A. Kristiani et al.

/ (IJAEST) INTERNATIONAL JOURNAL OF ADVANCED ENGINEERING SCIENCES AND TECHNOLOGIES

Vol No. 1, Issue No. 1, 038 - 042

Novel Sulfated TiO2-ZrO2 Mixed Oxides Prepared by

Modified Sol-Gel Method

A. Kristiani, S N. Aisyiyah Jenie, J A. Laksmono, S. Tursiloadi

Research Centre for Chemistry
Indonesian Institute of Sciences - LIPI
Kawasan PUSPIPTEK Serpong, Tangerang, 15314, Indonesia, Phone: +62217560929, Fax: +62217560549
Email: anis.kristiani87@gmail.com

Abstract— A series of TiO2-ZrO2 mixed oxides (TZ) selectivity. The high activity and selectivity is caused by the
with various titanium contents from 0 to 100 wt%, were nature of the active sites. The active sites can be defined by
prepared by hydrolysis of metal alkoxide in alcoholic solution, the presence of surface protons generating Brønsted acidity or
immersed into a surfactant solution of cetyltrimethyl ammonium coordinately unsaturated cationic centers, i.e. Lewis acid sites.

chloride (CTAC) before drying, and characterization by X-Ray
Diffraction, X-Ray Fluorescence, Transmission Electron
Microscopy, Fourier Transformed-Infra Red, Brunauer Emmett
Teller method and acidity after calcination at 500 oC for 2h. The
XRD patterns of mixed oxides containing TiO2 rich showed
anatase phase, while TZ with 10wt% of TiO2 (TZ 10/90) was
amorphous. On the other hand, in TZ without TiO2 (TZ 0/100),
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the crystalline of ZrO2 was observed. The higher loading of
titanium caused the increasing of crystallinity, which was
consistent with the result observed by TEM measurement. The
specific surface areas of the mixed oxides were higher than that
of each single oxide. The largest specific surface area was
obtained for the TZ mixed oxide with 50 wt% of TiO2 (TZ 50/50).
The acidity properties determined by base adsorption method,
both ammonia and pyridine showed that TZ 90/10 had the
highest acidity, both total and surface acidity. All the samples
showed two types of acidic sites, both Brønsted and Lewis acid
sites confirmed by FT-IR adsorption spectra.
Keywords-Modified Sol-gel; Solid acid catalyst; Sulfated TiO2-
ZrO2
A
I. INTRODUCTION
It is well known that catalysts, both homogeneous and
heterogeneous catalyst, play an important role in many
chemical reactions. Homogeneous catalyst such as liquid acids
(HF, HCl, H2SO4, and HNO3) are used for reactions such as
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Metal oxides, especially ZrO2, TiO2, Fe2O3, and zirconia
containing mixed oxides modified by sulfate ions have been
found to be promising catalysts for low temperature
esterification, isomerization, alkylation, and cracking reactions
[1-6]. One of solid superacid, sulfate-promoted zirconium
oxide was reported in 1979 by Hino et al [7] as a catalyst for
the room temperature isomerization on n-butene. A solid
superacid catalyst would lower the reaction temperature
required for the isomerization. Sulfate is usually introduced by
immersing zirconium hydroxide in a dilute solution of sulfuric
acid or by impregnation from a solution of ammonium sulfate
[5].
Aerogels with high surface area and high porosity
materials were prepared by the sol gel method. The first step
in the preparation is the formation of an alcogel using sol gel
method. In the sol gel method, a metal alkoxide undergoes
hydrolysis and subsequent condensation in an alcohol solvent,
forming a polymeric oxide network entraining the alcohol. For
catalytic uses, the liquid solvent must be removed from the
gel. During conventional drying, a liquid-vapor interface
forms in the pores and the corresponding surface tension
collapses the oxide networks, therefore reducing its surface
area [8].
It is well known that mixing two oxides can create acidity.
The most widely accepted model for the generation of acid

