Microporous and Mesoporous Materials 117 (2009) 233242

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Synthesis and characterisation of novel titania

impregnated kaolinite nano-photocatalyst
Meng Nan Chong a, Vipasiri Vimonses a, Shaomin Lei c, Bo Jin a,b,d,*, Chris Chow d, Chris Saint b,d
a

School of Chemical Engineering, The University of Adelaide, Adelaide, SA 5005, Australia

School of Earth and Environmental Sciences, The University of Adelaide, Adelaide, SA 5005, Australia
c
School of Resource and Environment Engineering, Wuhan University of Technology, Wuhan 430070, China
d
Australian Water Quality Centre, SA Water Corporation, Bolivar, SA 5110, Australia
b

a r t i c l e

i n f o

Article history:
Received 7 March 2008
Received in revised form 16 June 2008
Accepted 24 June 2008
Available online 9 July 2008
Keywords:
TiO2
Kaolinite
Photocatalysts
Heterocoagulation
Congo red
Solgel

a b s t r a c t
Nano-sized titanium dioxide (TiO2) has received a great attention in the eld of research and development as a promising photocatalyst to promote the degradation of organic contaminants in water. One
of the key technical challenges involved in separation and recovery of the photocatalyst particles from
the water treatment system makes this technology unviable as an industrial process. A novel titania
impregnated kaolinite (TiO2/K) photocatalyst was synthesized by a modied two step solgel method:
hydrolysis of titanium(IV) butoxide and heterocoagulation with pre-treated kaolinite (K) clay. The
TiO2/K photocatalysts were characterised using X-ray diffraction (XRD), scanning electron microscopy
(SEM), transmission electron microscopy (TEM) and BET specic surface area measurements (BET). The
photocatalytic activity was evaluated by the degradation of Congo red in aqueous solution. The TiO2/K
photocatalyst had a rigid porous layer structure and promising nano-size properties, and demonstrated
an enhanced adsorption and photocatalytic ability for the removal of Congo red. The TiO2/K photocatalyst
can be easily separated and recovered from the water treatment system. The TiO2/K photocatalyst is
expected to deliver a true engineering solution for an industrial water/wastewater treatment process.
2008 Published by Elsevier Inc.

1. Introduction
Heterogeneous photocatalysis employing nano-sized titanium
dioxide (TiO2) has been an attractive research and development
subject in water treatment owing to its proven capability in the
degradation of bio-recalcitrant organic contaminants [19]. The
high specic surface area (SSA) of the photocatalyst as a result of
its nanometer size has rendered its high efciency in degrading
indiscriminately any organic contaminants [1012]. However,
there are still some technical challenges that impede this novel
technology towards large scale implementation. One of the most
prominent challenges is the post separation and recovery of the
photocatalyst particles after water treatment due to the very ne
particle size and hence the reusability of the particles [13,6]. It
was reported that the small size (430 nm) of the TiO2 (Degussa
P25) can easily form aggregates in suspension, resulting in a significant reduction in both its effective surface area and photocatalytic
efciency [3].

* Corresponding author. Address: School of Earth and Environmental Sciences,

The University of Adelaide, Adelaide, SA 5005, Australia. Tel.: +61 8 8303 7056; fax:
+61 8 8303 6222.
E-mail address: [email protected] (B. Jin).
1387-1811/$ - see front matter 2008 Published by Elsevier Inc.
doi:10.1016/j.micromeso.2008.06.039

In recent years, numerous researches have been devoted in

searching for the suitable substrates that could be used as an
immobiliser to alleviate the problems involved in the post separation and aggregation. The immobiliser substrates, including glass
matrix, Raschig rings, bre optics, silica, stainless steel plates, synthetic membranes, and clay minerals were used in a number of
investigations [9,1317]. Direct coating of the TiO2 on the internal
surface of the photoreactor has been studied [18,19]. The selection
criteria for an ideal substrate for the immobilised-catalysts seem to
be a compromise of one another and depend on the reactor conguration. For instance, inorganic immobilisers such as clay minerals
(i.e., zeolites and montmorillonite) are meant for application in
suspension reactor system, while stainless steel plates and membranes are suitable for continuous operation processes.
TiO2 supported on inorganic clay minerals has received wide
attention. The natural structure and adsorption ability of the clay
materials can maintain large SSA, stability and consequently enhance the photocatalytic efciency of the photocatalysts [1,3,6,13,
2023]. This is because the photocatalytic reaction occurs on the
particles surface through the generated hydroxyl radicals (OH).
The enhanced adsorption provided by the clay minerals could direct
more contaminants to the surface of the particles prior to photocatalysis. Therefore, the selection for the suitable clay minerals is the
key step for the success in developing the immobilised-catalysts.

