Materials Science in Semiconductor Processing ∎ (∎∎∎∎) ∎∎∎–∎∎∎

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Materials Science in Semiconductor Processing

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Preparation of TiO2/WO3 composite photocatalysts by the adjustment of the

semiconductors' surface charge
Lucian Baia a,b,1, Eszter Orbán c,1, Szilvia Fodor c,1, Boglárka Hampel c,1, Endre Zsolt Kedves c,d,1,
Kata Saszet c,1, István Székely c,d,1, Éva Karácsonyi e, Balázs Réti f, Péter Berki f, Adriana Vulpoi a,b,
Klára Magyari a,b, Alexandra Csavdári d, Csaba Bolla c, Veronica Coșoveanu d, Klára Hernádi f,
Monica Baia a,b, András Dombi e, Virginia Danciu d, Gábor Kovács b,c,d,n, Zsolt Pap b,c,d,e,nn
a
Institute for Interdisciplinary Research on Bio-Nano-Sciences, Treboniu Laurian 42, RO-400271 Cluj-Napoca, Romania
b
Faculty of Physics, Babeş-Bolyai University, M. Kogălniceanu 1, RO-400084 Cluj-Napoca, Romania
c
Faculty of Chemistry and Chemical Engineering, Hungarian Chemical and Chemical Engineering Department, Babes-Bolyai University, Arany János 11, RO-400028 Cluj-Napoca,
Romania
d
Faculty of Chemistry and Chemical Engineering, Chemical Engineering Department, Babes-Bolyai University, Arany János 11, RO-400028 Cluj-Napoca, Romania
e
Research Group of Environmental Chemistry, Institute of Chemistry, University of Szeged, Tisza Lajos krt. 103, H-6720 Szeged, Hungary
f
Department of Applied and Environmental Chemistry, University of Szeged, Rerrich Béla tér 1, HU-6720 Szeged, Hungary

art ic l e i nf o a b s t r a c t

Article history: The present research focused on the preparation of TiO2/WO3 (76/24 wt. %) composite photocatalysts for
Received 31 May 2015 the photodegradation of methyl orange under UV light. The composites were prepared by the adjustment
Received in revised form of the surface charge of the individual semiconductors, achieving a homogeneous distribution of the
18 August 2015
components within the composite. This resulted in a homogeneous distribution of the components
Accepted 27 August 2015
within the composite. The individual WO3 and TiO2 nanocrystals were obtained either by sol–gel or by
hydrothermal synthesis. The produced nanomaterials were characterized by using TEM, SEM, XRD and
Keywords: DRS. Major differences in their photocatalytic performance depended on the nature of the precursors and
Semiconductor composites the synthesis pathway.
Surface charge
& 2015 Elsevier Ltd. All rights reserved.
Photocatalytic activity
Titania
Tungsten oxide

