Powder Technology 253 (2014) 809–813

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Powder Technology
journal homepage: www.elsevier.com/locate/powtec

The effect of sulfate contents on the surface properties of iron–manganese

doped sulfated zirconia catalysts
Fatah H. Alhassan a,b,⁎, Umer Rashid c, Mothanna Sadiq Al-Qubaisi d,
Abdullah Rasedee d,e, Yun H. Taufiq-Yap a,b,⁎
a
Catalysis Science and Technology Research Centre, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
b
Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
c
Institute of Advanced Technology, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
d
Institute of Bioscience, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
e
Department of Veterinary Pathology and Microbiology, Faculty of Veterinary Medicine, University Putra Malaysia, Malaysia

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

Article history: The iron–manganese doped sulfated zirconia catalysts were prepared via precipitation method; the sulfation was
Received 25 June 2013 carried out by impregnation with different amounts of sulfate (4%, 10% and 16% SO−2 4 by weight) with the addi-
Received in revised form 15 December 2013 tion of Fe–Mn doped and calcined at 600 °C for 3 h. The prepared catalysts were characterized by TGA-DTA, XRD,
Accepted 27 December 2013
BET, FT-IR, TEM, TPD-NH3 and XPS. XRD and BET results revealed that the addition of sulfate imparts special sta-
Available online 5 January 2014
bilization to the catalytically active tetragonal phase of zirconia. All the iron–manganese doped sulfated zirconia
Keywords:
catalysts were found to have strong acid sites, high surface area and small crystallite size.
Iron–manganese doped sulfated zirconia 4% © 2014 Elsevier B.V. All rights reserved.
SO−4
2
by weight (FMSZ-4)
Sulfation
Dopants
Crystallite size

1. Introduction
Zirconium oxide is an active catalyst for many reactions, whose sur-
face possesses four chemical properties: acidic, basic, reducing and oxi-
dizing. It has become well established that the performance of a
heterogeneous catalyst depends not only on the intrinsic catalytic activ-
ity of its components, but also on its texture and stability. One of the
most important factors in controlling the surface properties of a catalyst
involves the correct choice of additives. The adsorption of various an-
ions [1], particularly sulfate or phosphate anions, onto oxide, has been
attempted as a means of improving their catalytic activity. The increase
in activity is believed to arise from an increase in the surface acidity of
the modified oxide [2]. Modification of metal oxides with sulfate anion
can generate a strong acidity, even stronger than 100% sulfuric acid
and hence they tend to become superacid catalysts that are useful in re-
actions like isomerization, low temperature esterification, alkylation
and cracking [3].
The acid strength of iron–manganese doped sulfated zirconia cannot
be measured by the color-change indicators because of its dark color.
However, it is regarded as superacid, judging from its catalytic activities
for the isomerization of n-butane at room temperature [4,5]. The iron–
manganese doped sulfated zirconia is reported to be about three orders
in magnitude more active than sulfated zirconia for isomerization of re-
action [5], with large amount of superacid sites, which shows that it has
the highest acid strength among solid superacids containing sulfate ion
[6]. Findings from our literature review showed that no work has been
done so far on the influence of sulfate amounts on the surface properties
of iron–manganese doped sulfated zirconia catalyst.
The main purposes of this study therefore are to prepare zirconium
oxide catalyst acidified with sulfate anions, doped with iron and manga-
nese and to study the effect of sulfate amounts on the surface properties
of it. ZrO2 was prepared from zirconyl oxychloride ZrOCl 2 and has
been sulfated using ammonium sulfate with different loading levels
of support (4%, 10% and 16% SO − 2
4 ); Fe (1.5%) and Mn (0.5%) ions
were supported on SO− 2
4 /ZrO(OH)2 by stepwise equilibrium adsorp-
tion of Fe(NO3)3·9H2O and Mn(NO3)2·4H2O aqueous solutions. The
catalysts were characterized using different tools to determine the
effect of sulfate levels on their surface properties.
2. Experimental procedure

2.1. Materials
⁎ Corresponding authors at: Catalysis Science and Technology Research Centre, Faculty
of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia. Tel.: + 60 3
89466809; fax: + 60 3 89466758.
Iron nitrate nonahydrate, manganese nitrate tetra hydrate, ammoni-
E-mail addresses: abuohamid9090@gmail.com (F.H. Alhassan), taufiq@upm.edu.my um sulfate, zirconium oxy chloride, and ammonium hydroxide (28–30%)
(Y.H. Taufiq-Yap). were obtained from (Sigma-Aldrich—Malaysia).