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a clay mineral with the chemical composition of Al2Si2O5(OH)4

[26,27]. It is a layered silicate mineral with one layer of octahedral,
which reacts with one sheet (Si2)3(OH)2)n, resulting in a two-layer
sheet structure [24,27]. The siliceous side of K presents a surface of
oxygen, while the aluminous side provides a surface of hydroxyl
groups. These double layers are then stacked upon one another
with the OH groups of one such sheet against the oxygen of the
next sheets [28]. The interaction between the stacked layered in
K are bonded covalently to each other, rather than Van der Waals
or electrostatic forces [24]. This interaction force makes K suitable
as a structurally rigid substrate for supporting and immobilizing
the TiO2. The strong interaction forces make the immobilized particles chemically stable from swelling and can endure high temperature of up to 950 oC (Fig. 2). To our knowledge, no investigation
using the K clay as an inorganic support for TiO2 in photocatalysis
was reported in the literature.
This study was to synthesize a novel titania impregnated kaolinite (TiO2/K) nano-photocatalyst through a modied two step sol
gel method. A series of tests were carried out to characterise the
surface properties of the prepared photocatalyst. The photocatalytic ability was evaluated through the degradation of Congo red

O
OH
Si
Al

Fig. 1. The crystal structure of kaolinite, viewed on the left hand side along b-axis
and on the right hand side along a-axis. The c-axis is vertical. (Reproduction from
Barrer [3]).

The physical properties of the immobilised-catalysts used in the

suspension reactor system have to be considered. For instance,
montmorillonite shows a high capability in adsorption. However,
the clay minerals may be swelled rapidly in the suspension system,
resulting in particle sedimentation and poor hydrodynamics in the
photoreactor [3,13,24,25].
In this work, Australian kaolinite (K) clay was used as the TiO2
immobiliser. K (Fig. 1) belongs to the kandites mineral group and is

2
76.24C
399.9J/g

444.47C
239.5J/g

152.76C

984.99C

Heat Flow (W/g)

502.72C

-2

-4
1144.20C

-6
0

200

400

Exo Up

800

1000

1200

110

0.12
497.70C

108
0.10

106
104

0.08

Weight (%)

1.299% Component 1

102

(0.3488mg)

100

0.06

98
96

Onset temp:

94

0.04

442.51C

11.83% Component 2
(3 .178mg)

0.02

92

Residue:
87.34%
(23.46mg)

90

0.00

[] Deriv. Weight (%/C)

600

Temperature (C)

88
86
0

200

400

600

800

1000

-0.02
1200

Temperature (C)
Fig. 2. Differential thermal analysis and thermogravimetric proles for raw kaolinite. (a) Heat ow against temperature prole. (b) Weight loss against temperature prole.

M.N. Chong et al. / Microporous and Mesoporous Materials 117 (2009) 233242

in the laboratory photoreactor system. The characterisation study

on the TiO2/K would provide useful information for better understanding of the adsorption and degradation mechanisms, and the
role of K in providing a structurally rigid and thermally stable support, bonding interaction and photocatalytic enhancement for the
TiO2/K photocatalysts.
2. Experimental set up
2.1. Materials
Titanium(IV) butoxide (tetrabutyl orthotitanate, purum grade
P97% gravimetric, SigmaAldrich), absolute ethanol (AR grade,
Labserv Pronalys Australia) and sodium pyrophosphate (Analar
grade, BDH VWR, England) were used as received. Raw K materials
were obtained from Unimin, Australia. Nitric acid (AR grade 69
wt%, BDH VWR, England), sodium hydroxide (Analar grade, BDH
VWR, England) and Congo red (C32H22N6Na2O6S2, Labchem Ajax
Finechem, Australia) were prepared to a desired concentration by
the addition of Milli-Q water obtained from Barnstead Nanopure
Diamond Water ion exchange system with 18.2 M-cm resistivity.
2.2. Pre-treatments of kaolinite materials
The K clay was puried by a series of sedimentation, base treatment and outgassed at a temperature in accordance to the differential thermal analysis (DTATG), as shown in Fig. 2a and b. The
K has a low cation exchange capacity of 15 meq/100 g. The suspension with 20 g L 1 K was allowed to settle in a 20 cm high jar. The
supernatant containing approximately <10 lm K was decanted.
This supernatant was adjusted to pH 10 by 2 M NaOH, while the
resultant mixture was stirred rigorously for 30 min. The K suspension was then ltered, washed and dried at 70 oC for 4 h. The dried
K samples were outgassed at 750 oC for 1 h. The particle size distribution for the pre-treated K particles is shown in Fig. 3.
2.3. Preparation of TiO2/K photocatalysts
The TiO2/K nano-photocatalysts were prepared by hydrolysis
and condensation of titanium(IV) butoxide, heterocoagulation
and subsequent heat treatment. These preparation procedures involved two steps before heat treatment, where the titania sol
was rst produced under an acid catalysed condition before heterocoagulation with the base-treated K under constant hydrothermal conditions at 37 oC. Twenty-ve milliliter of titanium(IV)
butoxide was mixed with 30 mL of absolute ethanol under vigorous magnetic stirring. This mixture was denoted as mixture A.

