J Nanopart Res (2018) 20:23

https://doi.org/10.1007/s11051-018-4140-7

RESEARCH PAPER

Microwave-assisted synthesis of TiO2 nanoparticles:

photocatalytic activity of powders and thin films
G. S. Falk & M. Borlaf & M. J. López-Muñoz &
J. C. Fariñas & J. B. Rodrigues Neto & R. Moreno

Received: 1 June 2017 / Accepted: 19 January 2018

# Springer Science+Business Media B.V., part of Springer Nature 2018

Abstract A simple, rapid, and effective synthesis meth- that of a thin film of commercial TiO2 powder prepared
odology for the preparation of high-performance TiO2 under similar conditions.
nanoparticles and thin films by combining colloidal sol-
gel and microwave-assisted hydrothermal synthesis was Keywords TiO2 . Nanoparticles . Microwave synthesis .
developed. The obtained results indicate that the heating Thin films . Photocatalysis
with microwaves at 180 °C for 20 min was enough to
synthesize crystalline TiO2 nanoparticles, presenting an-
atase as a major phase with a crystal size of ~ 7 nm and a
Introduction
specific surface area of 220 m2 g−1. A secondary thermal
treatment improved the crystallinity and induced the
Titanium dioxide (TiO2) is a material of great interest
anatase-to-rutile transformation. The highest photocata-
due to its excellent set of chemical, physical, optical, and
lytic activity was found for the as-synthesized powder
electronic properties that make this material to be a
without any additional thermal treatment. Thin films
reference in several technological applications. A huge
were also prepared by dip-coating and its high photo-
number of applications such as air and water treatment
catalytic activity showed a kinetic curve comparable to
(Belver et al. 2015; Weon et al. 2017), self-cleaning
surfaces (Pinho et al. 2015), electronic devices (Kim
G. S. Falk (*) : M. Borlaf : J. B. Rodrigues Neto et al. 2016), and dye-sensitized solar cells (Liang et al.
Department of Mechanical Engineering, Federal University of
Santa Catarina, Florianópolis, SC 88040-900, Brazil
2016; Hou et al. 2016; Shen et al. 2016; Cui et al. 2017),
e-mail: gilbertofalk@outlook.com to name a few, have been reported in the literature.
In particular, TiO2 has been extensively studied in
M. J. López-Muñoz different photocatalytic systems, including the
Department of Chemical and Energy Technology, Chemical and
Environmental Technology, Mechanical Technology and
photodegradation of volatile organic compounds, hy-
Analytical Chemistry, Rey Juan Carlos University, C/Tulipán s/n, drogen production, and other environmental applica-
28933 Móstoles, Madrid, Spain tions due to its n-type semiconductor properties with a
band gap of 3.0 to 3.2 eV (dependent on crystallograph-
J. C. Fariñas : R. Moreno
Instituto de Cerámica y Vidrio, CSIC, Kelsen 5, 28049 Madrid,
ic variants), low toxicity potential, good chemical and
Spain thermal stabilities, surface acidity, and high selectivity,
as well as cheapness and availability (Fan et al. 2016; Li
et al. 2016; Cortéz-Lorenzo et al. 2017; Sun et al. 2017).
Present Address:
M. Borlaf
Different methods have been reported for the synthe-
Laboratory for High Performance Ceramics, Empa, sis of titanium dioxide, including hydrothermal methods
Überlandstrasse 129, 8600 Dübendorf, Switzerland and sol-gel processes using a variety of precursors such
23 Page 2 of 10
as titanium alcoxides, titanium tetrachloride (Kobayashi
et al. 2007; Adjimi et al. 2014; Elsellami et al. 2017). In
most cases, however, long periods of times are usually
required to achieve the crystallization of titania in a
specific phase (mainly anatase or rutile). In this context,
the microwave-assisted hydrothermal method is a rapid,
energy-saving, and efficient synthesis methodology for
the preparation of functional nanomaterials (Meng et al.
2016). It has received great attention in the technological
field because of its suitability for reducing the reaction
time from days to hours or minutes, demonstrating
advantages that include tailored microstructure, unique
properties, and an improved product yield, leading to a
reduction in manufacturing costs and enhanced versatil-
ity for the synthesis of new materials as compared to
conventional methods (Jiang et al. 2015; Esquivel-
Escalante et al. 2016; Mirzaei and Neri 2016). In addi-
tion, colloidal sol-gel is performed in water so that the
synthesis method is more economic and efficient than
other synthesis methods used elsewhere.
