Journal of Saudi Chemical Society (2017) xxx, xxx–xxx

King Saud University

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www.ksu.edu.sa
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ORIGINAL ARTICLE

Sol–gel synthesis of highly TiO2 aerogel

photocatalyst via high temperature supercritical
drying
Rebah Moussaoui a, Kais Elghniji a,b, Mongi ben Mosbah a,b, Elimame Elaloui a,b,
Younes Moussaoui b,c,*

a
Material Environment and Energy Laboratory (UR14ES26), Faculty of Sciences of Gafsa, University of Gafsa, Tunisia
b
Faculty of Sciences of Gafsa, University of Gafsa, 2112 Gafsa, Tunisia
c
Organic Chemistry Laboratory (LR17ES08), Faculty of Sciences of Sfax, University of Sfax, Tunisia

Received 12 February 2017; revised 26 March 2017; accepted 1 April 2017

KEYWORDS Abstract Nanocrystalline powders of TiO2 xerogel and aerogel were prepared by using acid-
Sol–gel; modified sol–gel approach. For TiO2 aerogel material (TA), the solvent was high temperature
Xerogel; supercritically extracted at 300 °C and 100 bars. However, the TiO2 xerogel material (TX) was dried
Aerogel; at 200 °C and ambient pressure. The effects of the drying processes on the crystalline structure,
Supercritical drying; phase transformation and grain growth were determined by Raman spectroscopy, SAED and X-
Photodegradation ray diffraction (XRD) analyses using Rietveld refinement method. The TiO2 aerogel was composed
of anatase crystalline structure. The TiO2 xerogel material was composed of anatase, brookite and
small amount of amorphous phase with anatase as dominant phase. The TX sample still contains a
relatively high concentration of carbon than that of TA, indicating the amorphous character of
TiO2 xerogel. These materials were applied as catalyst for the degradation of indigo carmine in
aqueous medium. Photo-degradation ability of TA and TX was compared to the TiO2 commercial
Degussa P25. The photo-catalytic results showed that the degradation efficiency was in the order
TA > P25 > TX. The photo-degradation of indigo carmine followed pseudo first order reaction
kinetics.
Ó 2017 King Saud University. Production and hosting by Elsevier B.V. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
* Corresponding author at: Faculty of Sciences of Gafsa, University
of Gafsa, 2112 Gafsa, Tunisia. Fax: +216 76210423.
E-mail address: y.moussaoui2@gmx.fr (Y. Moussaoui). Titanium dioxide semiconductor is considered to be the most
Peer review under responsibility of King Saud University. promising heterogeneous photo-catalyst, because of its high
photo-catalytic activity, chemical stability and favourable
optoelectronic properties [1,2]. TiO2 can exist in both crys-
talline and amorphous forms. The amorphous form of TiO2
Production and hosting by Elsevier is photo-catalytically inactive. There are three different crystal

http://dx.doi.org/10.1016/j.jscs.2017.04.001
1319-6103 Ó 2017 King Saud University. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article in press as: R. Moussaoui et al., Sol–gel synthesis of highly TiO2 aerogel photocatalyst via high temperature supercritical drying, Journal of
Saudi Chemical Society (2017), http://dx.doi.org/10.1016/j.jscs.2017.04.001
2 R. Moussaoui et al.

