C, b) 600˚C, c) 800ᵒC, d)
1000ᵒC measured before irradiation by sunlight (0 min) and after 30, 60, and 120 min exposure to direct sunlight
 Adawiya J. Haider et al. / Energy Procedia 119 (2017) 332–345 341
10 Adawiya J. Haider et al. / Energy Procedia 00 (2017) 000–000

4. Evaluation of antibacterial activity of TiO2

Table 3 summarizes the relative number of P. aeruginosa and S. aureus survived after the photocatalytic
experiment. The adsorption of bacterial cell wall on TiO2 coating were analyzed using (SEM) as shown in
Figures 9 and 10 with gram negative and positive bacteria.
The results show that there is no cells survived (CFU=0) after the photocatalysis experiment meaning no
bactericidal effect as illustrated in Figure (8a, b), suggesting that severe damage has occurred to the bacterium.
Attack on bacteria is caused by the exposure to reactive intermediates that transferred from the surface of TiO2
coatings to the outside of the bacteria, such as superoxide anions (O-2), hydrogen peroxide (H2O2), and hydroxyl
radicals (•OH), which can damage proteins, nucleic acids, etc.[33]. Initial attack takes place on the cell wall,
where the bactericide makes first contact with an intact bacterium [34]. Damage on cell wall will lead to the
perturbation of different cellular processes, and then the leakage of the cytoplasm, finally bacteria inactivation
and death [35].
These results show that both anatase and rutile have excellent results on bacteria as a photocatalysis after
2h irradiation by sunlight, which indicate that the TiO2 coatings are effective against S.aureus and P. aeruginosa
with a 100% efficiency kill. This result is in agreement with [36]. They illustrated that there were no considerable
differences between photocatalysis oxidation of Gram-positive and Gram-negative bacteria.

Table 3 Bacterial test results for TiO2 coated

TiO2 coated Sample, aCFU for Reduction of aCFU for P. Reduction of P.

calcined at S:aureus/ml S:aureus/% aeruginosa/ml aeruginosa/%

400 ᵒC 1 x 107 100 1 x 107 100

600 ᵒC 1 x 107 100 1 x 107 100
800 ᵒC 1 x 107 100 1 x 107 100
1000 ᵒC 1 x 107 100 1 x 107 100
a
CFU: Colony forming unite

a b

c d

Figure (8a) Photo image of S. aureus cells in contact with TiO2 nanocoating prepared at different calcination temperatures: a) 400ᵒC, b)
600ᵒC, c) 800ᵒC, d) 10000ᵒC
 342 Adawiya J. Haider et al. / Energy Procedia 119 (2017) 332–345
Adawiya J. Haider et al. / Energy Procedia 00 (2017) 000–000 11

a b

c d

Figure (8b) Photo image of P. aeruginosa cells in contact with TiO2 Nano coating prepared at different calcination temperatures: a) 400ᵒC, b)
600ᵒC, c) 800ᵒC, d) 1000ᵒC

a b

d c d

Figure 9 SEM images of S. aureus cells in contact with TiO2 nanocoating prepared at different calcination temperatures: a) 400ᵒC, b) 600ᵒC,
c) 800ᵒC, and d) 1000ᵒC
 Adawiya J. Haider et al. / Energy Procedia 119 (2017) 332–345 343
12 Adawiya J. Haider et al. / Energy Procedia 00 (2017) 000–000

a b

c d

Figure 10 SEM images of P. aeruginosa cells in contact with TiO2 nanocoating prepared at different calcination temperatures: a) 400ᵒC, b)
600ᵒC, c) 800ᵒC, and d) 1000ᵒC

5. Field application on window glasses

Uncoated glass Coated glass with TiO2

Figure 11 Comparison of the antifogging abilities of a glass substrate (left) and a TiO2 coated glass substrate (right)
344 Adawiya J. Haider et al. / Energy Procedia 119 (2017) 332–345
Adawiya J. Haider et al. / Energy Procedia 00 (2017) 000–000 13

To demonstrate that TiO2 transparent coating are effective as a self-cleaning coating, a local window was
coated with TiO2 coating and then exposed to the ambient environment after washing with water and compared
with uncoated one. Figure 11 shows the comparison between uncoated window (left) and window coated with
TiO2 (right).
The uncoated window immediately fogged to scatter light whereas the coated window remained original
transparence after exposure to humid air. The reason for the antifogging behavior is because of the super
hydrophilic surface of TiO2 that allows the complete spreading of the water droplet on the surface to form a
uniform transparent film. This Provides service to residential to prolong windows cleanliness and to reduce cost
of maintenance. When glass or windows for homes and office treated, it will never be dirty and never have to be
washed. No more spots and streaks. Simply use hose to rinse on the glass or windows and walk away to clean
glass and windows.

In summary, results obtained indicates that the TiO2 could be used for the production of coated surfaces
for application as a self-cleaning surface into outdoor building materials, such as windows, also to be placed in
microbiologically sensitive environments, such as hospitals.

Conclusions

The structural and optical properties of the TiO2 nanoparticles were found to be dependent on the calcination
temperature. As the calcination temperature increases, the crystallinity is improved and the crystallite size
becomes larger .
The optical band gap is dependent on the calcination temperature, for the lower calcination temperature, the
optical energy band gap is higher. The root mean square roughness (Rq) of the surface increases with the
increasing calcination temperature, due to phase transition from anatase to rutile and growth of TiO2 crystallites.
TiO2 coatings (1 mg cm-2) are effective against (Staphylococcus aurous) and (Pseudomonas aeruginosa) with
a 100% efficiency kill under sunlight irradiation.
TiO2 coated films presented higher transmittance, lower water contact angle, good photocatalyst activity, and
excellent antibacterial properties. These properties are fundamental for application as a self-cleaning surface.
 
Acknowledgments
The authors would like to thank the University of Technology, Department of Building and Construction
Engineering, Sanitary and Environmental Engineering Branch, Furthermore thanks and gratitude goes to the
Nanotechnology and Advanced Materials Research Center (Iraq) for help in conducting this work.

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