Journal of Colloid and Interface Science 426 (2014) 287–292

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Journal of Colloid and Interface Science

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Effect of surfactant type on platinum nanoparticle size of composite

Pt/a-Al2O3 catalysts synthesized by a microemulsion method
Shima Soleimani a, Alireza Salabat a,⇑, Rico F. Tabor b
a
Department of Chemistry, Faculty of Science, Arak University, 38156-8-8349 Arak, Iran
b
School of Chemistry, Monash University, Clayton 3800, Australia

a r t i c l e i n f o a b s t r a c t

Article history: A facile method for the generation of platinum-on-alumina hybrid materials with high-surface area is
Received 25 January 2014 presented, employing a microemulsion-based synthesis of metal nanoparticles. Pt nanoparticles (NPs)
Accepted 17 March 2014 supported on a-Al2O3 were prepared by the reduction of metal ions in water-in-oil microemulsion sys-
Available online 18 April 2014
tems stabilized by a range of different surfactants with cationic, anionic and nonionic headgroups,
namely AOT, CTAB, Tween80 and TX-100. The synthesized materials were characterized using Fourier
Keywords: transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscopy
Platinum nanoparticles
(SEM). It is demonstrated that choice of surfactant can be used to tailor the size of the generated Pt
Surfactant
Microemulsion
nanoparticles, and seen that surfactant charge has a determining role in this process. Pt NPs formed in
Alumina support microemulsion systems based on charged surfactants (AOT and CTAB) are smaller than those prepared
in nonionic microemulsion systems (TX-100 and Tween80). A solvent-induced demixing process was
used to cleanly obtain the hybrid materials from the reaction medium at low energy cost.
Ó 2014 Elsevier Inc. All rights reserved.

1. Introduction a water-in-oil microemulsion can be varied by the oil phase [15],

The synthesis of metal nanoparticles (NPs) and exploration of
their various potential applications is of considerable interest in
fields such as catalysis, electronics, biotechnology and energy
materials, due to the unique properties of metals at such small
scales [1–5]. In the catalysis field, the preparation of NPs can be
achieved by various chemical techniques including the co-precipi-
tation method [6–8], sol–gel process [9–11] and hydrothermal pro-
cesses [12,13]. An alternative, low-energy method to prepare
nanosized particles with a great deal of size and shape control is
in water-in-oil microemulsion systems [14]. Microemulsion sys-
tems represent excellent media for nanoparticle synthesis, as they
are isotropic liquids with nanosize water droplets on the order of
10–100 nm, dispersed in a continuous oil phase and stabilized by
surfactant molecules. Reduction of metal salts within the droplets
offers ‘nanoreactors’ that can be adjusted in size using the water-
to-surfactant ratio. Thus, using microemulsions, it is possible to
control synthesis parameters and produce tailor-made products
down to a nanoscale level with new and special properties. In pre-
vious work, we have shown that the size of the aqueous droplets in
⇑ Corresponding author. Fax: +98 861 4173406.
E-mail address: a-salabat@araku.ac.ir (A. Salabat).
also affecting the size of the nanoparticles [16].
Platinum-based catalysts supported on Al2O3 show excellent
activity and stability for use in important reactions such as cata-
lytic oxidation of naphthalene [17], hydrogen production for fuel
cells [18], 1,3-butadiene hydrogenation [19], selective CO oxida-
tion [20], diesel soot and NOx abatement [21], and so on. Karakaya
et al. established a simple and rapid chemisorption technique for
the quantification of metal dispersion in different types of sup-
ported metal catalysts, without the need for a sophisticated appa-
ratus and ultra-high vacuum conditions [22]. They presented
exemplary results for diesel oxidation catalysts based on Pt/
Al2O3. Another interesting feature of Pt-based catalyst supported
on Al2O3 is atmospheric desulfurization of diesel fuel. Haji et al.
investigated hydrodesulfurization of commercial diesel fuel at
atmospheric pressure using Pt/Al2O3 catalysts prepared by a super-
critical carbon dioxide deposition method [23].
In this work, we explore the effect of surfactant type on the size
of Pt NPs synthesized by the microemulsion method and deposited
on a-Al2O3. It is shown that by changing the surfactant headgroup
chemistry, the particle size of Pt NPs supported on a-Al2O3 can be
controlled. To prepare these systems, w/o microemulsions contain-
ing an aqueous solution of H2PtCl6 and stabilized by the surfactants
AOT, TX-100, Tween80 and CTAB were prepared. By addition of a
reducing agent, hydrazine, stable colloidal solutions of Pt NPs were