hydrolysis, alkylation, esterification and isomerization.
Problems related to the separation from product stream,
corrosion, pollution and low selectivity strongly restrict their
industrial application [1-2]. On the contrary, heterogeneous
catalysts, such as several solid acid catalysts (inorganic
oxides, clays, zeolite, cation-exchange resins) are more
popular used in order to solve the problems of homogeneous
ones [1-2]. Two main characteristics of catalyst, the activity
and selectivity of catalyst, are greatly influenced by the
method of catalyst preparation and the condition of
pretreatment. The physical and chemical properties of a
catalyst varies with the method of preparations [3-4].
Solid acid catalysts have an additional advantages which
are easy separation from products, high activity and
sites on the mixed oxides is that the surface acidity results
from the charge imbalance based on the generation of Ti-O-Zr
bonding[1,9]. Tanabe’s model predicts Lewis acidity for
zirconia rich and Brønsted acidity for titania rich chemically
mixed TiO2/ZrO. Tanabe’s hypotheses was tested by studying
the adsorption of pyridine. It was found that in TiO2/ZrO2
binary oxides the number of Lewis sites per square meter was
equivalent to that in the pore oxides [5].
Sol gel hydrolysis is widely employed due to its capability
in controlling the textural and surface properties of the
resulting oxides. The preparation of titania-zirconia mixed
oxides with various ZrO2 content in TiO2 by the sol gel
method was reported by Manriquez et al. The number of acid
sites is dramatically increased. Their activity in the