The reaction process for microwave-assisted hy-
drothermal synthesis is dependent on the interac-
tions of the microwaves with the materials and the
reaction medium, that is, under the action of the
electromagnetic field, the particles can produce dif-
ferent types of polarization (electron, atom, orienta-
tion, and space charge), being the microwave energy
transmitted directly to the material in terms of mo-
lecular interactions with the electromagnetic field,
leading to a fast and homogenous heating process
in short periods of time and generating a homoge-
neous nucleation and a uniform growth of the nano-
particles (Zhu and Hang 2013; Bhattacharya and
Basak 2016; Mirzaei and Neri 2016).
Although different routes of TiO2 syntheses have
been extensively described in the literature, documenta-
tion of microwave-assisted synthesis in short periods of
time and in water is still scarcely reported. In this con-
text, this research had the objective of both developing a
rapid, energy-saving, and promising clean method for
the synthesis of TiO2 nanoparticles by using a colloidal
sol-gel approach accelerated by microwave-assisted hy-
drothermal route, and evaluating the structural, morpho-
logical, and photocatalytic properties of the resulting
nanopowders as well as thin films obtained by dip-
coating from those nanopowders. With the purpose of
photocatalytic applications, the use of titania films
immobilized on supports transparent to UV radiation
can be of great interest, as it offers as main advantage,
J Nanopart Res (2018) 20:23
the easier recovery of the catalyst after the reaction in
comparison to slurry systems.
Experimental
Synthesis and characterization of the TiO2 nanoparticles
TiO2 nanoparticles were synthesized combining con-
ventional colloidal sol-gel with microwave-assisted hy-
drothermal method. The preparation started as in any
colloidal sol-gel process with the quick hydrolysis, un-
der continuous stirring, of titanium (IV) isopropoxide
(TIPO, 97%, Sigma-Aldrich, Steinheim, Germany) in a
mixture of deionized water (18.2 MΩ cm−1, ultra-pure
Milli-Q, France) and nitric acid (65%, Panreac, Barce-
lona, Spain) in H2O:Ti4+ = 100:1 and H+:Ti4+ = 0.2 mo-
lar ratios. Nitric acid was used as a dispersing agent/
catalyst.
The solution was stirred continuously at 700 rpm for
30 min, and then transferred to a 100-mL sealed vessel
made of high-purity TFM (modified teflon) placed in a
commercial microwave digestion system (Milestone
ETHOS One, Sorisole, Italy) where hydrothermal reac-
tions occurred at a microwave frequency of 2.45 GHz.
The container was surrounded by a safety shield. Tem-
perature and pressure during the synthesis were moni-
tored and controlled with a shielded thermocouple di-
rectly inserted into the vessel and with a pressure trans-
ducer sensor connected to the vessel, respectively. Built-
in magnetic stirring (Teflon-coated stirring bar) was
used. For each synthesis, the heating ramp was set in
10 min with holding times of 20 min at maximum
temperatures of 180 and 200 °C. After cooling at room
temperature, the obtained powders were carefully
washed for at least three times with deionized water
and centrifuged every time at a rotation speed of
2400 rpm using a multi-purpose bench top centrifuge
(Núve NF800, Ankara, Turkey).
Particle size distributions (PSD) before and after the
microwave process were measured by laser diffraction
(LD, Mastersizer, Malvern, UK) and dynamic light scat-
tering (DLS) in a Nanozetasizer ZEN 3600 equipment
(Malvern, UK).
The nanoparticles were obtained by freeze-drying
process as it has been shown that, in contrast to conven-
tional drying treatments, this procedure allows to obtain
quite homogeneous particle size distributions
(Eggenhuisen et al. 2013). This technique consists of
J Nanopart Res (2018) 20:23
two steps: freezing and drying. In the first one, the
solutions were frozen by cooling at − 50 °C, and in the
second, the sublimation of the solvent and other volatile
compounds was carried out with a vacuum pump at −
50 °C (CRYODOS-50, Telstar, Spain). Subsequently,
the obtained nanoparticles were submitted to thermal
treatments in air atmosphere using heating and cooling
rates of 10 °C min−1 and a dwell time of 1 h.
The specific surface area (SSA) was measured with a
one-point BET method (Monosorb Surface Area
Analyser, MS-13, Quantachrome Corporation, USA)
after degassing at 150 °C for 2 h.