1. Introduction properties: physical and chemical stability, non-toxicity, safety,

low cost, and resistance to photocorrosion [3,4]. Although, as ev-
Semiconductor photocatalysis is an efficient alternative in wa- erything in the balanced nature, using TiO2 can show some
ter and air purification [1,2], while TiO2 is the most frequently drawbacks. One of the most representative problems are the re-
used semiconductor photocatalyst, because of its several beneficial combination process and the UV excitability [5].
Hence, the efficiency of photocatalysts can be defined by the
lifetime of the photogenerated charges (electron/hole pairs),
n
Corresponding author at: Faculty of Physics, Babeş-Bolyai University, M. Ko- which are involved in oxidation/reduction reactions. In order to
gălniceanu 1, RO-400084 Cluj-Napoca, Romania. Fax: þ 40 264 590 818. maximize the lifetime of these charges, various approaches can be
nn
Corresponding author at: Faculty of Physics, Babeş-Bolyai University, M. Ko-
gălniceanu 1, RO-400084 Cluj-Napoca, Romania. Fax: þ 40 264 590 818.
considered: (i) depositing of noble-metals [6,7], (ii) creating
E-mail addresses: lucian.baia@phys.ubbcluj.ro (L. Baia), composites with other semiconductors [8,9], (iii) and the use of
eszterorban94@outlook.com (E. Orbán), fod_szilvia@yahoo.com (Sz. Fodor), carbon nanomaterials [10,11]. To obtain these composites several
hampelboglar@yahoo.com (B. Hampel), zsolty91@yahoo.com (E. Zs. Kedves), methods are available, like impregnation, physical mixing, in-situ
saszetkata@yahoo.com (K. Saszet), szistike@yahoo.com (I. Székely),
synthesis, but none of the methods listed above is an efficient
karacsonyi.eva@iems.u-szeged.hu (É. Karácsonyi),
retib@chem.u-szeged.hu (B. Réti), berkipeter@chem.u-szeged.hu (P. Berki), alternative for achieving high number of interparticle contacts
adriana.vulpoi@phys.ubbcluj.ro (A. Vulpoi), klara.magyari@ubbcluj.ro (K. Magyari), between the components.
acsavdari@chem.ubbcluj.ro (A. Csavdári), csbolla@chem.ubbcluj.ro (Cs. Bolla), The most efficient way is to contact these materials by elec-
vcosoveanu@chem.ubbcluj.ro (V. Coșoveanu), trostatic attraction. Generally, the surface of titania at acidic pH is
hernadi@chem.u-szeged.hu (K. Hernádi), monica.baia@phys.ubbcluj.ro (M. Baia),
dombia@chem.u-szeged.hu (A. Dombi), vdanciuik@chem.ubbcluj.ro (V. Danciu),
positively charged, which, after passing through the isoelectric
gkovacs@chem.ubbcluj.ro (G. Kovács), pap.zsolt@phys.ubbcluj.ro (Zs. Pap). (IEP) pH (E5.8) of the system is charged negatively [12]. This can
1
These authors contributed equally to this work. be exploited if another photocatalyst, at a given pH value is

http://dx.doi.org/10.1016/j.mssp.2015.08.042
1369-8001/& 2015 Elsevier Ltd. All rights reserved.

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charged oppositely to titania. WO3 can be a suitable candidate, of water. The solution was stirred for 15 min, followed by hydro-
because the isoelectric point of this material is well below thermal treatment (180 °C, 4 h) yielding a yellow colloidal sus-
(pHE1.5) in comparison with TiO2 [13]. Not only the relatively pension. The product was collected and washed by centrifugation
easy synthesis of the composite is important, but also that WO3 (1600 rpm, 15 min) with distilled water. After centrifugation the
can act as an efficient charge separator. The most efficient poly- precipitate was dried for 24 h at 40 ° C. Finally, the obtained ma-
morphs of WO3 in photocatalytic applications are monoclinic, or- terial was calcined at 500 °C for 30 min.
thorhombic and tetragonal crystal phases [14,15].
Therefore, in the present work a surface charge modification 2.2.4. Preparation of WO3–WA
was applied based on the determination of the IEP of the oxides. In this synthesis 2.5 g of H2WO4 was dissolved in a mixture of
This information was further used in the electrostatic charge at- 30 mL of hydrogen peroxide (H2O2) and 10 mL of distilled water by
traction based synthesis of TiO2/WO3 nanostructures from com- vigorous stirring (24 h), until it became a transparent solution. The
mercial (Aeroxide P25) and “home-made” (TiO2 xerogel and three solution was treated hydrothermally at 180 °C for 24 h, resulting a
different types of WO3) semiconductor oxides, focusing on their white colloidal suspension. The product was collected, washed by
optical, morpho-structural properties and photocatalytic activity centrifugation (3  10 min at 5000 rpm) with distilled water and
towards a model organic pollutant (methyl-orange). dried at 40 °C for 24 h.