forms of TiO2: rutile, anatase and brookite [2,3]. The two latter preparation started from the reaction of a solution of titanium
phases are metastable at all temperatures and transform com- (IV) isopropoxide in isopropylic alcohol (96%, Riedel-de
monly to rutile when they are heated. The three crystalline Haën) (molar ratio 1:4) with water (molar ratio between water
forms of Titania can be synthesised by various techniques. and alcohol 1:8) performed under constant stirring at room
These include dry methods such as flame synthesis [4–7], chem- temperature. A white precipitate starts appearing indicating
ical vapour deposition [8] and wet chemistry methods such as and the formation of hydrate titanium oxide. The precipitate
the chloride (TiCl4) method [9], hydrothermal processing so obtained was aged overnight at room temperature to ensure
[2,10–18] and the sol–gel methods [19–25]. The sol gel process the conclusion of the hydrolysis. The isopropanol was then
is predominant because it has got distinct advantage from evaporated in a rotary evaporator to yield concentrated white
others due to mixing of the constituents at the atomic scale; precipitate. The acetic acid CH3COOH was added drop wise to
simplicity of operation and low cost [3,23]. The sol–gel route the mixture. After gelation during two days, the wet gel was
involves a two step reaction process: hydrolysis and condensa- transferred to a 100 mL Teflon-lined stainless steel autoclave,
tion. Metal alkoxides (M–OR) are widely used as precursors followed by high temperature supercritical isopropanol drying
because, they readily react with water [26]. However, this pro- at T = 300 °C (T > Tc isopropanol 235 °C) and 100 bars for
cedure usually requires post heat treatment in order to convert 1 h. The sample was denoted as aerogel TA.
the xerogel into crystalline titanium oxide. This would remove A second ‘‘classical’’ procedure of drying in an oven at
the hydroxyl groups and organic residuals [7]. Because the syn- 200 °C and atmospheric pressure for ten days was used. The
thesis without calcination step would mean lower cost due to resulting powders, TiO2 xerogel (TX), were compared to aero-
less energy consumption. The number of papers on the prepa- gels to observe the effect of drying.
ration of nanosized crystalline TiO2 anatase particles at low
temperature is undergoing an exponential increase [27–29]. 2.2. Catalysts characterization
Titanium dioxide particles have been the subject of a great deal
of research because of their unique physicochemical properties The powder X-ray diffraction patterns were recorded at room
and applications in the areas of pigments, catalysts and sup- temperature (using advanced D8, Bruker, Germany): X-ray
ports, fine ceramics, cosmetics, gas sensors, inorganic mem- tube operating at 40 kV and 40 mA, 0.6 mm fixed divergence
branes, environmental purification, and dielectric materials slits, diffracted beam curved graphite monochromator (Cu
[30–34]. In this regard, a variety of synthetic methods to pre- Ka+1 radiation, k1 = 1.540600 Å, k2 = 1.544390 Å) and
pare TiO2 xerogel and aerogel have been utilized while varying 0.1 mm fixed slit in front of the scintillation detector. The data
the pH of solution (acid-catalyzed or basic–catalyzed) and the were collected in the 2h range 10–120° with a step size of 0.02°
drying processes such as supercritical (aerogel) or conventional and a counting time of 5 s/step. All peak data measured by
drying (xerogel). The application of TiO2 in photodegradation XRD analysis were assigned by comparing with those of
of organic pollutants in water has also been discussed in liter- PCD database. Raman spectra were recorded with a LAB-
ature [35–48] and it is reported that surface, structural proper- RAM HR800 Raman Spectrometer equipped with a He-Ne
ties and photocatalytic efficiency depend strongly on the ion laser emitting at a wavelength of (633 nm). The morphol-
method used for the preparation of materials. However, there ogy and size were observed by HRTEM micrographs with a
is no direct correlation between surface proprieties and photo- JEOL-JEM 2000EX microscope, working at a 100 kV acceler-
activity of TiO2 [49]. ating voltage. The scanning electron microscopy (SEM) and
The present work aims at complementing such investiga- the energy dispersive X-ray spectroscopy EDX measurements
tions comparing TiO2 xerogel and aerogel which are synthe- were carried out on a (Philips XL 30) system operating at
sized by the acid-catalyzed sol–gel method and two different 20 keV. Infrared absorption spectra were measured on a Shi-
drying processes. To avoid the esterification reaction between madzu FT-IR-8400 s spectrometer by the transmission method
acetic acid and isopropyl alcohol, the acid has been added after using the KBr pellet technique with 4 cm
1 resolution.
the evaporation of alcohol. An advantage of this step is to UV–vis absorption was recorded on a LAMBDA 1050 UV/
ensure that all acid quantity completely react with hydrate tita- Vis/NIR Spectrophotometer in the wavelength range of 200–
nium oxide Ti-OH. Another scope of this study is to confirm 800 nm. The widths of the effective band gap of the samples
that acid does not affect the crystallinity of anatase TiO2 aero- were determined using Kubelka–Munk theory [43,50].
gel obtained through the high temperature supercritical drying.
Contrary, the acidic catalyst enhances the phase transforma- 2.3. Photo-catalytic properties
tion of the TiO2 xerogel from amorphous to anatase and the
growth of brookite phase. The obtained TiO2 xerogel and
In order to test photo-catalytic behavior of the synthesized
aerogel were tested in the photo-degradation of indigo carmine
TiO2 xerogel and aerogel, photo-degradation of indigo car-
in water.
mine in water has been chosen as a test reaction. The reactor
used for the photo-degradation (Fig. 1) is constituted by Pyrex
2. Experimental
cover (A) (to filter the infra red radiations coming from the
lamp), a mercury steam lamp HPK-125 W emitting in the
2.1. Catalysts synthesis UV region (B), a cover (C), a one liter volume cylinder (D),
a thermo regulated bath to maintain a stable temperature in
Nanocrystalline powders of TiO2 xerogel and aerogel were pre- the reactor (E), a magnetic stirrer (F), and an oxygen supply
pared by using acid-catalysed sol–gel approach. Titanium (IV) (G).
isopropoxide [Ti(OC3H7)4, Sigma–Aldrich, 97%] was used as a 250 mg of photo-catalyst were added to 1000 mL of a
titanium source to prepare both TiO2 xerogel and aerogel. The 30 mg/L indigo carmine solution. The suspension was stirred