X-ray diffraction (XRD) analyses were conducted
with a PW-1830 diffractometer (Philips model X’Pert -
NL, Eindhoven, the Netherlands) with CuKα radiation
(k = 1.5406 Å) as X-ray source over 2-h range (10–80).
Raman spectroscopy analyses were performed with a
spectrometer (inVia, UK) coupled to an Olympus mi-
croscope (BX41 TM). All spectra were obtained using
an argon laser (λ = 514.5 nm).
Transmission electron microscopy (TEM) analyses
were performed on a Philips Technai 20 T electron
microscope operating at 200 kV and with a 2.7-Å reso-
lution. The samples were dispersed in acetone applying
1 min of sonication and then a droplet of the suspension
was deposited onto a carbon-coated copper grid.
The UV-Vis diffuse reflectance spectra were collect-
ed using a spectrophotometer PerkinElmer Lambda 950
precisely (USA). From the spectra, the optical band gap
was determined using the Tauc plot (Tauc 1970) for an
indirect semiconductor:
ðαhν Þ0:5 vs:hν ð1Þ
where α is the absorption coefficient and hν is the
photon energy in electronvolt.
The photocatalytic activity of the synthesized sam-
ples was evaluated through the degradation of methy-
lene blue (MB) using a batch reactor with an effective
solution volume of 1 L. The light source was a medium
pressure Hg lamp (150 W, TQ-150, Heraeus Instru-
ments, Germany; maximum intensity at λ = 365 nm)
axially immersed inside the reactor and provided with
a cooling tube. An aqueous copper sulphate solution
(0.01 M) kept at 25 °C was circulated through the
cooling tube both to prevent the overheating of the lamp
and the solution and to avoid photolytic processes. To
achieve a stabilized radiation emission, the lamp was
switched on 20 min before being fitted into the reactor.
Page 3 of 10 23
In the meantime, prior to irradiation, the 20 mg L−1 MB
aqueous solution containing 0.25 g L−1 of photocatalyst
was magnetically stirred for 30 min in the dark to reach
an equilibrated MB adsorption. The amount of dye
adsorbed onto the catalyst was calculated by the differ-
ence between the initial MB concentration and that
remaining in the solution after the equilibration interval.
Photocatalytic reactions were carried out at pH = 5.
Samples were periodically taken from the reactor for
analysis. The MB degradation was quantified by mea-
suring the absorbance at 665 nm (the maximum of the
absorption band of MB) in an UV-Vis spectrophotome-
ter (JASCO V-630, JASCO Inc., Japan). The commer-
cial TiO2 (anatase TiO2 nanopowder < 25 nm, 99.7%,
SSA = 45–55 m2 g−1, Sigma-Aldrich, Germany) and
TiO2 P25 (SSA ~ 50 m2 g−1, Evonik, Essen, Germany),
which are customarily used as references due to their
excellent photocatalytic properties, have also been eval-
uated for comparative purposes.
Thin film preparation and characterization
TiO2 thin films supported on glass slides were obtained
by dipping technique using a withdrawal rate of 1 mm s−1
at room temperature. Glass substrates were used after
washing with deionized water, acetone, and finally eth-
anol. A suspension was prepared by dispersing 1 g of
TiO2 nanoparticles (obtained by microwave-assisted
hydrolysis after centrifugation and subsequent freeze-
drying) in a mixture of 1 mL deionized water
(18.2 MΩ cm−1, ultra-pure Milli-Q, France) and 9 mL
of ethanol absolute (EtOH, ≥ 99.8%, Sigma-Aldrich,
Germany). The pH = 3 was adjusted with nitric acid
and ultrasonication (UP 400s, Hielscher Ultrasonics
GmbH, Teltow, Germany; power = 400 W) was applied
for 1 min in order to improve the dispersing conditions.
The thin films were dried at room temperature for
30 min and subsequently stabilized in a muffle at
200 °C for 1 h to remove the solvent and to induce the
condensation process. Stabilized films were then ther-
mally treated at 500 °C for 1 h in air. The same proce-
dure was followed to obtain coatings by dipping of a
commercial nanosized TiO2 powder (P25, Evonik, Es-
sen, Germany) which is customarily used as a reference
due to its excellent photocatalytic properties.
The thickness and the refractive index (RI) of the thin
films were determined by ellipsometry (GES5E Spec-
troscopic Ellipsometer from SOPRALAB, Courbevoie,
France). The measurements were done from 1.22 to
23 Page 4 of 10 J Nanopart Res (2018) 20:23
35
3.00 eV at an incidence angle of 75°. The obtained After microwave process
curves were analyzed with the help of the WINSE 30
180 °C
software.
25
Atomic force microscopy (AFM; 200 °C Before microwave process