2.3. The determination of the IEP

2. Experimental
The IEP was determined using a well-known method in the
2.1. Materials literature. In the first step a stock solution of 0.01 M NaCl was
prepared. In the five containers, 50 mL of NaCl solution was in-
All chemicals used were of analytical grade. Titanium iso- troduced. In each beaker the pH was adjusted accordingly (with
propoxide (TTIP), ammonium metatungstate hydrate 0.1 M HCl or 0.1 M KOH): in the case of TiO2 the pH values of 3.5, 4,
((NH4)6H2W12O40  H2O), tungstic acid (H2WO4) were purchased 4.5, 5, 5.5 and 6 were selected, while for WO3 1, 1.5, 2, 2.5, 3 and
from Sigma-Aldrich, while hydrochloric acid (HCl), hydrofluoric 3.5 were chosen according to the literature [13].
acid (HF) and potassium hydroxide (KOH) were purchased from After setting the desired pH values, 50 mg of the sample was
Nordic-Invest. Evonik Aeroxide P25 (Germany) was used, as re- introduced in each solution. After 3 h, the pH of the resultant
ceived, without further purification for the preparation of the suspensions were measured and plotted: pH(measured) ¼f(pH
composite materials. (initial)). The intersection of this curve with the theoretical pH
(initial) ¼pH(final) line yielded the IEP. Where the intersection was
2.2. Synthesis of materials not determinable graphically, the solution of the equation systems
formed from the equation of the two curves has yielded the IEP.
The composite materials were obtained from two types of TiO2 The obtained pH values for the obtained composites were sum-
and three types of WO3: marized in Table 1.

 In the case of TiO2: the general reference in photocatalysis 2.4. Preparation of the composites
(Aeroxide P25) vs. classical sol–gel made anatase titanias
 In the case of WO3: each of the WO3 contained different crystal The TiO2/WO3 composites contained 76 wt. % TiO2 and 24 wt. %
phases. WO3 [16,17]. The synthesis of the composites was performed as
follows: the pH of 100 mL distilled water (in a beaker) was ad-
The above listed materials have totally different crystal size and justed (adding 0.1 M HCl or 0.1 M KOH solutions) to the average of
crystal phase composition, which was necessary if the validation the IEP of the used TiO2 and WO3. After setting the pH, 608 mg of
of a composite synthesis method is desired. Hence, the present TiO2 was added to the distilled water and sonicated for 10 min.
paper focuses on the properties of the composite materials, rather The suspension was stirred for 15 min. In the next step 192 mg of
than on the individual peculiarities of the oxides. WO3 was added in the suspension and stirred for further 15 min.
The suspension was dried in an oven 12 h at 80 °C.
2.2.1. Preparation of TiO2–SG TiO2/WO3 composites were also obtained using physical mixing
HCl was added into 50 mL distilled water, until the pH has of the semiconductor powders in order to verify the efficiency of
reached 1. In the acidic solution, 5 mL TTIP was added drop. The
pH of the suspension was raised up to 4.5 with 1 M KOH solution. Table 1
The volume ratio of the precursor: distilled water was 1:10. The Synthesis parameter (pH), optical and photocatalytic properties of the composites.

obtained white dispersion was centrifuged and washed with dis- Sample Synthesis Band- Conversion after rMO (mol  L  1
tilled water. The precipitate was calcined at 400 °C in a muffle (pH) gap (eV) 2 h (%)  s  1)
furnace, for 3 h at a heating rate of 5 °C/min.
P25 n.a. 3.11 84.7 1.241
P25–AMT 2.85 3.02 91.5 0.399
2.2.2. Preparation of WO3–AMT(HF)
(HCl)
0.644 g of ammonium metatungstate (AMT) was dissolved in P25–WA 3.05 3.02 94.4 4.615
88.48 mL of 5 M HCl solution. After 20 min of homogenization P25–AMT 2.77 2.96 73.7 0.280
1.52 mL HF (40 v/v %) and 10 mg functionalized multiwall carbon (HF)
nanotube was added to the solution. After that the suspension was
hydrothermally treated at 180 °C for one hour. The final product SG n.a. 3.07 Inactive Inactive
was washed with deionized water by centrifugation (3  5 min). SG–AMT 3.35 3.05 45.6 0.755
The WO3 microcrystals were dried at 40 °C for 24 h. (HCl)
SG–WA 3.55 3.07 38.7 0.555
SG–AMT 3.27 2.93 Inactive Inactive
2.2.3. Preparation of WO3–AMT(HCl) (HF)
0.768 g of AMT and 0.525 mL of HCl were introduced in 12.5 mL