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 A. Kristiani et al. / (IJAEST) INTERNATIONAL JOURNAL OF ADVANCED ENGINEERING SCIENCES AND TECHNOLOGIES
isopropanol decomposition showed a good correlation
between the acid-basic properties and the selectivity to
propene, acetone, and isopropyl ether [11].
Lonyi et al. studied the acidic and catalytic properties of
sulfated TiO2-ZrO2 mixed oxides and found that the addition
of titania as a second oxide to zirconia hindered the
aggregation of the oxide components [5]. Tursiloadi et al.
prepared mesoporous titania alumina ceramic by modified sol
gel method using surfactant templating, CTAC and
supercritical extraction and indicated that the thermal stability
of the microstructure of mesoporous titania alumina was
improved by surfactant immersion or supercritical extraction
[4]. Weissman et al. adopted a SCF extraction analogy to
obtain TiO2-ZrO2 mixed oxide aerogels [11]. In the SCF
method solvents were extracted from the gel without
collapsing its structure, which would often occur in the
conventional drying. They obtained an aerogel having a high
specific surface area [12].
In the present work, titania zirconia sulfated catalysts were
synthesized by the sol-gel method with surfactant templating.
The characterization of the catalyst samples was performed by
means of X-Ray Diffraction (XRD), X-Ray Fluorescence
(XRF), Transmission Electron Microscopy (TEM), Fourier
Transformed Infra Red (FTIR), BET Method, and NH3 also
Pyridine adsorption method. The novelty of our mixed metal
CTAC.
II. MATERIALS AND METHODS
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oxides is the preparation method of mixed oxides titanium and
zirconia sulfated via sol gel method modified by surfactant,
A. Catalyst Preparation
The precursors employed in the preparation of the sol gel
catalysts were titanium n-butoxide (98% Aldrich), zirconium
n-butoxide (99% Aldrich) and n-butanol (100% Merck).
Reference Titania was prepared as follows : 3.0 mol of n-
Butanol was put in a glass system at low temperature (0 °C)
A
with constant stirring. After, 0.5 mol of Titanium n-butoxide
were drop-wise added to the solution and then the pH was
adjusted to 3.0 with HNO3 (65% Merck). The flask was put
under reflux at 70 °C and stirred for 5 h. Finally 3.3 mol of
H2O were added to the reaction system and the resulting
suspension was maintained under reflux and constant stirring
until gelling was achieved. The ZrO2 reference was
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synthesized in the same using way but Zirconium n-butoxide
as Zirconia precursor.
TiO2-ZrO2 mixed oxides were synthesized following the
above procedures. Appropriate amounts of the Titanium and
Zirconium alkoxides were simultaneously added dropwisely
by drop to the n-Butanol solution at 0 °C and the pH was
adjusted at 3.0 with HNO3. The mixture was added by H2SO4
then put in reflux at 70 °C for 5h.Water for the hydrolysis step
was added drop wise. The amounts for the two alkoxides used
for the different synthesis are reported in Table 1.
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Vol No. 1, Issue No. 1, 038 - 042
TABLE I. EXPERIMENTAL RATIO USED IN THE SYNTHESIS OF THE
TIO2-ZRO2 MIXED OXIDES
TiO2-ZrO2 weight ratio
Titanium Zirconia
(wt%)
butoxide butoxide
(mol) (mol)
10-90 0.05 0.29
50-50 0.25 0.17
90-10 0.45 0.03
After gelling, all the samples of catalyst were immersed
overnight at room temperature in cetyltrimethyl ammonium
chloride (CTAC) solution, decanted, and then dried overnight
at 70 °C. Finally, the catalyst were calcinated at 500 °C
during 2h in air.
B. Characterization
X-Ray Diffraction
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Specimen were prepared packing the powder samples in a
glass samples holder. The X-Ray diffraction spectra were
obtained with MAX SCIENCE MXP3V diffractometer, using
Cu Kα radiation 0.5418 nm at 25 kV and 10 mA. The
measurements were recorded in scanning speed 1.00°/min
with divergence split 1°, scattering split 1°, receiving split
0.15 nm and sampling width 0.020° in the 2θ range of 20-60°.
Transmission Electron Microscopy
Samples prepared by dissolving in alcohol and stirred by
using ultrasonic. After prepared, samples were placed in grid
and observed by TEM JEM-1200EX.
Fourier Transformed-Infra Red (FT-IR)
To determine the nature and types of groups and their
bonding with TiO2-ZrO2 mixed oxides, all 500 °C calcined
samples were characterized by FT-IR spectroscopy in KBr
phase using FT-IR spectrometer (Shimadzu, Prestige-21) with
ATR 4000 attached to an automatic data acquisition center.
BET Method
The specific surface area of the samples was determined
using N2 adsorption/desorption method at 77 K by standard
BET method (Sorptomatic 1800 Carlo Erba Instruments).
Prior to each measurement all samples were degassed at 150
°C to evacuate the physisorbed moisture.
NH3 and Pyridine adsorption method
Acidity of all samples was determined by the irreversible
adsorption of organic bases, pyridine and ammonia. The
amount of base adsorbed is the acidity of samples in mmol/g.
III. RESULTS
A. Transmission Electron Microscopy
The TEM image of nanocatalyst are shown in Fig.1.
In Fig. 1(a), the image of TZ 100/0 which is pure TiSO4
without the addition of zirconia was observed as spherical
crystal with the particle size of 20 nm. In Fig.1(b), the image
of TZ 0/100 which is pure ZrSO4 without the addition of
titanium was observed as spherical crystal with the particle
size of 15 nm. In Fig.1(c), mixed oxide of TZ 50/50 shows
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 A. Kristiani et al. / (IJAEST) INTERNATIONAL JOURNAL OF ADVANCED ENGINEERING SCIENCES AND TECHNOLOGIES
Vol No. 1, Issue No. 1, 038 - 042

two images which are spherical and rods. In Fig.1d), TZ 90/10

As for sample TZ 10/90, it shows an amorphous spherical due
to the low concentration of titanium addition.