235

The 60 mL diluted nitric acid (HNO3) was then added drop wise
into the mixture A. The mixture A was stirred constantly until
the dispersion became rst milky white and subsequently transparent homogeneous sol with no visible precipitation. The stirring
was continued for 30 min until a transparent sol with certain viscosity was attained.
As the second step of the synthesis process, the K particles were
dispersed in 100 mL of Milli-Q water and the resultant K suspension was placed in a three necked round bottom ask. This ask
was then set in a water bath set at 37 oC. The K suspension was
mixed completely. The resultant homogeneous sol from the rst
step of the synthesis was then added drop wise into the K suspension with the aid of a separatory funnel. The mixture in the ask
was then continuously stirred for 4 h before the mixture was
cooled down to the room temperature. The resultant heterocoagulated mixture, denoted as mixture B, was then aged for 1316 h,
depending on the concentration of HNO3 used. The mixture B
was ltered and washed repeatedly three times with Milli-Q water,
and then dried at 6570 oC for 24 h. A 3 h heat treatment was carried out at an increasing rate of 2 K/min to desired temperature.
After calcination, the samples were cooled down to room temperature. The newly prepared photocatalyst of TiO2/K was stored in
the desiccators before use. For the bare TiO2, the K suspension step
was taken off and the resultant mixture A was also stirred in the
water bath at 37 oC before being washed, ltered, dried and calcined under the same conditions as those stated above.
2.4. Characterisations of TiO2/K photocatalysts
The particle size distribution of the K sample was measured
using a particle sizer (static light scattering laser diffraction)
instrument (Malvern Mastersizer 2000), which covers the measurement range from 0.02 to 2000 lm. For this size measurement,
the K particles were dispersed in water with sodium pyrophosphate added with agitation and sonication until a stable dispersion
was achieved.
The differential temperature analysis (DTA) coupled with thermogravimetric analyser (TGA) (TA Instruments) were used to analyse the weight loss of K as a function of elevated temperature. The
K sample was heat treated in the range of room temperature up to
1200 oC at a heating rate of 10 oC/min under high purity nitrogen
gas to avoid any possible oxidation by atmospheric oxygen or air.
Scanning electron microscopy (SEM) images were obtained
using the Nanoscope II Electrochemical electron microscope at an
accelerating voltage of 5 kV. The images of transmission electron
microscopy (TEM) were obtained using Philips CM-100 TEM at an
accelerating voltage of 100 kV. The prepared TiO2/K photocatalysts

Fig. 3. The particle size distribution curve for the pre-treated particles.

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M.N. Chong et al. / Microporous and Mesoporous Materials 117 (2009) 233242

were suspended in ethanol (approximately 0.01% (w/v)), followed

by ultrasonic treatment before being dropped onto the measurement copper grids of 2 mm in diameter. The particle size for the
coated TiO2 crystallites were estimated using the image analysis
software analySIS.
The BrunauerEmmettTeller (BET) specic surface area of the
TiO2/K photocatalysts under different HNO3 concentration were
determined by a micromeritics gas adsorption analyser (Gemini
Type 2375) at 77 0.5 K in liquid nitrogen. Prior to the surface area
measurements, the sample vessels loaded with ca. 0.51.0 g were
pre-treated in vacuum at 378.15 K and evacuation pressure of
50 mTorr for overnight. The adsorption isotherms were then analysed for the corresponding specic surface area using the BET
equation.
X-ray diffraction (XRD) measurements were performed on a
Philips PW Diffractometer (Co X-rays k = 1.7902 ) over the range
of 590 2h for the solid K powder samples. Samples were spiked
with 10 wt% of zinc oxide before analysis to facilitate the
calculation for the weight percent of the amorphous phase. The basal distances, dL, were calculated from the Bragg reections using
the automated powder diffraction software. The average crystallite
diameters of the particles, Dhkl, were obtained by using the Debye
Scherrer equation [Dhkl = ka/b cosh], where b is the line broadening
(b = bsbo, where bs and bo are the half-widths of the XRD peak of
the standard), k is related to the crystalline shape and taken to be
0.89 with Warrens correction for instrumental broadening, and a
and h are the radiation wavelength and Bragg angle, respectively.
A standard for this instrumental measurement based on single
crystal anatase TiO2 was used as a mean for calibration.
2.5. Photocatalytic experiments on Congo red
Congo red was used as a surrogate indicator to evaluate the
photocatalytic degradation ability of the newly synthesized TiO2/
K nano-photocatalysts. Congo red, a secondary diazo dye, is a recalcitrant azo dye found in textile wastewater. It has been involved in
several photocatalysis studies including those using TiO2 and
hence is appropriate in making comparisons for the current study.
The chemical structure of the Congo red is as shown in Fig. 4.
The photocatalytic degradation of the Congo red was performed
in a crude box reactor system. The reaction solution was placed in a
beaker and stirred using a magnetic stirrer. An 11 W UV light
(Davis Ultraviolet, Australia) was positioned on the top of the beaker with an intensity of approximately 300 lW/cm2 on the surface
of the swirling uid. A simple sampling unit was connected to the
beaker where a 50 mL syringe was used to withdraw the reaction
solution into a connected screw cap vial for sample collection.
The air ventilation in the reactor box was controlled using a vacuum pump, where the air inside the box was replenished at a rate
of 2 L/min through a 1 cm diameter opening on the both side of the
box.
The reaction solution contained 40 mg L 1 of Congo red. The
reaction solution was then stirred vigorously for 30 min on the
magnetic stirrer to ensure homogeneous mixing. A triplicate of
the reaction solution was then sampled where the absorption spec-

Fig. 4. Chemical structure of Congo red (a secondary diazo dye).

tra for the solution was scanned using UVvisible spectrophotometer (Helios Gamma, England). From the absorption spectra scan
ranging from 200 to 700 nm, it was found that the most intense
peak for the reaction solution was at 496.5 nm. Then a series of
absorption spectra measurements were conducted for each of the
quarterly diluted reaction solution in order to plot the absorbance
concentration prole. Each measurement for the diluted points
was repeated three times to minimise measurement errors.
Then 100 mL of the reaction solution was introduced into the
beaker placed on the magnetic stirrer with 1 g of TiO2/K photocatalysts. The suspension was allowed 30 min dark adsorption before
the UV light was switched on. The samples were collected every
1 h and centrifuged at 5000 rpm for 10 min. The supernatants were
then ltered using Millex VX lter (Millipore 0.45 lm) to ensure
the reaction samples were free of TiO2/K solids. Finally, the concentration of Congo red in the ltered supernatant was measured and
calculated using the UVvisible spectrophotometer (at 496.5 nm)
and the absorbance concentration prole. The sampling and sample tests were carried out in triplicate.