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the above listed composite synthesis method. Hence, the same 3. Results and discussion
amount of TiO2 and WO3 was mixed in an achate mortar. The
homogenization time of the composites was 15 min. The nomen- 3.1. Characterization of the photocatalysts
clature of the composites: composite name þm (e. g. SG–WO3–
WAm). 3.1.1. X-ray diffraction
As already detailed in the previous sections, two types of TiO2
2.5. Methods and instrumentation were used in the preparation of the composite materials. Hence,
XRD was applied in order to investigate the crystal structure and
X-ray diffraction (XRD) measurements were performed on a phase composition of the nanomaterials to ascertain that in the
final composite, the components are in the appropriate ratio. The
Shimadzu 6000 diffractometer using Cu-Kα radiation
(λ ¼ 1.5406 Å). Diffractograms were recorded in 2θ range from 20° XRD patterns of P25 shows the well-known 89 wt. % and 11 wt. %
anatase and rutile content [18], while in the SG TiO2 only the
to 40° (with a speed of 1°/min). JASCO-V650 spectrophotometer
anatase phase can be found (Fig. 1). The crystal size obtained for
with an integration sphere (ILV-724) was used for measuring the
sample P25 was between 25 and 40 nm and, while 10 nm was
DRS spectra of the samples (λ ¼ 250–800 nm). The band-gap was
calculated for sample SG. In all composites the estimated WO3
obtained from the plot of [F(R) E]1/2 vs. energy of the exciting light
content was 23–25% which coincides with the theoretical value
(E). FEI Quanta 3D FEG dual beam electron microscope (equipped
proposed in the experimental section.
with an Apollo-X SDD Energy Dispersive X-ray (EDX) detector) was
Besides the identified titania crystal phases (anatase and rutile
used to obtain quantitative elemental analyzes and elemental
JCPDS cards no. 21-1272 and 21-1276), several WO3 crystal
distribution maps.
structures were detected (each of the bare WO3 was obtained in
different conditions): monoclinic WO3 (JCPDS card no. 43-1035),
2.6. Photocatalytic experiments tungstit WO3  H2O (JCPDS card no. 18-1418), hexagonal and or-
thogonal WO3 (JCPDS cards no. 75-2187, 20-1324). In the SG
The photocatalytic activity was evaluated by methyl-orange sample series the same WO3 crystal phases were identified, as
degradation using a double walled photoreactor (170 mL), sur- described above.
rounded by a thermostating jacket (25 °C). The continuously stir-
red reactor was surrounded and irradiated by six fluorescent 3.1.2. Diffuse reflectance spectroscopy
lamps (6 W power, λmax E365 nm). The amount of catalyst in- Next critical parameter from the point of view of the photo-
troduced in the suspension was 170 mg (1 g  L  1), while the catalytic activity was investigated, namely, the light-absorption
concentration of the methyl-orange (MO) was 0.15 mmol  L  1. The properties of the TiO2/WO3 nanostructures (Fig. 2).
concentration of MO was measured with the spectrophotometer It can be clearly observed that the different composites have
described in Section 2.5., at λdet E513 nm. At the beginning of the induced significant changes in the optical properties of the na-
measurement, the mixture was kept in dark for 15 min and the nostructures depending of the precursors used during the synth-
concentration of the methyl-orange was measured before/after to esis, consequently, the evaluation of the band-gap values was
ensure the adsorption of the model contaminant. mandatory. Using the Kubelka–Munk equation, it was found that

Hexagonal WO3 Hexagonal WO3 WA

Ortogonal WO3 Ortogonal WO3
P25-WA

Tungstite WO3·H2O
Tungstite WO3·H2O AMT (HF)

P25-AMT (HF)
Intensity (a. u.)
Intensity (a. u.)