Fig.2. XRD Pattern of a) TZ 0/100; b) TZ 100/0; c) TZ

50/50; d) TZ 90/10 and e) TZ 10/90
(a) (b)

TABLE II. THE WEIGHT OF TI AND ZR IN TIO2-ZRO2 MIXED OXIDES

T
Catalysts wt% Ti by XRF wt% Zr by XRF
TZ 0/100 0.08 96.61
TZ 10/90 11.50 82.75
TZ 50/50 51.06 46.49
TZ 90/10 91.04 5.81
TZ 100/0 99.00 0.20
(c)
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(d)

C. Specific Surface Area

The specific surface areas of the pure and mixed oxides are
reported in Table 3. For TiO2 and ZrO2 the corresponding
specific surface areas were 56.4607 m2/g and 51.9638 m2/g,
respectively. In mixed oxides, the BET specific surface area
varies depending of the ZrO2 content, which were 110.2076
(TZ 90/10), 181.9822 (TZ 50/50) and 79.3421 m2/g (TZ
10/90). The largest specific surface area was obtained for TZ
10/90 mixed oxide.
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(e) (f)
TABLE III. SPECIFIC SURFACE AREA OF TIO2-ZRO2 MIXED OXIDES
Fig.1. TEM images of (a) TZ 100/0;( b) TZ 0/100; (c) TZ
Catalysts BET Area (m2/g)
50/50; (d) TZ 90/10 and (e) TZ 10/90
TZ 0/100 51.9638
TZ 10/90 79.3421
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B. XRD Diffraction
TZ 50/50 181.9822
XRD pattern for catalysts samples prepared are shown in
TZ 90/10 110.2076
Fig.2. For TZ 0/100, tetragonal crystalline phase were
observed. For TZ 100/0, the spectrum at peak  = 25 TZ 100/0 56.4607
corresponds to the anatase crystalline phase. In mixed oxides,
anatase phase was observed for the TiO2 rich region, while
sample TZ 10/90 is amorphous. On the other hand, in TZ D. Acidic Properties
0/100 the crystalline of ZrO2 was observed. No crystalline of The values of acidity are reported in Table 4. For TiO2
ZrO2 in TiO2-ZrO2 mixed. and ZrO2 the surface acidity was 0.8626 and 0.1309 mmol/g,
The real mole percent of titanium and zirconia in the TiO2- respectively. In mixed oxides, the acidity varies in depending
ZrO2 mixed oxides are reported in Table 2. It shown that the of the ZrO2 content, they were 1.9474 (TZ 90/10), 1.1615 (TZ
real mole of titanium and zirconia is approximately similar to 50/50) and 0.3686 mmol/g (TZ 10/90). The highest acidity
the mole ratio reacted. was obtained in the TZ 90/10 mixed oxide.

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Vol No. 1, Issue No. 1, 038 - 042

TABLE IV. THE ACIDITY OF TIO2-ZRO2 MIXED OXIDES 100/0 is bigger than TZ 0/100. Mixed oxide of TZ 50/50
Catalysts Surface Acidity Total Acidity shows two images which are spherical and rods. In this
using Pyridine using Ammonia sample, the addition of zirconia with the same concentration
Adsorption (mmol/g) Adsorption (mmol/g) resulted in a competition between two crystal structures,
TZ 0/100 0.1309 0.6330 anatase and rutile. TZ 90/10 shows spherical structure with
TZ 10/90 0.3686 1.0825 particle size of 10 nm due to the low concentration of zirconia.
The low concentration of zirconia which is 10% inhibited the
TZ 50/50 1.1615 1.7992
anatase spherical crystal growth from titanium hence produces
TZ 90/10 1.9474 3.1055 a smaller particle size. As for sample TZ 10/90, it shows an
TZ 100/0 0.8626 1.2096 amorphous spherical due to the low concentration of titanium
addition.
A detailed study of crystalline phases formed during the
E. FTIR-Ammonia Adsorption preparation process is of a great importance, because the
Ammonia adsorption is a valuable method to determine the nature of the crystalline phase can affect the catalytic
nature of acid sites in the mikropore of materials. In Fig.4, behavior. XRD pattern for catalysts samples prepared are
FTIR-ammonia adsorption spectra for TZ 0/100, TZ 100/0, shown in Fig.2. For TZ 0/100, tetragonal crystalline phase
TZ 90/10, TZ 50/50 and TZ 10/90 are shown. The broad peak was observed. For TZ 100/0, the spectrum at peak  = 25
at 3400 cm-1 is attributed to O-H stretching vibration of water corresponds to the anatase crystalline phase. In mixed oxides,
associated with the oxide matrix. In TZ 100/0, TZ 90/10, TZ anatase phase was observed for the TiO2 rich region, while