3. Results and discussion

3.1. Pre-treatments of kaolinite
Natural clay minerals consist of surface bounded water, zeolitic
water, other chemicals and impurities [13,25]. These impurities
might affect the interlayer pore space and hence the total effective
surface area that are necessary for the subsequent heterocoagulation process with titania sol [24]. Some foreign chemicals existing
in the kaolinite might induce internal reactions during the process
of the catalyst preparation, consequently affecting the properties
and photocatalytic activities of the TiO2/K. [25]. An appropriate
treatment to remove these impurities from the raw kaolin clay is
needed.
The natural K materials were subjected to thermogravimetric
analysis (DTATG) in order to obtain the weight loss prole against
the temperature gradient. The DTATG curves can be useful to
determine the maximum applicable outgassing temperature to remove these impurities. It is important to note that outgassing K
materials beyond or above the maximum applicable temperature
could cause an abrupt decrease in the pore volume owing to the
irreversible collapses of the clay structure [24,25]. Both Fig. 2a
and b show the thermal analysis thermogravimetric (DTATG)
curves. The rst weight loss of the K as shown by the broad endothermic peak was found at 150 oC, which was attributed to remove
the surface bound water. The second endothermic peak at 503 oC
corresponds to the dehydroxylation of the single layer of water between each pair of silicate sheets in the K. DTATG curves show
that an exothermic peak onset exists at 985 oC, corresponding to
the maximum applicable outgassing temperature. This temperature denoted the onset of the irreversible collapse to the K structure and hence outgassing of the K particles should not be done
beyond or above this temperature. Therefore, the outgassing temperature was chosen at 750 oC for 1 h.
The BET specic surface area (SSA) measurements were carried
out to examine the effect of the chosen outgassing temperature on
the physical properties of the K. The result shows that the outgassed K particles have a lower SSA than the K particles which
were dried at 70 oC. The SSA of the outgassed K decreased from
15.24 0.02 m2/g to 14.54 0.09 m2/g. This SSA decrease may be
the result of collapse in the oxide layer between the silicate sheets
in the K structure. The c spacing of the K structure shrank from
10 to 7.2 when the single water layer was driven off. Barrer
[24] reported that the tunnels in the outgassed K will be impeded
as a consequence of the outgassing treatment. This impedance only

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M.N. Chong et al. / Microporous and Mesoporous Materials 117 (2009) 233242

allows small polar molecules to replace the water layer but the ne
brous habit of the crystals sustains a large surface area [24].
Hence, the resultant outgassed K particles present an enhanced rigid structure with large surface area that can minimise the possibility of chemical intercalation and promotes the reuse potential
for the prepared photocatalysts.
3.2. Synthesis of titania sol
The synthesis of the titania sol was carried out by the modied
two step solgel method. Titanium(IV) butoxide was used as the
titanium precursor in the initial gelation step of the acid catalysed
solgel process. We found that the transparent titania sol was not
formed using 1 M HNO3, which was the recommended HNO3 concentration in previous reports [29,30]. Suh et al. [31] reported that
the formation of a transparent titanium aerogel only occur in a
small range of HNO3 concentration. The treatment of titania coated
substrates with certain acid concentration can improve the photocatalytic ability [4,32,33]. It is important to nd a suitable HNO3
concentration to control the formation of titanium sol [5]. A study
on the impact of the HNO3 concentration on the preparation of the
solgel and photocatalytic activity of the TiO2 has not been reported in the literature.
Fig. 5 indicates that the HNO3 concentration ranging from 0.05
to 1 M has a varying impact on the formation of solgel. The optimal HNO3 concentration range of 0.250.30 M can contribute to
the formation of transparent titanium sol (i.e., denoted as clear
gel (hard)) after aging for 1316 h. The HNO3 plays an important
role in controlling the rates of hydrolysis and condensation reaction of the titanium alkoxides precursor, so that the TiOH monomers can be slowly condensed associated with the growth of
strong TiOTi polymeric network [31]. When an excessive
amount of HNO3 was used, the hydrolysed solution of titanium
precursors exhibited an extensive degree of uidity even after
aging for 1316 h [34]. The excessive use of HNO3 can retard the
condensation process and further affects the monomer cluster
cluster growth to form the TiOTi polymeric network in the titanium sol [7,31,34]. However, once a low concentration of HNO3
was used, the gelation rate increased until a precipitation occurred.
It was note that a suitable HNO3 concentration contributes to not
only the formation of suitable homogeneous transparent titanium
sol but also the gelation behaviour and textural properties. Fig. 5
shows that the titanium sol exhibited four gelation behaviours
and textural properties. A HNO3 concentration lower than the optimal range of 0.250.30 M resulted in increasing the gelation rate
and forming a precipitated gel. Suh et al. [31] reported that the pre-