Monoclinic WO3
Monoclinic WO3
AMT (HCl)
P25-AMT (HCl)

Anatase TiO 2
SG
Anatase TiO2
Rutile TiO2 P25

20 22 24 26 28 30 32 34 36 38 40 20 22 24 26 28 30 32 34 36 38 40
2θ (degree) 2θ (degree)
Fig. 1. XRD patterns of the P25 (a) and individual oxides (b).

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Fig. 2. DRS spectra of the TiO2/WO3 composites.

the band-gap energy values were decreased significantly for the P25 P25
100 P25 P25-WA P25-WAm
AMT(HCl) AMT(HCl)m
composites based on the commercial titania (from 3.11 eV to
3.02 eV for P25–AMT(HCl) and P25–WA reaching a value of 2.96

Methyl orange conversion (%)

80
for P25–AMT(HF), respectively), while a less significant decrease
was determined for the composites based on SG–titania. The only
exception was observed for SG–AMT(HF) where the band-gap 60
value for this composite reached 2.93 eV, the lowest value of the
investigated composites (Table 1).
40

3.1.3. SEM-EDAX measurements 20

One of the important task of the present work was to obtain
composites with a high degree of homogeneity. In the classical
0
composite fabrication techniques, the components are mixed by
physical means [16]. This results in a relatively high degree of Fig. 4. Photodegradation curves of MO in the presence of TiO2–WO3 nanocompo-
sites under UV irradiation (a) and comparison between conversion rates obtained
isolated particle agglomerations, which can be distinguished easily
with classical composite synthesis (m) and surface charge-based method (b).
at micron scale (Fig. 3a, sample P25–WAm). If the surface charge
based composite materials were investigated a high degree of 3.2. Photodegradation of methyl-orange
homogeneity could be observed. The largest aggregates for these
composites were in the range of 200–500 nm (Fig. 3b, sample In order to have information about the photocatalytic proper-
P25–WA). ties of the composites, photodegradation measurements were
The latter observation hints, that these materials contain carried out on methyl-orange (Fig. 4).
semiconductor oxides homogenously dispersed within the com- It can be observed that the SG–AMT(HF) and the pure SG are
posite, which means the existence of a higher number of inactive. On the “other end” of the photocatalytic efficacy we can
TiO2–WO3 contacts. A high interparticle connection network also observe that two of the P25-based composites have shown a
means higher charge transfer possibilities between the two oxides higher efficiency, degrading more than 90% of the MO (91.5% and
[19]. 94.4% for P25–AMT(HCl) and P25–WA, respectively), while the

Fig. 3. EDAX elemental mapping of sample P25–WAm (a) and P25–WA (b).

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Fig. 5. Schematic representation of the electrostatic attraction based composite synthesis.