http://dx.doi.org/10.1016/j.jcis.2014.03.033
0021-9797/Ó 2014 Elsevier Inc. All rights reserved.
288 S. Soleimani et al. / Journal of Colloid and Interface Science 426 (2014) 287–292

obtained from reduction of Pt4+ ions. A simple phase separation
method, using THF as a destabilizing solvent, was used to break
the colloidal dispersions and release the Pt NPs onto a colloidal
a-Al2O3 support. Infrared spectroscopy (IR), scanning electron
microscopy (SEM) and X-ray diffraction (XRD) were used to char-
acterize all of the prepared samples, showing that nanosized plat-
inum particles were dispersed uniformly on the a-alumina.
2. Materials and methods
2.1. Reactants
Hexachloroplatinic acid (H2PtCl6) (99%) and cyclohexane were
obtained from Merck–Schuchardt and used as received. The purity
of the cyclohexane was checked by gas chromatography and
confirmed to be >99%. The surfactants Sodium 1,4-bis(2-ethylhex-
oxy)-1,4-dioxobutane-2-sulfonate (AOT, 96%), cetyltrimethylam-
monium bromide (CTAB, 99+%), poly(oxyethylene) sorbitan
monooleate (Tween80, 99%) and poly(ethylene glycol) p-(1,1,3,3-
tetramethylbutane)-phenyl ether (TX-100, 98%) were purchased
from Acros Organics and used without future purification (see
Table 1). a-Al2O3 was obtained from Shijiazhuang Baicheng Chem-
ical Co., Ltd. (surface area 16–18 m2/g and particle size 80-100 nm).
2.3. Preparation of Pt/a-Al2O3
The a-Al2O3, as a supporting material on which to adsorb the Pt
NPs, was added to the Pt NPs colloidal suspensions in a 50:1
Al2O3:Pt mass ratio. After addition of the alumina, the colloidal
system was destabilized by slow addition of THF to 3 times the vol-
ume of the initial colloidal dispersion. The suspension was then
stirred for 20 h to facilitate demixing and adsorption of Pt NPs onto
the a-Al2O3. The harvested products were filtered and washed with
excess THF. The absence of a UV–visible absorption peak of Pt NPs
in the remaining solution confirmed that the Pt NPs had fully
adsorbed on Al2O3 and were eliminated from the colloidal precur-
sor systems. Subsequently, the final Pt/a-Al2O3 products with
1.2 wt% Pt were dried at room temperature for 24 h and calcined
for 1 h at 600 °C to remove adsorbed organic material.
2.4. Characterization
2.4.1. Scanning electron microscopy (SEM)
SEM images were made using a Philips XL30 instrument. The
prepared samples were sonicated for 20 min using a Pulse 570s
POT Riscaldamento W.400 instrument, and one droplet of the sam-
ple was transferred to an aluminum plate, dried at room tempera-
ture and then sputtered with gold.

2.2. Synthesis of platinum colloidal suspensions 2.4.2. X-ray diffraction (XRD)

Colloidal suspensions of Pt NPs were prepared in w/o micro-
emulsions containing cyclohexane as the continuous oil phase
and one of four surfactants: AOT, TX-100, Tween80 and CTAB.
A suitable amount of 0.01 M aqueous H2PtCl6 was added to the
0.12 M surfactant solution in cyclohexane such that [H2O]/
[surfactant] = 5. Thus four separate microemulsions containing
H2PtCl6 were prepared, each stabilized by a different surfactant.
These samples were equilibrated for 3 hours with stirring, after
which the platinum ions were reduced by addition of a separate
microemulsion system containing N2H4. The molar ratio of
N2H4:Pt was kept at 10:1. After 4 h of stirring to ensure complete
mixing and reduction, the reaction was considered complete. UV–
visible spectroscopy was used to monitor the formation of Pt NPs
for all prepared colloidal systems. The stability of all colloidal
systems as prepared was more than 2 months at ambient
conditions.
XRD measurements were obtained using a Philips diffractome-
ter with a 40 kV generator tension and 30 mA generator current
with Cu Ka radiation (Cu Ka1:1.54056 Å, Cu Ka2:1.54439 Å). The
2h angular region between 20° and 100° was explored at a step
time of 2.0 s and temperature of 25 °C.
2.4.3. Spectroscopy
Infra-red spectra were obtained using a Galaxy FT-IR 5000, and
samples were prepared using KBr pressed disks. UV–visible spectra
were acquired using a Specord S600 JENA AG Model spectrometer.
3. Results and discussion
3.1. UV–visible study of Pt NPs in colloidal systems
Fig. 1 shows the typical change in the UV-visible absorption
spectrum of the H2PtCl6 microemulsion system after addition of

Table 1
Chemical structures and corresponding abbreviations of various surfactants used in microemulsion systems.