Volume (%)
NanotecElectronica, Madrid, Spain) was used to ob- 20
serve the surface topography of selected thin films.
15
The films were also characterized by Raman spectros-
copy using the same procedure previously cited for the 10
analysis of the synthesized nanosized powder.
5
The photocatalytic activity of the nanocrystalline
titania coatings was evaluated in a batch reactor
consisting of a Pyrex cylinder of similar size to that 0 20 40 60 2000 4000 6000 8000
Particle size (nm)
described above for the reactions carried out with the
powdered samples, provided with the same lamp as Fig. 1 Particle size distribution before and after the microwave
process
source of irradiation. The initial concentration of MB
was set at 10 mg L−1. Six glass slides, each one covered
formation of uniform nanoparticles in just few minutes
with an area of 3 × 7 cm2 of titania, were placed around
whereas the conventional methods require longer pe-
the lamp in a symmetrical arrangement to ensure they
riods of time to obtain the nanoparticles (Delekar et al.
got the maximum UV radiation. The total amount of
2012; Borlaf et al. 2014; Zhang et al. 2016).
catalyst was calculated to be approximately 0.05 g L−1.
The colloidal stability of the TiO2 nanoparticles ob-
To keep the slides at upright position along the reaction
tained after the microwave process was evaluated by
time throughout the continuous magnetic stirring of the
measuring the zeta potential as a function of pH (Fig. 2).
solution, the slides were hold by a polymer rack.
It can be observed that at either acid pH values ≤ 5 or
basic pH ≥ 9, the zeta potential absolute values vary
between 30 and 40 mV, which are considered sufficient
Results and discussion
to maintain the stability of the nanoparticles (Moreno
2012). For pH values between 6 and 8, the zeta potential
Synthesis and characterization of the TiO2 nanoparticles
values are lower than 20 mV, not considered enough for
keeping the nanoparticles stable in the system. The
Measurements of PSD, displayed in Fig. 1, were per-
isoelectric point is observed at pH ~7.5, within the range
formed in order to evaluate the effectiveness of the
reported in the literature for TiO2 anatase (Kosmulskil
microwave-assisted hydrothermal method in the prepa-
1992; Song et al. 2008; Borlaf et al. 2014).
ration of TiO2 nanoparticles. As it can be observed, the
Figure 3 shows the XRD patterns of the as-prepared
fast hydrolysis of TIPO initially generates large agglom-
samples obtained after the microwave-assisted synthesis
erates ranging from 2 to 7 μm. Subsequently, after the
microwave process, nanoparticles with a size ranging
50
from 7 to 28 and 13 to 52 nm were obtained for the
40
samples synthesized at 180 and 200 °C/20 min, respec-
30
tively. This increase in particle size with temperature
20
Zeta Potential (mV)