“pure” P25 has converted less than 85% of the organic dye. above-mentioned method can give composites with higher effi-
If the comparison is made between the composites containing ciencies than those obtained with “classical” methods.
the two types of titania, it can be concluded that the conversion
rates for composites based on P25 are higher than for SG-based
composites. On the other hand the rate constants are higher for SG Acknowledgment
sample series than for the P25–AMT-composites (the only excep-
tion being P25–WA vs. SG–WA composite). The most important The Romanian authors wants to acknowledge the financial
issue is that in both P25 and SG series at least two composites support from the Romanian National Authority for Scientific Re-
showed better photocatalytic performance than the appropriate search, CNCS-UEFISCDI (National Research Council-Executive
reference (bare P25 and SG). Agency for Higher Education, Research, Development and In-
To be able to quantify the efficiency of the surface charge-based novation Funding), Project number PN-II-ID-PCE-2011-3-0442. For
method vs. the classical physical mixing method, photodegrada- É. Karácsonyi this research was realized in the frames of TÁMOP
tion measurements were carried out on the analogs (P25–WAm 4.2.4. A/2-11-1-2012-0001 “National Excellence Program – Ela-
and P25–AMT (HCl)m) of the best-performing P25-based compo- borating and operating an inland student and researcher personal
sites (Fig. 4b). From the conversion rates can be concluded that the support system convergence program”. The project was subsidized
surface charge-based composites are more efficient than their by the European Union and co-financed by the European Social
classical analogs (91.5 vs. 84.6% for the AMT(HCl)-based compo- Fund.
sites and 94.4 vs. 76.3% for WA-based composites – the difference
in these activities are shown with a double arrow in Fig. 4b).
References
3.3. Classical synthesis method vs. surface charge-based composite
synthesis: differences between photocatalytic activities [1] S. Chaturvedi, P.N. Dave, Environmental application of photocatalysis, Mater.
Sci. Forum (2013) 273–294.
[2] J.M. Herrmann, Titania-based true heterogeneous photocatalysis, Environ. Sci.
As it is well illustrated by the observed activities, the compo- Pollut. Res. 19 (2012) 3655–3665.
sites assembled by electrostatic attraction have shown enhanced [3] R. Vinu, G. Madras, Renewable energy via photocatalysis, Curr. Org. Chem. 17
activity. Their performance was superior compared to the bare (2013) 2538–2558.
[4] J. Xu, W. Dai, J. Li, Y. Cao, H. Li, H. He, et al., Simple fabrication of thermally
titanias, while their registered photocatalytic performance was
stable apertured N-doped TiO2 microtubes as a highly efficient photocatalyst
even higher than the materials made by simple physical mixing. under visible light irradiation, Catal. Commun. 9 (2008) 146–152.
The main reason behind of this interesting behavior lies within [5] R. Michael, S.T.M. Hoffmann, Wonyong Choi, Detlef W. Bahnemann, Environ-
mental applications of semiconductor photocatalysis, Chem. Rev. 95 (1995)
the high homogeneity of the composites, as it was demonstrated
69–96.
by SEM-EDX and illustrated in Fig. 5. The very homogenous [6] V. Tiwari, J. Jiang, V. Sethi, P. Biswas, One-step synthesis of noble metal–tita-
composite system resembles to the noble metal – semiconductor nium dioxide nanocomposites in a flame aerosol reactor, Appl. Catal. A: Gen.
oxide composites, where each of the noble metal nanoparticles is 345 (2008) 241–246.
[7] G. Kovács, L. Baia, A. Vulpoi, T. Radu, É. Karácsonyi, A. Dombi, et al.,
in contact with the semiconductor, assuring efficient charge se- TiO2/WO3/Au nanoarchitectures’ photocatalytic activity, “from degradation
paration (electron transfer). Furthermore, as the number of the intermediates to catalysts’ structural peculiarities”, Part I: Aeroxide P25 based
contacts is higher, a higher photocatalytic activity can be obtained composites, Appl. Catal. B: Environ. 147 (2014) 508–517.
[8] G. Kovács, Z. Pap, C. Coteț, V. Coșoveanu, L. Baia, V. Danciu, Photocatalytic,
[20]. As WO3 is a rather good electron acceptor (can be easily re- morphological and structural properties of the TiO2–SiO2–Ag porous struc-
duced), the same mechanism can be presumed. tures based system, Materials 8 (2015) 1059–1073.
When the composite components are combined using physical [9] W. Smith, A. Wolcott, R.C. Fitzmorris, J.Z. Zhang, Y. Zhao, Quasi-core–shell
TiO2/WO3 and WO3/TiO2 nanorod arrays fabricated by glancing angle de-
mixing, the larger aggregates formed cannot be disassembled position for solar water splitting, J. Mater. Chem. 21 (2011) 10792.
neither by ultrasonication, neither mechanically. In consequence a [10] R. Quesada-Cabrera, A. Mills, C. O’Rourke, Action spectra of P25 TiO2 and a
high number of the same semiconductor particles are situated in visible light absorbing, carbon-modified titania in the photocatalytic de-
gradation of stearic acid, Appl. Catal. B: Environ. 150–151 (2014) 338–344.
agglomerates where they cannot be contacted efficiently by the [11] C.H. Kim, B.-H. Kim, K.S. Yang, TiO2 nanoparticles loaded on graphene/carbon
other semiconductor. This results in a lower contact number and composite nanofibers by electrospinning for increased photocatalysis, Carbon
lower efficiency (Fig. 4b). 50 (2012) 2472–2481.
[12] J.P. Holmberg, E. Ahlberg, J. Bergenholtz, M. Hassellöv, Z. Abbas, Surface charge
and interfacial potential of titanium dioxide nanoparticles: experimental and
theoretical investigations, J. Colloid Interface Sci. 407 (2013) 168–176.
4. Conclusions [13] S. Prabhu, A. Nithya, S. Chandra Mohan, K. Jothivenkatachalam, Synthesis,
surface acidity and photocatalytic activity of WO3/TiO2 nanocomposites-an
overview, Mater. Sci. Forum (2014) 63–78.
Titania/tungsten oxide-based nanocomposites were synthe- [14] S.A.K. Leghari, S. Sajjad, F. Chen, J.L. Zhang, WO3/TiO2 composite with mor-
tized using the IEPs of the semiconductors. Analysis of the com- phology change via hydrothermal template-free route as an efficient visible
posites was performed taking under the loupe the morphological light photocatalyst, Chem. Eng. J. 166 (2011) 906–915.
[15] I. Szilágyi, B. Fórizs, O. Rosseler, Á. Szegedi, P. Németh, P. Király, P. Tarkányi,
and optical peculiarities of the materials (using DRS, XRD, SEM- B. Vajna, K. Varga-Josepovits, K. László, A. Tóth, P. Baranyai, M. Leskela, WO3
EDAX). From the photocatalytic tests it can be concluded that the photocatalysts: influence of structure and composition, J. Catal. 294 (2012)