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Saudi Chemical Society (2017), http://dx.doi.org/10.1016/j.jscs.2017.04.001
Sol–gel synthesis of highly TiO2 aerogel photocatalyst via high temperature supercritical drying 3

Figure 1 Reactor used on the photocatalytical degradation of indigo carmine.

for 40 min in dark to ensure even dispersion of the photo- X-rays [54]. However, the TX sample reveals the presence of
catalyst and to allow the establishment of an adsorption–des- a mixed phase anatase and brookite (peak in circle,
orption equilibrium. Then, the mixture was irradiated using 2h  30.8°) (PCD # 1906427) and small amount of amorphous
mercury lamp (Philips HPK 125 W). The reaction progress phase with anatase as dominant phase. The sample obtained
was followed by systematic sampling. The taken samples were by conventional drying seems to be the one retaining some
filtered through 0.45 lm membrane filter and the concentra- amorphous hydrous gel obtained from the hydrolysis-
tion of carmine indigo measured by UV–Visible spectropho- polycondensation reaction. These results suggest that the prob-
tometer at 610 nm. ability of preferentially establishment of anatase phase is much
higher with supercritical condition due to the influence of high-
3. Results and discussion pressure on network cross-linking. HRTEM and the well
defined diffraction SAED patterns were applied as an addi-
3.1. Effect of drying process on crystallinity of the prepared tional tool for the detection of mixed phase anatase and broo-
materials kite. The diffraction rings (Fig. 2c) demonstrates that TA is
only composed of anatase crystalline structure with high crys-
tallinity (1 0 1), (0 0 4), (2 0 0) and (1 0 5) planes. In contrast, the
In order to study the effects of the drying processes on relative
diffraction rings of TX (Fig. 2d) reveals the presence of anatase
crystallinity of the prepared materials, Rietveld refinement
and brookite (1 2 0) and (1 2 1) planes [29].
method [51] was applied on the analysis of XRD data of TX
We performed a supplementary experiment, using basic–
and TA (Fig. 2). The quality of the agreement between
catalysed (NH4OH) sol–gel approach to study the effect of
observed and calculated patterns for each phase gives the crys-
the nature of solution on the crystalline structure (Fig. 3).
tallinity degree of anatase phase.
Apparently, the TA and TA0 produce the same XRD patterns
The diffractogram of TA mainly composed of anatase crys-
and both contain only the anatase phase. There is, however, a
talline structure with high crystallinity (Pearson’s Crystal Data
small difference in crystallinity between TA and TA0 . This
PDF# 1003622). Apparently the supercritical conditions,
result indicates well that the use of either NH4OH or CH3-
adopted to remove the solvent in the case of the aerogel, are
COOH does not play a key role in the crystallization process
such as to provoke the growth of the crystallites and to pro-
under high temperature supercritical drying. In contrast, the
mote the formation of the anatase polymorph [52]. Crys-
addition of basic catalysis during hydrolysis influences the
tallinity is often much higher for high-temperature
phase structure and crystallization of the anatase under con-
supercritical aerogels compared to low-temperature supercriti-
ventional drying. The XRD spectral pattern of xerogel TX0
cal aerogels. Kong et al. [53] developed a direct synthesis of
does not show any strong diffraction peak except weak noise.
anatase TiO2 aerogel by drying the gel in high-temperature
These results are similar to those observed by Yu et al. [55],
supercritical ethanol. These authors claim that the supercritical
who synthesized TiO2 xerogel by sol–gel method using nitric
ethanol drying led to the decomposition of most of the organic
acid. These authors claim that the presence of an acidic cata-
groups in the TiO2 gel and formation of anatase TiO2. In the
lyst enhances the phase transformation of the TiO2 powders
case of low-temperature supercritical drying with CO2
from amorphous to anatase and the growth of brookite phase
(Tc = 31 °C, Pc = 73.8 bar), the as-synthesized samples
at 100 °C with weight fractions of 65.2 and 34.8%, respec-
derived by aerogel approach are completely amorphous to
tively. In contrast, the NH4OH retards the phase transforma-