could be associated to an excess of energy, which pro-

10
vokes the re-agglomeration of the nanoparticles (Falk
et al. 2016; Ashok and Rao 2017). In addition, the lower 0
pH
2 4 6 8 10
temperature led to a narrower monomodal distribution, -10

so that keeping in mind the goal to get homogeneous -20

titania particles with high specific surface area, 180 °C -30

was chosen as temperature for microwave processing. -40

In general, this demonstrates that this method -50
coupled with the rapid and homogeneous heating ob- Fig. 2 Variation of zeta potential of the synthesized nanoparticles
tained by microwave radiation is capable of inducing the as a function of pH
J Nanopart Res (2018) 20:23 Page 5 of 10 23

R
R 143 600 °C
600 °C
A R

R A R
R R
AR A R
R R A
Intensity (a.u.)

A
446 640
514 608
500 °C
A 195 398
A AA A
A A A
B
A

Intensity (a.u.)
as-prepared 500 °C
A A 144
A A
B A A

20 30 40 50 60 70 80
2 (degrees)
398 517 640
Fig. 3 XRD patterns of the as-prepared and calcined powders at 195
500 and 600 °C/1 h. (A—anatase, B—brookite, and R—rutile)

and after subsequent calcination at different tempera- 150 as-prepared

tures. It is possible to observe that the microwave-
assisted hydrothermal method without further heat treat-
ments was sufficient for the successful crystallization of
titania, with well-defined peaks typical of the anatase
TiO2 phase (JCPDS No. 01-071-1166), although a mi-
nor contribution of brookite (JCPDS No. 01-076-1936)
is also present as evidenced by the small peak centered
at ca. 31°. Up to 500 °C/1 h, the crystallinity of the
anatase phase increased, according to the narrowing of
diffraction peaks, and at 600 °C/1 h, the anatase-to-rutile
(JCPDS No. 01-087-0710) transformation is observed
while brookite phase completely disappears. Even
though at 600 °C/1 h the rutile fraction is higher than
anatase one, the full conversion of the anatase-to-rutile
phase requires higher temperatures.
The Raman spectra of the samples obtained by the
microwave processing as well as after thermal treat-
ments at different temperatures are shown in Fig. 4. It
can be seen that the as-prepared sample shows Raman
bands centered at 150, 195, 398, 517, and 640 cm−1
which are assigned to Eg(1), Eg(2), B1g, B1g, and Eg(3)
modes in anatase phase, respectively (Tompsett et al.
1995; Huang et al. 1997; Chen and Mao 2007). The
spectrum of the sample calcined at 500 °C/1 h exhibits
similar features. The main difference is related to the
shift of the band Eg(1) to 144 cm−1, which, together with
the decrease of the width of the band, is associated to the
larger particle size reached after the thermal treatment
(Borlaf et al. 2015). At 600 °C/1 h, the bands associated
to the rutile phase are observed at 446 and 608 cm−1,
attributed to the Eg and A1g modes (Tompsett et al.
1995; Chen and Mao 2007). These results are therefore
398 517 640
200 400 600 800
-1
Raman Shift (cm )
Fig. 4 Raman spectra of the as-prepared and calcined TiO2
nanoparticles
in good agreement with the XRD analysis. Neverthe-
less, it should be noticed that according to the XRD
patterns, brookite is present in much lower proportion in
comparison to anatase. Considering that the most in-
tense Raman band of brookite is centered at ca.
153 cm−1 (Tompsett et al. 1995) but also that all the
bands are less intense than the anatase or rutile ones, if
present, it must be overlapped by the band at 150 cm−1
ascribed to Eg(1) mode of anatase and the rest of the
bands would be very difficult to detect.
High-resolution TEM micrographs of the samples are
shown in Fig. 5. A disordered three-dimensional num-
ber of nanoparticles with different morphologies and
unit dimensions lower than 7 nm are clearly observed
in the sample obtained by the microwave-assisted hy-
drothermal method (Fig. 5a). After calcining at 500 °C/
1 h (Fig. 5b), the crystals are larger, as it is expected after
a thermal treatment, with sizes larger than 10 nm. No
significant difference is observed in the selected area
electron diffraction (SAED) analysis between the two
samples. In both cases, it shows the typical diffuse
23 Page 6 of 10 J Nanopart Res (2018) 20:23