Surfactant name Abbreviation Structure

Sodium 1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate AOT
O
O
O
O O
S
Na O O
Cetyltrimethylammonium bromide CTAB –
N+ Br
Polyoxyethylene (20) sorbitan monooleate Tween80
O
O
W
O OH
O X W+X+Y+Z=20
HO OH
O O Y
Z

Polyethylene glycol P-(1,1,3,3-tetramethylbutane)-phenyl ether TX-100 O H

O
n
 S. Soleimani et al. / Journal of Colloid and Interface Science 426 (2014) 287–292
Fig. 1. UV–visible absorption spectra (a) the 0.01 molar aqueous solution of
2
platinum complex ( PtCl6 ) system, (b) absorption spectra of suspension platinum
nanoparticles synthesized in microemulsion systems containing different surfac-
tants: (A) AOT, (B) CTAB, (C) T-X-100 and (D) Tween80.
the reductant N2H4 microemulsion. The 0.01 M aqueous solution of
2
platinum complex ions (PtCl6 ) absorbs strongly in the UV with
peaks at 318 and 368 nm, which is attributed to the charge transfer
from the ligand of Cl to Pt4+ [24]. As can be seen from Fig. 1, after
reduction of the Pt4+ ions to platinum atoms, platinum particles are
formed and these two bands disappear. A new characteristic
absorption peak due to the formation of metallic Pt nanoparticles
appears at 345–354 nm after 15 min reaction time. It is clear from
Fig. 1 that the peak absorption wavelength and intensity for the
NPs depend on the surfactant type used in the microemulsion sys-
tems. In general for nanoparticle systems, the maximum absorp-
tion peak position in the UV–visible spectrum is strongly
dependent on particle size, due to the surface plasmon resonance
effect [25]. The Pt NPs formed in the microemulsion based on the
anionic surfactant AOT, the cationic surfactant CTAB and the non-
ionic surfactants TX-100 and Tween80 showed peaks at around
345, 353.5, 347 and 350.5 nm, respectively. The characteristic red
shift of the wave length indicates that the size of the Pt NPs
increased in order from anionic to nonionic to cationic surfactants.
On the other hand, the intensity of the UV absorption peaks for Pt
NPs prepared in nonionic surfactants, TX-100 and Tween80, are
higher than systems containing ionic surfactants, AOT and CTAB.
These spectral changes indicate that particle size and therefore
concentration are affected by the type of surfactant used, and that
changes in nucleation rate may be the controlling parameter [14].
In order to explore these effects further, particles sizes were mea-
sured directly using scanning electron microscopy.
3.2. Scanning electron microscopy (SEM) results
The morphology of the various synthesized Pt/a-Al2O3 samples
was observed by scanning electron microscopy (SEM). Fig. 2 shows
SEM micrographs of Pt/a-Al2O3 prepared with anionic, cationic and
nonionic surfactants. Fig. S1 in the Supporting information also
shows SEM image of the bare a-Al2O3. In the SEM image of
Fig. 2, the raised points corresponding to Pt NPs on the a-Al2O3 sur-
faces are clearly visible. The SEM micrographs illustrate that Pt
particles are evenly spread over the a-Al2O3 support with average
diameters up to 132 ± 0.5 nm depending on the surfactant type
used. The smallest particles, with average diameter of 92.4 nm
were obtained for the catalyst prepared based using ionic surfac-
tants. On the other hand, larger particles with average diameter
289
of 127-130 nm were obtained for samples prepared using nonionic
surfactants. This trend can be seen also from transmission electron
microscopy (TEM) images of Pt particles prepared in microemul-
sions of various surfactants (Fig. S2). The Pt particle size distribu-
tions obtained from SEM and TEM analysis confirm the data from
UV–visible spectra that particles had indeed been produced. As
can be seen from SEM images in Fig. 2, the Pt NPs are well-dis-
persed on the alumina support with moderate to high surface
coverage.
3.3. X-ray diffraction results
In order to further confirm the presence and structural charac-
teristics of the Pt NPs on a-Al2O3, X-ray diffraction (XRD) measure-
ments were performed. Fig. 3 shows the XRD patterns of Pt/a-
Al2O3 prepared using various surfactants. The marked peaks at
2h = 68.54, 77.68 and 95.69 in all of the samples are attributed to
the diffractions of [2 2 0], [3 1 1] and [4 0 0] planes of a face-cen-
tered-cubic (fcc) phase of Pt. The remaining unmarked diffraction
peaks observed in XRD patterns are from the alumina particles
[26]. The XRD patterns of the Pt/a-Al2O3 also support the fact that
Pt NPs are highly dispersed on the surface of a-Al2O3. The average
crystal sizes of the platinum particles were estimated by using the
Debye–Scherrer equation [27]:
kk
Dhkl ¼ ð1Þ
Bhkl cos h
where Dhkl is the crystallize size and k is the wavelength of incident
radiation. The value of k is a constant usually taken as 0.89, and Bhkl
is the full width at half-maximum (FWHM) of the peak. Increasing
the FWHM implying the decrease of the particles size, as reported in
Table 2. The average crystal sizes of Pt particles, estimated from the
strongest peak, were obtained as 55.4 nm, 84.5 nm, 90.9 nm and
109.4 nm for Pt/a-Al2O3 hybrid materials prepared using AOT,
CTAB, Tween80 and T-X-100, respectively. These data suggest that
the particles produced are broadly mono-crystalline when com-
pared to the sizes from SEM.
3.4. FTIR spectra results
Pt/a-Al2O3 composites prepared using the microemulsion
method and calcined at 600 °C for 1 h in air were characterized
by IR spectroscopy. As can be seen in Fig. 4a, the broad peak at
3433.51 cm1 is due to the surface OH stretching (Al–OH) of the
a-Al2O3 particles. The intensity of this peak indicates the number
of hydroxy groups on the surface of a-Al2O3; the peak at
1639.60 cm-1 is due to the –OH bonding vibration. The broad
absorbance ranging from 300 to 1000 cm1 is characteristic of
–Al–OH and –O–Al–O–Al vibrations for Al2O3 [28]. Fig. 4b shows
that Pt/a-Al2O3 prepared via the microemulsion route has a quite
similar spectrum with respect to the a-Al2O3 particles, but the
intensity of the –OH band at 3450 cm1 for alpha alumina is dra-
matically lowered for the Pt/a-Al2O3 system. This indicates that the
number of surface hydroxy groups on the alumina decreases in the
presence of Pt particles adsorbed to the alumina surface. Unfortu-
nately, the characteristic peak at around 430–450 cm1 due to
expected Pt–O bonds is hidden by the broad and intense absorp-
tion of the alpha alumina.
Much of the behavior observed in these systems can be ratio-
nalized by the different surfactant headgroup chemistries encoun-
tered. There is a clear disconnect between the ionic and nonionic
systems, whereby ionic surfactants favor much smaller final parti-
cle sizes.
The UV–visible study of the colloidal dispersions indicated that
the difference of the size of Pt NPs synthesized by the microemul-
290 S. Soleimani et al. / Journal of Colloid and Interface Science 426 (2014) 287–292