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4 R. Moussaoui et al.

Figure 2 X-ray powder diffraction spectra and Rietveld plot of (a) TA (aerogel); (b) TX (xerogel). The Figures (c) and (d) show the
corresponding selected area electron diffraction SAED of TA and TX, respectively. *(1 2 0) and *(1 2 1) brookite planes.

of these particles causes them to form amorphous titanium.

When acid is added, hydroxylated titanium agglomerates are
electrostatically charged, breaking into small particles, and
the solution becomes clear; this phenomenon is called petiza-
tion. At 100 °C, the number of collisions between particles
increases, leading to a higher crystallization rate and resulting
in the formation of the metastable polymorphs anatase or
brookite.
Raman spectroscopy is a powerful technique for the inves-
tigation of various phases of titanium dioxide. Typically, for
anatase TiO2 TA, there are four Raman active fundamental
modes at 142 (Eg), 197 (Eg), 397 (B1g), 518 (A1g + B1g), and
640 cm
1 (Eg) (Fig. 4), respectively [56]. The result indicates
that the anatase is the predominant phase structure. Compared
to TiO2 TA, additional peaks at 243, 284, 320, 363 and
450 cm
1 were observed for TX sample (Fig. 4) characteristic
of brookite phase in agreement with XRD results [57].

Figure 3 X-ray powder diffraction spectra of TX0 (xerogel) and 3.2. Effect of drying process on morphology of prepared
TA0 (aerogel) samples prepared by basic-catalysed method. materials

SEM micrographs were applied as an additional tool to

tion of the TiO2 powders from amorphous to anatase but also
observe the effect of drying methods on final morphology
suppresses the growth of brookite phase. Indeed, when the
(Fig. 5a,b). The high temperature supercritical drying leads
alkoxide is added directly to the water and isopropanol, it
to a homogeneous and uniform dispersion of particles which
reacts very fast, producing a large quantity of hydroxylated
that are still coherent together. The evolution to a more homo-
titanium. This can be seen as a white polymer suspended in
geneous microstructure can be expected for TA sample
the solution. Subsequently, because of the constant stirring this
(Fig. 5a). Under high temperature supercritical isopropanol
polymer breaks into small particles, forming a white precipi-
drying, that is above critical temperature (Tc = 235 °C) and
tate; these are large agglomerates of colloidal particles joined
critical pressure (Pc), there is no distinction between the liquid
together by vander Waals attractions. The high nucleation rate

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Sol–gel synthesis of highly TiO2 aerogel photocatalyst via high temperature supercritical drying 5

From electron dispersive spectroscopy (EDS) (Fig. 5c,d), it

Eg was clear that the TX sample still contain fairly high concen-
trations of carbon then that of TA. This can be connected to
the residual organic groups that hardly removed from the
xerogel. As we have reported in our previous work [61], further
increases of temperature to 550 °C can remove all carbon
impurities in the solid.