a)
5


 h 
2

1 as-prepared
500 °C
600 °C
0
2 3 4
h (eV)
b) Fig. 6 Tauc representation of the UV-Vis spectra obtained from
the as-prepared and calcined samples at 500 and 600 °C/1 h. The
arrows indicate the band gap value calculated by extrapolation

The photocatalytic efficiency of the synthesized ma-

Fig. 5 TEM images of the as-prepared TiO2 nanoparticles (a) and
the calcined ones at 500 °C/1 h (b)
polycrystalline pattern for a TiO2 anatase phase, with the
main planes identified in (101), (004), (200), and (105),
being the first one of greater intensity and the rest with
similar intensity.
Figure 6 shows the Tauc plot of the samples obtained
by microwave process and as a function of the calcina-
tion temperature. The average band gap was estimated
from the intercept of the linear portion of the (νhν)0.5 vs.
terials under UV radiation was evaluated by the oxida-
tion of MB. The evolution of normalized MB concen-
tration as a function of the irradiation time is displayed
in Fig. 7. Adsorption experiments carried out in the dark
prior to irradiations evidenced a scarce adsorption of the
dye (less than 0.8% of initial MB concentration) on all
materials. The extent of direct photolysis of the dye was
evaluated by irradiation of the MB solutions without any
catalyst. As can be seen in Fig. 7, in these conditions,
only 10% of initial MB was degraded after 150 min of
reaction, thus giving a reference for the catalyst effect in
all other experiments.
As it can be seen, for equal catalyst loading, the
sample obtained by microwave-assisted hydrother-
mal method without subsequent heat treatments
1,0
0,8