0032-5910/$ – see front matter © 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.powtec.2013.12.045
810 F.H. Alhassan et al. / Powder Technology 253 (2014) 809–813
Fig. 1. TGA and DTG profile for zirconyl hydroxide gel.
2.2. Catalyst preparation
5 g of hydrate zirconyl oxychloride ZrOCl2 was dissolved in about
100 ml of deionised water, dropwise addition of 2.63 g of a 25% aqueous
solution of ammonia led to precipitation; as much of the ammonia solu-
tion necessary to reach a pH of ≈9–10 was added. The precipitate was
allowed to age overnight, filtered by vacuum, washed several times
until it tested negative to chloride ion, and then dried for about 24 h
at 120 °C.
Fe(NO3)3·9H2O, Mn(NO3)2·4H2O and ammonium sulfate were dis-
solved in about 100 ml of deionised water in amounts corresponding to
the desired stoichiometry, solution was added dropwise to zirconium
oxyhydroxide solution and the mixture was vigorously stirred at room
temperature for 4 h. The mixture dried at 120 °C overnight and calcined
at 600 °C −3 h [7].
2.3. Catalyst characterization
The TGA analysis was carried out on a Mettler Toledo TG-SDTA
apparatus (Pt crucibles, Pt / Pt − Rh thermocouple) with the purge
gas (nitrogen) flow rate of 30 ml min − 1 and the heating rate of
10 °Cmin− 1 from 25 to 1000 °C.
The powder X-ray diffraction analysis was performed using a
Shimadzu diffractometer model XRD 6000. The diffractometer employed
Fig. 2. TGA and DTG profile for FMSZ-4.
Fig. 3. XRD patterns of sample Z, (FMSZ-4), (FMSZ-10), and (FMSZ-16) calcined at
600–3 h: (♦) tetragonal phase; (O) monoclinic phase.
Cu-Kα radiation to generate diffraction patterns from powder crystalline
samples at ambient temperature. The Cu-Kα radiation was generated by
Philips glass diffraction X-ray tube broad focus 2.7 kW type. The crystal-
lite size D of the samples was calculated using the Debye–Scherrer's rela-
tionship [8–11].
D ¼ 0:9λ=ðB cosθÞ
where D is the crystallite size, λ is the incident X-ray wavelength, β is the
full width at half-maximum, and θ is the diffraction angle.
The Fourier transform infrared (FT-IR) analysis was done with
PerkinElmer spectrometer model 100 series (sample preparation
UATR). The total surface area of the catalysts was obtained using
Brunauer–Emmer–Teller (BET) method with nitrogen adsorption at
− 196 °C. Analysis was conducted using a Thermo Fisher Scientific S.p.A
(model: SURFER ANALYZER) nitrogen adsorption–desorption analyzer.
The transmission electron microscopy (TEM, Model Hitachi H-7100,
Japan) was used to determine the crystal shape and homogeneity of the
zirconia and iron–manganese doped sulfated zirconia nanoparticles.
Briefly, the powder was dispersed in deionized water, dropped onto
carbon-cover copper grids placed on a filter paper and dried at room
temperature.
The acidity of the catalyst was evaluated by temperature pro-
grammed desorption using NH3 as probe molecule. The TPD-NH3 exper-
iment was conducted by Thermo Finnigan TPDRO 1100 apparatus
equipped with a thermal conductivity detector. About 0.1 g of catalyst
was placed in the reactor, treated under 150 °C for 15 min in N2
(20 ml/min). 10% NH3 in helium gas was ramped at 1 °C/min for
Table 1
Influence of sulfate loading on the surface area, pore volume and crystallite size.
Sample Specific surface area (m2 g−1), pore volume (cm3 g−1),
and crystallite size (nm)
Z 34.8 0.00056 25.5
FMSZ-4 72.0 0.01887 14.0
FMSZ-10 139.0 0.05336 9.5
FMSZ-16 149.0 0.05966 8.0
 F.H. Alhassan et al. / Powder Technology 253 (2014) 809–813
Fig. 4. FT-IR of Z, (FMSZ-4), (FMSZ-10), (FMSZ-16).
60 min. The purging with N2 was done at room temperature for 45 min
to remove NH3 in the gas phase. The analysis of NH3description was
then carried out between 50 °C and 900 °C under helium flow
(15 °C min−1, 20 ml min−1) and detected by a thermal conductivity
detector.
XPS spectra were obtained using a modified AXIS ULTRA DLD
(KRATOS) photoelectron spectrometer, equipped with a hemispherical
analyzer. For excitation, AlKα (1486.6 eV) radiation was used. The ana-
lyzer was operated in the fixed analyzer transmission mode at 40 eV
pass energy. The X-ray gun was operated at 4 mA emission current
and 15 kV acceleration voltage. Samples were pretreated under vacuum
(1 × 10−9 Torr) at 22 ± 2 for 2 h before measurements. The base pres-
sure of the analyzer chamber was 1 × 10−9 Torr; during data collection,
the pressure was still always b 1 × 10−9 Torr. Binding energy (BE) cor-
responding to C 1 s, Zr 3d, Fe 2p, Mn 2p, S 2p, and O 1s were measured.
All binding energies are relative to C 1s peak taken as 284.5 eV.
3. Results and discussion
3.1. Thermal analysis
The thermal behavior of zirconyl hydroxide (Fig. 1) showed three
stages of weight loss between 38 °C and 600 °C. The first weight loss
step between 38 °C and 105 °C was attributed to the removal of sur-
face physisorbed water molecules with 14.6%, the second mass loss
Fig. 5. TEM image of zirconia (a) and FMSZ-4 (b).
811
Table 2
The distribution of acid site strength of the catalysts under
investigation.
Catalysts NH3 desorbed (μmol/g)
Z 630.4
FMSZ-4 4318.4
FMSZ-10 5458.0
FMSZ-16 7544.0
step approximately between 413 °C and 437 °C with about 0.315%
mass reduction was due to dehydroxylation of zirconyl hydroxide
while the third stage between 447 °C and 743 °C of about 0.7% weight
reduction was assigned to the dehydration of hydrated zirconium
oxide. Correspondingly, the differential thermogravimetric profile
showed two peaks at around 105 °C and 432 °C [12]. Therefore, the ex-
hibited thermal events involved in general, elimination of water of dif-
ferent strengths with a final formation of ZrO2 agree well with the data
of XRD [13].
The iron–manganese doped samples exhibited a higher thermal sta-
bility. The commencement of decomposition in these cases occurred
only above 700 °C. Thus, it can be inferred that, besides delaying the
crystallization process, the addition of iron–manganese also helps in
stabilizing the surface sulfate species.
The TGA profile of iron–manganese doped sulfated zirconia 4% SO−2 4
by weight (FMSZ-4) sample depicted five mass loss steps (Fig. 2). The
first step, which ends at 236 °C, was attributed to the removal of phys-
ically adsorbed water, whereas the other three stages, which began at
around 238 °C and finished at about 518 °C, were assigned to the
decomposition of iron and manganese nitrate and dehydroxylation
process of ZrO(OH)2 [14]. The mass loss at higher temperature,which
began at about 673 °C and ended at 926 °C, was referred to as the
decomposition of sulfate group [15–17].
The delay in the transition from amorphous to crystalline material
by sulfate doping was supported by thermal analysis results. Consistent
with earlier reports [18–21], an increase in the sulfate loading shifted
the peak maxima towards the high temperature region.
3.2. X-ray diffraction
The XRD patterns of pure ZrO2 and iron–manganese doped sulfated
zirconia samples were illustrated in Fig. 3. The high temperature calci-
nation seems essential for the formation of the catalytically active te-
tragonal phase. Pure zirconia was crystallized even at 500 °C with
only the tetragonal phase.
812 F.H. Alhassan et al. / Powder Technology 253 (2014) 809–813