3.3. FT-IR studies

A1g +B1g
Eg B1g Eg Fig. 6 shows the FT-IR spectra of the xerogel TX and aerogel
b b b b TA after drying at 200 °C in the range from 4000 cm
1 to
TX
600 cm
1. Compared to xerogel TX, the aerogel TA did not
TA shown bands at 1006, 1127 and 1168 cm
1, characteristic of
Ti(O–C) stretching vibration of the isopropoxy groups
200 400 600 800 1000 1200 (OC3H7) bonded to titanium ions [62] (Fig. 6, inset). No bands
Raman shift (Cm ) -1 at 1795, 1296 and 1410 cm
1, characteristic of free acetic acid
could be detected in TA spectrum. This result indicates that the
Figure 4 The Raman spectra of TA (aerogel) and TX (xerogel). high temperature supercritical drying (300 °C) was able to
b represents brookite. remove the unreacted acetic acid which has a critical tempera-
ture close to 300 °C.
The peaks at 1027, 1351, 1438 and 1545 cm
1 are assigned
and vapour phases, i.e., there is no liquid/vapor meniscus, and to adsorbed acetate groups on Ti sites. In particular, the dou-
thus no capillary pressure, preventing the shrinkage of gel [58]. blet in 1551 and 1451 cm
1 are assigned to the asymmetric
The volume of grains and pores remain homogeneous. In con- masym(COO) and symmetric msym(COO) stretching vibrations
trast, the SEM image of the TX sample (Fig. 5b) represents of the acetic acid group coordinated to Ti as a bidentate acet-
some stacked particles with a high density (circled areas). Note ate ligands [63]. These results reveal that the acetic acid group
that under conventional treatment (subcritical solvent condi- may play not only acidic catalyst in the medium, but as chelat-
tions), the evaporation of solvent from the wet gel leads to high ing agent coordinated to titania surface. However, we note
stresses in the structure of xerogel due to the capillary pres- that Ti(OC2H5)4 are hydrolyzed rapidly and form Ti(OC2H5)-
sures at the gel/solvent interface [59,60]. This may create addi-
xOHy (nucleophilic attack) as reported in our previous work
tional random porosity, cracks and breaking of the amorphous [64]. The formation of hydrated titanium Ti–OH is favored
structure. with high hydrolysis rates for a medium amount of water. In

Figure 5 SEM images and EDX spectra of: (a) and (c) of TA; (b) and (d) TX.

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6 R. Moussaoui et al.

0,8
2,0

0,6

0,4
1,5
1168 1127
0,2

Transmittance (a.u) 1,0 0,0

1300 1200 1100 1000 900
a

0,5

1545
1438

1027

660
b

c
0,0

4000 3000 2000 1000

-1
wavenumber (Cm )

Figure 6 The FT-IR spectra of TA and TX.

this stage, some acetic acid molecules can miss the chance of band gap energies of TiO2 aerogel (TA) and xerogel (TX) were
bonding with Ti atoms and then act as acidic catalyst mole- found to be 3.19 and 3.27 eV respectively.
cules. The rest can strongly coordinate to metal oxide surfaces
as a bidentate ligand via dissociative adsorption. Liu et al. [65] 3.5. Photo-catalytic activity
synthesized highly active mesoporous TiO2 photocatalyst by
hydrothermal route using acetic acid aqueous solutions. These Indigo carmine was employed to assess the photo-catalytic
authors showed that the strong chelating effect and acidity of activity of the as-prepared TiO2 xerogel and aerogel samples.
acetic acid leads to a significant control of hydrolysis reaction To compare the performance of the as-prepared photo-
of titanium precursors. However, the chelating effect of acetic catalysts, commercial material Degussa P25-TiO2 was used.
acid has been neglected in the present work. Furthermore, the The 95% photo-degradation times are 12, 18 and 18 min
TA shows a broad shoulder around 700–900 cm
1 reflects the for TiO2 aerogel (TA), Degussa P25-TiO2 (P25) and TiO2
cross-linking degree of –Ti–O in Ti–O–Ti anatase structure. xerogel (TX), respectively (Fig. 8). The reaction kinetics of
The intensity of this band was decreased for TX sample, indi- UV light assisted photo-degradation of indigo carmine in
cating that the material powder was present in some amor- water was studied. The first order kinetic Langmuir Hinshel-
phous form with some hydrated water molecules. wood model was followed:

3.4. UV–vis diffuse reflectance studies lnðC0 =CÞ ¼ kt

where, C0 is the initial concentration, C is the concentration at
The UV–vis adsorption spectra of TiO2 aerogel (TA) and xero- any time t and k is the apparent rate constant.
gel (TX) samples were depicted in Fig. 7. The typical absorp- The plots of ln(C0/C) versus time yielded straight lines indi-
tion edges of the tow samples were around 387 nm. The cating the photo-catalytic degradation of indigo carmine
obeyed pseudo-first order reaction kinetics (Fig. 8). The appar-

(a) (b)
TA TX TX TA
Absorbance (a.u.)

(αhν)2 (a.u.)

200 400 2.5 2.7 2.9 3.1 3.3 3.5

Wavelengh (nm) 600 800 hν (eV)

Figure 7 UV-vis spectra of TA and TX (a); band gap of TA and TX (b).

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Sol–gel synthesis of highly TiO2 aerogel photocatalyst via high temperature supercritical drying 7

TA TX P25

30
C (mg/L)

4 -ln(C/C0) = 0.1669t
R² = 0.9944
-ln(C/C0)= 0.2493t
20
3 R² = 0.9923

-ln(C/C0) = 0.1253t
-ln(C/C0)

R² = 0.9940
2

10 1
TA TX P25

0
0 5 10 15 20 25 30
Time (min)
0
-40 -30 -20 -10 0 10 20 30
Time (min)

Figure 8 Kinetics of the photocatalytic degradation of indigo carmine. In the insert: first-order linear transforms ln(C0/C) = f(t).

decreased from TA > P25 > TX. The as-prepared TiO2 aero-
Table 1 BET surfaces area of materials. gel (TA) exhibited a significantly faster degradation rate for
Reference A1 P25 X1 indigo carmine compared to commercial material Degussa
SBET (m2/g) 89 52 203 P25-TiO2. The higher photo-catalytic efficiency of TA com-
pared to P25-TiO2 may be attributed to the much higher sur-
face area (Table 1).
However, for TiO2 xerogel, even if its specific surface area is
ent rate constants of TA, P25 and TX are 0.2493, 0.1669 and greater than that of TA and P25, it shows lower photo-
0.1253 min
1 with R2 0.9923, 0.9944 and 0.9940, respectively. catalytic efficiency [66]. Indeed, in addition to the specific sur-
The catalytic activity of the degradation of indigo carmine face, photo-catalysis of organic pollutants is largely related to

30

TA

2nd

-ln(C/C0) = 0.1584t 3rd

20 4 R² = 0.9912
-ln(C/C0) = 0.1095t
-ln(C/C0) = 0.2493t
R² = 0.9908 10th
C (mg/L)

R² = 0.9923
3
-ln(C/C0)

2 -ln(C/C0) = 0.0865t
R² = 0.9883
10
1
1st 2nd 3rd 10th
0
0 10 20 Time (min) 30 40

0
-40 -30 -20 -10 0 10 20 30 40
Time (min)

Figure 9 Kinetics of the photocatalytic degradation of indigo carmine during the recyclability test. In the insert: first-order linear
transforms ln(C0/C) = f(t).

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8 R. Moussaoui et al.

the crystalline quality of the photo-catalyst [34,67,68]. The Acknowledgements

crystalline phase promotes photo-catalysis while the specific
surface area is responsible for the catalysis part. Thus, the oxi- We greatly acknowledge financial support of the Ministry of
dant radicals are formed when the charge carriers created by Higher Education and Scientific Research of Tunisia.
absorbed UV-photons are trapped in the surface. Trapping
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Saudi Chemical Society (2017), http://dx.doi.org/10.1016/j.jscs.2017.04.001
Sol–gel synthesis of highly TiO2 aerogel photocatalyst via high temperature supercritical drying 9

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Please cite this article in press as: R. Moussaoui et al., Sol–gel synthesis of highly TiO2 aerogel photocatalyst via high temperature supercritical drying, Journal of
Saudi Chemical Society (2017), http://dx.doi.org/10.1016/j.jscs.2017.04.001