Please cite this article as: L. Baia, et al., Materials Science in Semiconductor Processing (2015), http://dx.doi.org/10.1016/j.
mssp.2015.08.042i
6 L. Baia et al. / Materials Science in Semiconductor Processing ∎ (∎∎∎∎) ∎∎∎–∎∎∎

119–127. Crystalline composition analysis, reconstruction from isolated pure particles

[16] É. Karácsonyi, L. Baia, A. Dombi, V. Danciu, K. Mogyorósi, L.C. Pop, et al., The and photocatalytic activity test, J. Photochem. Photobiol. A: Chem. 216 (2010)
photocatalytic activity of TiO2/WO3/noble metal (Au or Pt) nanoarchitectures 179–182.
obtained by selective photodeposition, Catal. Today 208 (2013) 19–27. [19] N. Siedl, S.O. Baumann, M.J. Elser, O. Diwald, Particle networks from powder
[17] Z. Pap, É. Karácsonyi, L. Baia, L.C. Pop, V. Danciu, K. Hernádi, et al., mixtures: generation of TiO2–SnO2 heterojunctions via surface charge-in-
TiO2/WO3/Au/MWCNT composite materials for photocatalytic hydrogen pro- duced heteroaggregation, J. Phys. Chem. C 116 (2012) 22967–22973.
duction: Advantages and draw-backs, Phys. Status Solidi (B) 249 (2012) [20] G. Kovács, S. Fodor, A. Vulpoi, K. Schrantz, A. Dombi, K. Hernádi, et al., Poly-
2592–2595. hedral Pt vs. spherical Pt nanoparticles on commercial titanias: is shape tai-
[18] B. Ohtani, O.O. Prieto-Mahaney, D. Li, R. Abe, What is Degussa (Evonik) P25? loring a guarantee of achieving high activity? J. Catal. 325 (2015) 156–167.

Please cite this article as: L. Baia, et al., Materials Science in Semiconductor Processing (2015), http://dx.doi.org/10.1016/j.
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