50/50 and TZ 10/90 samples, the adsorption bands around
986 cm-1 – 1140 cm-1 of TZ 100/0 shows bidentate sulfate
coordinated to Ti 4+. Moreover, the adsorption bands around
1400 cm-1 shows an ammonium ion which is formed on the
Brønsted acid sites and ammonia coordinately bonded to
Lewis sites in adsorption bands around 1627 cm-1 - 1635 cm-1.
In TZ 0/100, the adsorption bands around 1041 cm-1 shows
ES
bidentate sulfate ion coordinated to the metal Zr4+ and strong
band S=O stretching in adsorption bands around 1380 cm-1 –
1370 cm-1. Furthermore, the adsorption bands around 1402
cm-1 shows ammonium ion which is formed on the Brønsted
acid sites and the adsorption bands around 1618 cm-1 shows
ammonia coordinately bonded to Lewis acid sites.
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sample TZ 10/90 is amorphous. On the other hand, in TZ
0/100 the crystalline of ZrO2 was observed. No crystalline of
ZrO2 in TiO2-ZrO2 mixed. In both cases an inhibiting
crystallite size growth effect by Zr4+ or Ti4+ in TiO2 and ZrO2,
respectively, may occur. The oxide at low content will be
found as a large dispersed oxide in the ZrO2 or TiO2 structure,
respectively [11].
In sample TZ 10/90, the high concentration of
zirconia added lead to amorphous system. The higher loading
of titanium resulted in the increasing of crystalinity in the
order : TZ 90/10 < TZ 50/50 < TZ 100/0, respectively. The
XRD pattern of TZ 50/50 shows two phases, both anatase and
rutile. It were supported by TEM image of TZ 50/50 showed
two image, both spherical and rods. Moreover, as observed in
XRD pattern, the width of diffraction peak tend to increase in
order : TZ 100/0 < TZ 50/50 < TZ 90/10 < TZ 10/90,
respectively. The increase of width of the diffraction peak
indicated that the crystallite size of samples become smaller.
The specific surface area are also affected by the
preparation method. The specific surface areas of the pure and
mixed oxides are reported in Table 3. Aiken et al. reported
that sulphate, coordinated to two different atoms (sulphate in
bridged form) caused an increase in surface area. For TiO2 and
ZrO2 the corresponding specific surface area were 56.4607
m2/g and 51.9638 m2/g, respectively. In mixed oxides, the

BET specific surface area varies depending of the ZrO2

Fig.4. FTIR-ammonia adsorption spectra for a) TZ 0/100,
b) TZ 10/90, c) TZ 50/50, d) TZ 90/10 and e) TZ 100/0
IV. DISCUSSIONS
The effect of the preparation methods on the
microstructure of the samples can be seen in the TEM image.
The TEM image of nanocatalyst are shown in Fig.1. The
image of TZ 100/0 was observed as spherical crystal with the
particle size of 20 nm. TZ 0/100 was observed as spherical
crystal with the particle size of 15 nm. The particle size of TZ
content, which were 110.2076 (TZ 90/10), 181.9822 (TZ
50/50) and 79.3421 m2/g (TZ 10/90). The largest specific
surface area was obtained for TZ 10/90 mixed oxide showing
an amorphous form, as observed by XRD, Fig.1.The
dependence of the hydrolysis condensation rate between
titanium or zirconium alkoxides may affect the particle
agglomeration behavior and different textural properties of the
mixed oxides are a result of such effects [10]. The FTIR
patterns along with the specific surface area data in Table 3,
may suggest that sulphate in these oxides are bidentately
coordinated with a bridged structure.