Fig. 2. XRD patterns of Pt/a-Al2O3 synthesized in microemulsions of various surfactants and calcinated at 600 °C for 1 h.

Table 2
Average crystal size of Pt NPs released on a-Al2O3 using different surfactants,
calculated from XRD patterns by Debye–Scherrer formula.

Surfactant FWHM Average crystal size (nm)

AOT 0.174 55.4 ± 0.05
CTAB 0.113 84.5 ± 0.05
Tween80 0.108 90.9 ± 0.05
TX-100 0.101 109.4 ± 0.05

sion method is related to the charge of the polar headgroup of the

surfactants used (which in this case is +1, 0 or 1). It is known that
the process of collision, fusion, separation and restructuring among
the microemulsion droplets leads to the nucleation and subse-
quent growth of the product, resulting in the formation of nano-
particles. Thus, the dynamic exchange process of the reactants in
different water nanoreactors plays an important role in controlling
the particle size. Based on this model, the effect of headgroup
charge can be rationalized in terms of the electrostatic interaction
2
on the rate control of PtCl6 ion diffusion and reaction with the
N2H4. Obviously, there are six moles of Cl- ions per mole of
2
PtCl6 . The chemistry of reduction with hydrazine is somewhat
complex in terms of the ions present and produced. Hydrazine in
aqueous solution is present as hydrazine hydrate, N2H4  H2O,
which is a powerful reductant due to its ability to liberate electrons
by reacting with hydroxide ions in water [29]:

N2 H4  H2 O þ 4OH ! N2 þ 5H2 O þ 4e

Fig. 3. Scanning electron microscopy (SEM) of Pt/a-Al2O3 synthesized in micro- It is clear that the reaction of the Pt4+ with the associated ionic spe-
emulsions of various surfactants. cies required for reduction will be diffusion limited, and that this
 S. Soleimani et al. / Journal of Colloid and Interface Science 426 (2014) 287–292
Fig. 4. FTIR spectra of (a) a-Al2O3 and (b) Pt/a-Al2O3, after 1 h calcination at 600 °C.
diffusion will be modulated by the Debye length (i.e. electrostatic
screening length) within the microemulsion water domains. Ionic
surfactant headgroups and their associated counterions contribute
strongly to the screening, and would therefore be expected to heav-
ily influence the nucleation and growth of the Pt particles.
It is also important to note that the final particle size (100 nm)
is considerably larger than the size of the ‘nanoreactor’ droplets in
the microemulsion (a few nm) and so many there may be addi-
tional processes such as the fusing of nuclei or collisional growth
mechanisms at play. Although the exact mechanism by which
these complex processes modulate the final particle size is still
not entirely clear, the influence of headgroup charge is undisputed
[14].
We posit here that the screening caused by ionic surfactants
favors the formation of a larger number of smaller crystal nuclei,
whereas the nonionic surfactants tend to favor fewer, larger parti-
cles. The rationale for the significant difference in size between
particles produced by anionic vs cationic surfactant is less clear.
For nonionic surfactants, as can be seen from Fig. 1, the concen-
tration of Pt NPs increased with the increase of hydrophobic chain
length from TX-100 to Tween80. It is known that the slow relaxa-
tion time of micelle formation-breakup (i.e. micellar lifetime), is
strongly dependent on the hydrophobicity of the surfactant; the
longer the hydrophobic tail, the greater the micellar lifetime [30].
This may affect the inter-droplet exchange rate, and thus the
growth rate of the nanoparticles.
Results from analysis of XRD measurements demonstrated that
the different sizes of the crystallized Pt nanoparticles on alumina
are consistent with the results from direct imaging using SEM.
According to the XRD results in Table 2, the crystal size of Pt NPs
synthesized using different surfactants was in the order AOT < C-
291
TAB < Tween80 < T-X-100, i.e. anionic surfactant < cationic surfac-
tant < nonionic surfactant.
4. Conclusions
The synthesis of hybrid materials comprising Pt metallic nano-
particles on a-Al2O3 was successfully achieved using a microemul-
sion method with different surfactants. The obtained results
confirmed that the head group charge of the surfactants has an
obvious effect on the size of the Pt NPs on the a-Al2O3. Specifically,
the Pt NPs formed in microemulsion systems based on ionic surfac-
tants were smaller than those prepared using nonionic surfactants.
XRD analysis indicated that the nanoparticles were broadly crystal-
line; the smallest crystal size was also obtained for Pt/a-Al2O3 pre-
pared using the anionic surfactant AOT, and the largest crystal size
was obtained using the nonionic surfactant T-X-100. The synthesis
and preparation method offers considerable advantages over con-
ventional routes to these composite materials [20,23] as it provides
morphological and size control and is a much lower-energy route.
We posit that the ionic character of the charged surfactants
plays a central role in the nucleation and growth mechanism of
the Pt nanoparticles by contributing to electrostatic screening
within the microemulsion droplets. Previous models implicate
the role of surfactant film flexibility [31] and bonding strength
with the particle surfaces [32] as contributing factors. However,
in this case, a clear dependence on headgroup charge is evident,
which could be expected to have overriding control of the nascent
charged particle nuclei inside the aqueous droplets. This is sup-
ported by recent experiments demonstrating the controlling effect
of surfactant counterion character on the morphology of gold
nanocrystals [33].
The materials generated are of interest as catalysts in a range of
specialist reactions of industrial importance [17–21]. Significantly,
the new synthesis method presented here offers a unique route to
these materials, with controllable particle size and reproducibly
crystalline morphologies. By using an antisolvent to capture the
synthesized materials, this process can be achieved cleanly and
at low energy cost.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jcis.2014.03.033.
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