cipitated gel was due to the presence of precipitates in the polymeric gel network. The hard gel performed a low degree of
uidity and has a negative impact on the subsequent heterocoagulation process with the pre-treated K particles. Therefore, the concentration of 0.250.30 M HNO3 was used in the following
experiments.
It was observed that the photocatalysts prepared with different
HNO3 concentrations performed variable initial absorption ability
for the Congo red. Fig. 6 shows that the TiO2/K prepared with
0.28 M HNO3 contributed to an optimal 30% removal of Congo
red by initial adsorption. This adsorption ability is generated by
the strength of the polymeric gel network formed under different
molarity of HNO3. This strength can be further enlarged when
the TiO2/K is heat treated, resulting in TiO2/K particles with variable particle sizes and SSA [3537]. The different network structure of the TiO2/K can be proven through the direct comparison
of SEM images e.g., in Fig. 7a and b, which shows the surface
images of the prepared photocatalysts under the optimal 0.28 M
of HNO3 and the pre-treated K, respectively. The original prototype
of the K surface was in a at sheet pattern. A highly porous structure was observed after the attachment of TiO2 crystallites. The results shown in Section 3.3 revealed that the K prepared under the
optimal molarity of HNO3 had a signicant larger SSA of
35.24 0.11 m2/g than the pre-treated K (14.54 0.09 m2/g), as
stated in Section 3.1.
Robert et al. [38] stated that the resultant titanium sol should
have its pH adjusted to pH 3 with the addition of 1 M sodium
hydroxide (NaOH). We found that the pH value for the resultant
titania sol was 1.76. The use of NaOH to adjust the initial pH up
to 3 likely contributed to the formation of large dense TiO2 crystallite after calcination. This was evidenced from the peak broadening in X-ray diffraction. Although the mechanism for the
formation of the dense crystallites was unclear, it can be seen that
the pH adjustment had an important impact on the formation of
dense crystallites, the porosity of the structure, and consequently
the adsorption capacity of the TiO2/K. Thus it was proposed here
that the pH adjustment of the titania sol should not be carried
out to preserve the high specic surface area, but instead the
molarity of HNO3 or other preparation conditions should be
altered.
It can be concluded that the titania sol required for the subsequent heterocoagulation with pre-treated K can be synthesised under the optimal HNO3 range of 0.250.30 M without further pH
adjustment with NaOH. This is certainly benecial as the enhanced
adsorption capability promotes the surface reaction and hence the
photocatalytic efcacy of the TiO2/K.

Precipitation
Gel Precipitated (Hard)
Clear Gel (Hard)
Very Clear Gel (Soft)
No Gel

Ti 0

0.2

0.4

0.6

0.8

mol/LHNO3

Fig. 5. The textural properties of titania sol under different concentration of nitric acid.

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M.N. Chong et al. / Microporous and Mesoporous Materials 117 (2009) 233242

Fig. 6. Initial adsorption tests of Congo red (40 ppm) for the photocatalysts prepared under different molarity of nitric acid. The other preparation conditions were constant;
volume ratio Ti: EtOH: HNO3: 5:6:12. The K suspension loading used is 10% (w/v) (i.e., 10 g in 100 mL water). Calcination temperature is 600 oC.

3.3. Heterocoagulation process

Fig. 7. SEM images for sample K (a) After outgassed; (b) After coated with TiO2
(0.28 M HNO3).

The TiO2/K nano-photocatalysts were synthesised using the

pre-treated K materials. Heterocoagulation process constitutes
the second step of the preparation of the titanium sol. The titanium
sol was slowly added into the K suspension. This procedure is
anticipated to promote interaction and attachment of the positively charged titanium sol onto the slightly negatively charged
pre-treated K particles [13].
Through the heterocoagulation process, it was noted that the
quantity of the K added in the suspension has a direct impact on
the property of the photocatalysts. The quantity of the settled K
particles was independent of the amount of K in the suspension.
Two separate phases were clearly distinguished in the heterocoagulated mixture, representing coated particles and independently
precipitated K particles.
K suspension was tested with three different K loadings during
the preparation. At a low concentration of 5% (w/v) (i.e., 5 g of K in
100 mL of Milli-Q water), no individual precipitation of K particles
was found in the heterocoagulated mixture after aging. This
showed that the K particles could interact fully with the titanium
sol without generating any excess K particles. However when the
coated particles were examined under the TEM, massive crystal
structures with relatively thick and inconsistent coated layer could
be observed (Fig. 8a and b). It was believed that the bulkiness of
the crystals led to a decrease in the total SSA and the reproducibility of the synthesis method. Size quantication on the thickness of
the coated layer was carried out by taking the images of a specic
particle by tilting the focus angles on the TEM. The inhomogeneity
of coating layer has affected the thickness measurement in this
case. Hence, a higher concentration of K in the suspension is
preferred.
The suspension with 10% (w/v) and 15% (w/v) of the K were
determined for controlling the thickness of the coated layer on
the K particles. This was based on the rationale that an increase
in the K particles could provide more crystal nucleation sites for
the titanium sol, resulting in a decrease in the thickness of the
coating layer [39,40]. At 10% (w/v), a uniform layer of coated
TiO2 thickness was formed on the surface of the K particles. The
coated layer was made up by small subunits of TiO2 crystals with
an average particle size distribution of 7 nm (Fig. 8c and d),