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 A. Kristiani et al. / (IJAEST) INTERNATIONAL JOURNAL OF ADVANCED ENGINEERING SCIENCES AND TECHNOLOGIES
The nature of acid sites may be defined by the presence of
surface protons leading to the Brønsted sites or cationic
centers due to unsaturation in coordination, which explain the
Lewis acidity. The acidity, both surface and total acidity of the
pure and mixed oxides is determined by the irreversible
adsorption of pyridine and ammonia. Pyridine adsorbs only on
the strong acid sites. While, ammonia being a stronger base
adsorbs on all the samples [1]. The value of acidity are
reported in Table 4. For TiO2 and ZrO2 the surface acidity
were 0.8626 and 0.1309 mmol/g, respectively. In mixed
oxides, the acidity varies in depending of the ZrO2 content,
they were 1.9474 (TZ 90/10), 1.1615 (TZ 50/50) and 0.3686
mmol/g (TZ 10/90). The highest acidity was obtained in the
TZ 90/10 mixed oxide showing a large specific surface area,
as measured by BET method, Table.3. The specific surface
area correlated with the acidity of the samples. The large
specific surface area is more possible to adsorb base molecule
so will give the high acidity.
Ammonia adsorption is a valuable method to determine the
nature of acid sites in the surface of materials. In Fig.4, FTIR-
ammonia adsorption spectra for TZ 0/100, TZ 100/0, TZ
90/10, TZ 50/50 and TZ 10/90 are shown. The broad peak at
3400 cm-1 is attributed to O-H stretching vibration of water
associated with the oxide matrix[1]. In TZ 100/0, TZ 90/10,
TZ 50/50 and TZ 10/90 samples, the adsorption bands around
986 cm-1 – 1140 cm-1 of TZ 100/0 shows bidentate sulfate
ES
coordinated to Ti 4+. Moreover, the adsorption bands around
1400 cm-1 shows an ammonium ion which is formed on the
Brønsted acid sites and ammonia coordinately bonded to
Lewis sites in adsorption bands around 1627 cm-1 - 1635 cm-1.
In TZ 0/100, the adsorption bands around 1041 cm-1 shows
bidentate sulfate ion coordinated to the metal Zr4+ and strong
band S=O stretching in adsorption bands around 1380 cm-1 –
1370 cm-1. Furthermore, the adsorption bands around 1402
cm-1 shows ammonium ion which is formed on the Brønsted
acid sites and the adsorption bands around 1618 cm-1 shows
ammonia coordinately bonded to Lewis acid sites. [1,3,6].
A
This indicates the presence of both Brønsted and Lewis acid
sites on the surface of samples.
V. CONCLUSIONS
In the preparation of TiO2-ZrO2 mixed oxides by sol gel
method, solid acid catalysts with high surface area and acidity
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were obtained. The acidity determined by NH3 and pyridine
adsorption showed that in the mixed oxides the number of acid
sites is notably increased. FTIR-pyridine adsorption identified
the acid sites, both Brønsted and Lewis acid sites. XRD
pattern of samples shown that anatase as the predominant
crystalline phase in TiO2 and in the rich TiO2 mixed oxide (TZ
90/10 and TZ 50/50). In the mixed oxide at TZ 10/90
composition the sample is amorphous. On the other hand, in
the pure ZrO2 sample a mixture of tetragonal and monoclinic
crystalline phases were observed.
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Vol No. 1, Issue No. 1, 038 - 042
ACKNOWLEDGMENT
The authors gratefully acknowledge that the Ministry of
Research and Technology Republic of Indonesia for Basic
Insentive Research supported this study.
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