hν plots on energy axis at (νhν)0.5 equal to 0. The band

0,6
gap calculated for the as-prepared samples was ~ 3.1 eV
C/C0

and decreased at higher calcination temperatures up to ~ 0,4

3.0 eV. This fact can be explained by the transformation
of the anatase phase into rutile (600 °C/1 h), as rutile is 0,2 Photolysis
as-prepared
characterized by a lower theoretical band gap value in 500 °C
600 °C
comparison to anatase (3.2 and 3.0 eV for anatase and 0,0 TiO2 Aldrich
TiO2 P25
rutile, respectively) (Henderson 2011). Nevertheless,
0 20 40 60 80 100 120 140 160
not only the crystalline composition but other factors Irradiation Time (min)
can affect to the observed decrease of the band gap value
Fig. 7 Kinetic curves of the methylene blue photodegradation
as, for example, different defects such as oxygen vacan- using the as-prepared and calcined TiO2 samples as a function of
cies, which are typical in TiO2 (Diebold 2003). the exposure time under UV radiation
J Nanopart Res (2018) 20:23
shows the highest photocatalytic activity, followed
by the sample calcined at 500 °C/1 h (anatase) and
600 °C/1 h (anatase + rutile). In the first two cases,
the photoactivity was higher compared to commer-
cial anatase TiO2 nanoparticles (from Sigma-Aldrich)
used as a reference. The SSA of the samples was
measured, obtaining 220, 65, and 43 m2 g−1 for the
samples prepared by freeze-drying process without
further thermal treatment and calcined at 500 and
600 °C/1 h, respectively. It is well-known that the
SSA influences the photocatalytic activity, that is, the
larger the specific surface area, the larger number of
active sites, and consequently, an enhanced photocat-
alytic activity of the material should be expected. In
this case, we can observe this direct relation for the
materials synthesized in the present work. Moreover,
it has been reported that the phase structure and
composition, and crystallite size have great influence
on the photocatalytic activity and
photoelectrochemical properties of semiconductors
(Aguado et al. 2006). The kinetic profiles shown in
Fig. 7 point out that crystallization to anatase also
plays a crucial role, as the sample calcined at 500 °C/
1 h consisting only in anatase phase shows a signif-
icantly higher activity than that calcined at 600 °C/
1 h despite their SSA is not so different. In this case,
the presence of rutile in the sample calcined at
600 °C/1 h is presented in Fig. 3. It is worthy to note,
however, that commercial TiO2 P25 also consists on
anatase and rutile phases and has a SSA close to that
of the sample calcined at 600 °C/1 h. However, its
photocatalytic activity is significantly higher, what
some authors have explained as due to a synergy
effect between both anatase and rutile phases leading
to an effective suppression of charge carrier recom-
bination (Ohno et al. 2001; Hurum et al. 2003). It is
therefore plausible to propose that, by contrast to
TiO 2 P25, in the case of the sample calcined at
600 °C/1 h, defects generated in the phase transition
can act as recombination centers of charge carrier
pairs, and therefore this might be responsible for its
lower photocatalytic performance.
Despite the greater photocatalytic activity of the ma-
terials when used in the form of powder, the main
drawbacks of this system are the difficult recovery of
the photocatalyst. In this context, a plausible alternative
investigated in this work is the use of films, where the
nanoparticles were impregnated in the form of a thin
film on a glass substrate.
Page 7 of 10 23
Thin film preparation and characterization
Once confirmed the photocatalytic activity of titania
nanopowders obtained by the microwave-assisted
hydrothermal synthesis, the next goal was to prepare
titania films on glass supports. In comparison to
powdered samples, the main interest of using
immobilized titania is the possibility of reusing the
photocatalyst.
The suspension was prepared under acidic conditions
at pH = 3 due to the higher stability of the particles
according to zeta potential results (Fig. 2). In these
conditions, the nanoparticles have sizes ranging from
10 to 35 nm (measured by DLS, not shown), demon-
strating that there is almost no agglomeration of the
particles as compared with the distribution shown in
Fig. 1, despite the use in that case of a mixture of water
and ethanol as dispersion medium for the nanoparticles.
In order to optimize the dip-coating experiments, a
preliminary study of the withdrawal rate was performed
ranging from 0.5 to 3 mm s−1. Although the experimen-
tal values are not shown for the sake of simplicity, it was
appreciated that the homogeneity of the film was better
at low withdrawal rates, between 0.8 and 1.1 mm s−1.
Accordingly, the thin films were prepared at a withdraw-
al speed of 1 mm s−1. After the drying process (200 °C/
1 h), they were calcined at 500 °C/1 h in order to get a
dense film with good adhesion to the glass substrate.
The obtained films were characterized in terms of sur-
face texture through AFM observations, as displayed in
Fig. 8. An overview of the thin film topography was
recorded, showing a roughness ranging from 10 to
35 nm. The topography confirms a coating of high
homogeneity with nanoparticle features with granular
morphology.
To verify the presence of the anatase phase, Raman
measurements were performed (Fig. 9). It can be seen
that the normalized Raman spectrum of the thin film is
in accordance with that of the powders calcined at
500 °C/1 h, presenting four major bands centered at
145, 195, 398, 517, and 640 cm−1 associated to the
anatase phase.
The photocatalytic activity behavior of TiO2 thin
films was evaluated by the MB degradation under UV
light irradiation (Fig. 10). For comparison purposes, a
thin film of commercial TiO2 P25 was prepared and
tested under the same conditions. It can be seen that
the percentages of MB degradation achieved with irra-
diation time along the reaction were significantly higher
 23 Page 8 of 10 J Nanopart Res (2018) 20:23