M.N. Chong et al. / Microporous and Mesoporous Materials 117 (2009) 233242

239

Fig. 8. TEM images for photocatalysts prepared under different loading in kaolinite suspension. (a and b) 5% w/v; (c and d) 10% w/v; (e and f) 15% w/v.

depending on the extent of the heat treatment condition. As a result of the smaller subunits of TiO2 crystal, the formation of the
uniform coating layer contributed to an increase in the SSA. These
results were shown in Section 3.4. A higher K concentration of
(15% w/v) resulted in a relatively distant dispersion of crystal
growth as presented in Fig. 8e and f, in which there were only
a few crystals formed on a K particle with inconsistent particle
size around 610 nm. This is due to an increase in the crystal
nucleation sites from 10% (w/v) to 15% (w/v) that superseded
the xed amount of titanium sol that will be attached onto the
K particles. Therefore, 10% (w/v) of K suspension was chosen for
all the subsequent experiments. A further study needs to be conducted to effectively determine the exact weight percentage in
controlling the coating lm thickness, so that the optimal particle
size to SSA can be found.

3.4. Heat treatment of the photocatalyst

The heat treatment is a pre-requisite step for the transformation of titanium sol into structural rigid and stable TiO2 crystallites
that are attached rmly onto the K particles. This is because the
coated titanium sol is amorphous in nature, and further heat treatment could transform the coated TiO2 layer into the photoactive
crystalline phase. Many researchers reported that the temperature
for the heat treatment could alter the crystal structure, SSA, particle size, as well the photoactive phase of TiO2 crystalline [2,3537].
In the prepared photocatalysts, the heat transformation of
amorphous into the TiO2 crystalline involves the shrinkage and collapse of the polymeric TiOTi gel network onto the K particles
[2,31]. During the course of shrinkage, the TiOTi polymeric network is believed to form an interaction bonding with the siliceous

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M.N. Chong et al. / Microporous and Mesoporous Materials 117 (2009) 233242

side of K that presents a surface of oxygen and resulting in the formation of TiOSi bonding. Gates et al. [41] reported that the presence of such bonding is highly benecial in inuencing the stability
of the prepared photocatalysts and its application for the utilisation in catalysis. Besides this, it was also reported that the existence of such TiOSi bonds could suppress the phase
transformation of anatase to rutile [2]. This is highly benecial,
as most of the self-synthesized TiO2 is highly photoactive in its
anatase form. All these have shown the inuences of K, apart from
providing a structural rigid support. However, the existence of
such bonding is highly inuenced by the preparation conditions,
mainly the calcination temperature. In order to synthesise a highly
photoactive photocatalyst that compromises the essential criteria
such as the particle size, SSA and crystalline phase, an extensive
study needs to be conducted to govern the correlation between
each of the criteria.
Fig. 9 shows the correlation between the particle sizes and SSA,
and the calcination temperature. The size of the TiO2 crystallites
coated on the K particles has direct relationship with the calcination temperature. When the calcination temperature increased

from 500 oC to 700 oC, the particle size increased from approximately 6 nm to 18 nm. The increase in the particle size which is
due to the formation of agglomerates and accompanying crystal
growth (as evidenced from SEM and XRD peak) led to a reduction
in the SSA of the prepared photocatalysts. The SSA changed slightly
from 39.23 0.10 m2/g to 35.24 0.11 m2/g between 500 oC and
600 oC. An abrupt decrease in the specic surface area to
25.51 0.12 m2/g was observed when the particles were treated
at 650 oC.
Table 1
The characteristics of the titania/kaolinite nano-photocatalysts prepared under
different degrees of heat treatment
Calcination
temperature (oC)

Photoactive
phase (A/R)

BET specic surface

area (m2/g)

Particle
diameter (nm)

500
550
600
650
700

Anatase
Anatase
Anatase
Anatase/rutile
Anatase/rutile

39.23 0.10
37.87 0.10
35.24 0.11
25.51 0.12
24.04 0.12

6.13
6.50
7.09
12.76
18.32

Fig. 9. The correlation between specic surface area (m2/g) with calcination temperature (oC) and particle diameter (nm).

Fig. 10. X-ray diffraction (XRD) patterns for the titania/kaolinite nano-photocatalysts under different heat treatment conditions. (A) 500 oC; (B) 550 oC; (C) 600 oC; (D) 650 oC;
(E) 700 oC. A: Anatase; R: Rutile.

M.N. Chong et al. / Microporous and Mesoporous Materials 117 (2009) 233242

241

Fig. 11. The kinetics for the photo-degradation of 40 ppm of Congo red in the reactor system.

The abrupt decrease in SSA found at 650 oC may be due to the

phase transformation of the crystalline TiO2 [31,35]. Although the
phase transformation of anatase to rutile has been widely reported,
there is rarely a discussion on the structural change in TiO2 lattice
associated with the SSA change. A temperature for phase transformation from anatase to rutile was reported to be in a range between
550 oC and 800 oC, depending on the preparation conditions and
chemicals used [2]. We found that the phase transformation of crystalline anatase to rutile occurred at 650 oC, which was evidenced
from the XRD results shown in Fig. 10. Beydoun et al. [2] reported
that the anatase to rutile phase transformation involves the rupture
of TiO bonds. Thus, the breakage of the TiO bonds at 650 oC can
lead to a small SSA as the Ti lattice structure collapses. Apart from
this detrimental effect on the SSA, the heat treatment at 650 oC also
affects the cracking of the TiOSi bonds, as discussed earlier, and
alters the thermal stability of the photocatalysts (Table 1). It can
be concluded that the optimal heat treatment for the phase transformation of 600 oC is needed to maintain the highly photoactive
pure anatase phase with justiable particle size and specic surface
area for photocatalysis.
3.5. Photocatalytic degradation of Congo red
The photocatalytic degradation of Congo red was used as the
model reaction to evaluate the photocatalytic ability of the newly
synthesized TiO2/K photocatalysts. Congo red, a secondary diazo
dye is known to be a recalcitrant dye that presents a complication
in its removal from various sewage and industrial treated wastewater [8,42,43]. It was proposed that the photocatalytic oxidation
of Congo red commences with the oxidation on both of the azo
N@N bonds, resulting in the decolourisation and liberation of
molecular nitrogen [42,43].
Various studies on photocatalytic degradation of Congo red
have been conducted using TiO2 prepared from different synthesis
methods [8,14,4245]. Wahi et al. [43] prepared nine nano-sized
TiO2 photocatalysts with different particle size, SSA and anatase
to rutile phase composition for the photo-degradation of Congo
red. Their outcomes showed that the anatase nanorods prepared
using a surfactant concentration of 0.17 mmol L 1 tetraethyl
ammonium hydroxide performed a complete degradation of
14 lmol L 1 in 10 h.
In this study, the synthesized TiO2/K photocatalyst was applied
for the photocatalytic degradation of 40 ppm (57.4 lmol L 1) of
Congo red. Fig. 11 shows that both the initial adsorption and photocatalytic degradation of the Congo red was enhanced using the
TiO2/K. Approximately 30% colour removal was due to the initial

adsorption of the Congo red by the photocatalysts. The bare TiO2

(without immobilisation on K) demonstrated low photo-degradation ability. This can be explained by the fact that formation of
dense crystallites impeded up swirling and mixing in the reactor
system. The TiO2/K photocatalysts performed a high efciency in
the crude reactor system to degrade 40 ppm Congo red in 6 h. It
is important to note that the TiO2 coated on the K can improve
the homogeneity mixing by partitioning the titanium sol onto its
surface, and provides a structural support to enhance adsorption
capability, photocatalytic efciency and ease of separation.
4. Conclusion
A reproducible modied two step solgel method was developed to synthesise a novel TiO2/K nano-photocatalyst in this study.
The systematic manipulation in addition of the HNO3 to establish
the optimal concentration in the process not only provides titania
sol with optimal gel behaviours but a highly porous coating layer
that enhances adsorption ability. The TiO2/K photocatalyst synthesised using 10% (w/v) pre-treated K had a constant coating
thickness of 7 nm. The variation in the temperature of the subsequent heat treatment contributed to the TiO2/K photocatalysts
with different physical properties in terms of particle size, specic
surface area and the photoactive phase. The optimal heat treatment was suppressed at 600 oC. This was proposed to be primarily
due to the appearance of rutile phase at 650 oC, which resulted in
the rupture of TiO bonds and abrupt decrease in SSA.
The TiO2/K photocatalysts had desirable porous layer and nanosize structure and promising properties to demonstrate a high
adsorption and degradability for the removal of Congo red. Importantly, the immobilised TiO2/K particles can be easily separated
and recovered from a water treatment system. All this makes
TiO2/K nano-particles a novel photocatalyst for a viable industrial
water/wastewater treatment process.
Acknowledgments
This work was supported by the Australian Research Council
Linkage Grant (LP0562153) and Australian Water Quality Centre
through the Water Environmental Biotechnology Laboratory
(WEBL) at the University of Adelaide.
References
[1] A. Arques, A.M. Amat, L.S. Juanes, R.F. Vercher, M.L. Marin, M.A. Miranda,
Journal of Molecular Catalysis A: Chemical 271 (2007) 221226.