Fig. 8 AFM images (topography channel) of the TiO2 thin film calcined at 500 °C/1 h

than the results of direct photolysis, thus demonstrating
the photocatalytic efficiency of the thin titania films. In
comparison with the reactions carried out with pow-
dered photocatalysts, it is observed that the rate for
MB degradation with the films is slower, which is an
expected result since the active interface with the liquid
phase is higher in a slurry configuration in comparison
195
145
to an immobilized catalyst system. Despite this draw-
back, as indicated above, the use of supported titania
films avoids the filtration of the catalyst.
As can be observed in Fig. 10, both titania samples
were found to have fairly similar kinetics and, after
120 min, almost half of MB was degraded. Taking into
account not only the high photocatalytic activity of the
TiO2 P25 sample, which is customarily taken as a

398

517

640

1.0

0.9
Intensity (a.u.)

TiO2 powders
0.8
C/C0

0.7

0.6
Photolysis
Thin Film TiO2
0.5 TiO2 P25

200 400 600 800 0 20 40 60 80 100 120

-1
Raman Shift (cm ) Irradiation Time (min)
Fig. 9 Raman spectra of the TiO2 thin film and TiO2 powders Fig. 10 Kinetic curves of the methylene blue degradation using
both calcined at 500 °C/1 h the TiO2 and thin films of prepared commercial TiO2 P25
J Nanopart Res (2018) 20:23
reference in many photocatalytic experiments, but also
the differences between both materials in terms of SSA,
particle size and structure, we can conclude that the TiO2
thin film prepared in this work using the TiO2 synthe-
sized by a colloidal sol-gel enhanced by a microwave
thermal process, has an excellent photocatalytic activity,
comparable to that of titania P25. This evidences the
great capabilities of the TiO2 nanoparticles obtained by
microwave-assisted green synthesis for applications in
the field of photocatalysis, both in the form of nanopar-
ticles and as thin films.
Conclusions
TiO2 nanoparticles with an average crystal size of ~
7 nm and a well-defined anatase crystalline phase
without additional heat treatments were successfully
obtained by microwave-assisted hydrothermal syn-
thesis in a simple, soft, fast, and energy-efficient
manner in a process of 20 min at a temperature of
only 180 °C.
Heat treatments at higher temperatures lead to an
increase of the average crystal size up to ~ 10 nm
as observed in the TEM analysis and also to a
higher crystallinity of the nanoparticles in the ana-
tase phase (500 °C/1 h). At higher temperatures
(600 °C/1 h), the transformation of the anatase-
rutile phase occurs.
The as-synthesized anatase TiO 2 nanoparticles
showed the highest photocatalytic activity which is
comparable to the TiO2 P25. In this context, the pre-
pared TiO2 thin films (using the as-synthesized and the
TiO2 P25) calcined at 500 °C/1 h also presented a
similar kinetic curve for the MB degradation.
Acknowledgments The authors thank the resources provided
by CAPES under the International Cooperation Program Science
without Borders for Special Guest Researcher, PVE (MEC/MCTI/
CAPES/CNPQ/FAP/71/2013), Project No. A011/2013.
Funding This work was supported by Ministerio de Economía,
Industria y Competitividad (Government of Spain) and FEDER
Funds under the Grant No. MAT2015-67586-C3-2-R and
CTM2015-69246-R.
Compliance with ethical standards
Conflict of interest The authors declare that they have no con-
flict of interest.
Page 9 of 10 23
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