242

M.N. Chong et al. / Microporous and Mesoporous Materials 117 (2009) 233242

[2] D. Beydoun, R. Amal, Materials Science and Engineering B 94 (1) (2002) 7181.
[3] A. Bhattacharyya, S. Kawi, M.B. Ray, Catalysis Today 98 (2004) 431439.
[4] B. Cheng, J.G. Yu, X.Q. Zhang, X.J. Zhao, Journal of Materials Science Letters 22
(2003) 967970.
[5] H. Choi, Y.J. Kim, R.S. Varma, D.D. Dionysiou, Chemistry Materials 18 (2006)
53775384.
[6] Z. Ding, H.Y. Zhu, G.Q. Lu, P.F. Greeneld, Journal of Colloid and Interface
Science 209 (1998) 193199.
[7] D.D. Dunuwila, C.D. Gagliardi, K.A. Berglund, Chemistry Materials 6 (1994)
15561562.
[8] S. Erdemoglu, S.K. Aksu, F. Sayilkan, B. Izgi, M. Asilturk, H. Sayilkan, F. Frimmel,
S. Gucer, Journal of Hazardous
Materials, 2007, doi:10.1016/j.jhazmat.
2007.11.087.
[9] J. Fernandez, J. Kiwi, J. Baeza, J. Freer, C. Lizama, H.D. Mansilla, Journal of
Applied Catalysis B: Environmental 48 (3) (2004) 205211.
[10] L. Jing, X. Sun, B. Xin, B. Wang, W. Cai, H. Fu, Journal of Solid State Chemistry
177 (2004) 33753382.
[11] M.S. Lee, S.S. Hong, M. Mohseni, Journal of Molecular Catalysis A; Chemical 242
(2005) 135140.
[12] H. Yang, R. Shi, K. Zhang, Y. Hu, A. Tang, X. Li, Journal of Alloys and Compounds
398 (2005) 200202.
[13] K. Mogyorosi, I. Dekany, J.H. Fendler, Langmuir 19 (2003) 29382946.
[14] R. Molinari, F. Pirillo, M. Falco, V. Loddo, L. Palmisano, Chemical Engineering
and Processing 43 (2004) 11031114.
[15] S. Takeda, S. Suzuki, H. Odaka, H. Hosono, Thin Solid Films 392 (2) (2001) 338
344.
[16] Z. Xiong, Y. Xu, L. Zhu, J. Zhao, Langmuir 21 (2005) 1060210607.
[17] W. Yan, B. Chen, S.M. Mahurin, E.W. Hagaman, S. Dai, H. Overbury, Journal of
Physical Chemistry B 108 (9) (2004) 27932796.
[18] L. Zhang, Y. Zhu, Y. He, W. Li, H. Sun, Journal of Applied Catalysis B:
Environmental 40 (4) (2003) 287292.
[19] D. Zhao, J. Zhou, N. Liu, Materials Science and Engineering A 431 (2006) 256
262.
[20] I. Ilisz, A. Dombi, K. Mogyorosi, A. Farkas, I. Dekany, Applied Catalysis B:
Environmental 39 (2002) 247256.
[21] K. Mogyorosi, A. Farkas, I. Dekany, Environmental Science and Technology 36
(2002) 36183624.
[22] T. Mori, J. Suzuki, K. Fujimoto, M. Watanabe, Y. Hasegawa, Journal of SolGel
Science and Technology 19 (2000) 505510.

[23] Y. Xu, C.H. Langford, Journal of Physical Chemistry B 101 (1997) 31153121.
[24] R.M. Barrer, Zeolites and Clay Minerals as Sorbents and Molecular Sieves,
Academic Press Incorporation Ltd, London, 1978.
[25] H.I. Inyang, S. Bae, G. Mbamalu, S.W. Park, Journal of Materials in Civil
Engineering 19 (1) (2007) 8490.
[26] H.Z. Ma, B. Wang, Journal of Hazardous Materials: B 136 (2006) 365370.
[27] B. Wang, L. Gu, H. Ma, Journal of Hazardous Materials 143 (2007) 198205.
[28] Q. Zhuo, H. Ma, B. Wang, L. Gu, Journal of Hazardous Materials 142 (2007) 81
87.
[29] B.L. Bischoff, M.A. Anderson, Chemistry Materials 7 (1995) 17721778.
[30] K.P. Kumar, J. Kumar, K. Keizer, Journal of American Ceramic Society 77 (5)
(1994) 13961400.
[31] D.J. Suh, T.J. Park, Chemistry Materials 8 (1996) 509513.
[32] J.C. Yu, J. Yu, J. Zhao, Applied Catalysis B: Environmental 36 (2002) 3143.
[33] J.C. Yu, J. Yu, W. Ho, Z. Jiang, L. Zhang, Chemistry Materials 14 (2002) 3808
3816.
[34] M. Guglielmi, G. Carturan, Journal of Non-Crystalline Solids 100 (1988) 1630.
[35] N. Negishi, K. Takeuchi, Materials Letters 38 (2) (1999) 150153.
[36] Y. Tanaka, M. Suganuma, Journal of SolGel Science and Technology 22 (2001)
8389.
[37] B. Xia, H. Huang, Y. Xie, Materials Science and Engineering B 57 (2) (1999)
150154.
[38] D. Robert, J.V. Weber, Journal of Materials Science Letters 18 (1999) 9798.
[39] B. Aiken, E. Matijevic, Journal of Colloid and Interface Science 126 (22) (1998)
645649.
[40] I.U. Haq, E. Matijevic, Journal of Colloid and Interface Science 192 (1) (1997)
104113.
[41] B.C. Gates, H. Knozinger, Advances in Catalysis, Elsevier Science Book Edition,
2004.
[42] C. Guillard, J. Disdier, C. Monnet, J. Dussaud, S. Malato, J. Blanco, M.I.
Maldonado, J.M. Herrmann, Applied Catalysis B: Environmental 46 (2003)
319332.
[43] R.K. Wahi, W.W. Yu, Y. Liu, M.L. Mejia, J.C. Falkner, W. Nolte, V.L. Colvin,
Journal of Molecular Catalysis A: Chemical 242 (2005) 4856.
[44] I.K. Konstantinou, T.A. Albanis, Applied Catalysis B: Environmental 49 (2004)
114.
[45] Y. Yang, Q. Wu, Y. Guo, C. Hu, E. Wang, Journal of Molecular Catalysis A:
Chemical 225 (2005) 203212.