Fig. 6. XPS spectra of zirconia (a–b) and FMSZ-4 (c–g).

The XRD patterns of catalysts calcined at 600 °C of zirconia consist of dispersed Fe2 O3 and MnO particles along with bulky sulfate species
a mixture of monoclinic and tetragonal phases. The sharp diffraction on the surface of zirconia particles prevent their agglomeration during
peaks at around 2θ = 30.1, 35.1, 50.3 and 60.1° are due to the tetrago- calcination [23].
nal form of zirconia (JSPDS file no.: 01-081-1545). While the diffraction
lines at about 2θ = 17.2, 24.1, 27.8, 31.4, 34.2, 38.7, 41.2, 45.5, 49.3,
3.3. FT-IR spectroscopy
54.2, 55.7, 57.5, 58.0, 63.1, 66.0, 69.2, 71.1 and 73.2° are attributed to
the monoclinic phase of zirconia ((JSPDS file no.: 00-065-2357). XRD
Fig. 4 displays the FT-IR spectra of FMSZ (4-6-16). From these spec-
patterns of iron–manganese doped catalysts showed metastable phase
tra, the presence of sulfate groups was confirmed by the peak at a range
of tetragonal ZrO2 which appeared at 2θ = 30.1, 35.1, 50.4 and 60.1°
of 1225 to 1070 cm−1, which were due to the asymmetric and symmet-
(JSPDS file no.: 01-081-1545). Whereas, all the XRD patterns showed
ric stretching frequency of the O_S_O and O\S\O group. The band
only peaks of ZrO2 phases.
which is around 1380 cm −1 is characteristic for the surface sulfate
The intensity of the peak corresponding to the monoclinic phase was
species having S_O covalent bonds. The only effect of sulfate loading
not shown in the iron–manganese-doped samples signifying the stabi-
resulted in increasing the band intensities of the sulfate group [2,24].
lization of the tetragonal phase. The absence of characteristic peaks
matching to Fe2O3and MnO implies that the metal oxides are present
in the form of solid solution or it is well dispersed on the zirconia sur- 3.4. Influence of sulfate loading on the surface area and pore volume
face. The dispersion of Fe2O3 and MnO particles causes the stabilization
of the tetragonal phase and also imparts a higher surface area [11]. The variation in the surface area and pore volume with sulfate load-
To know the effect of sulfate content on the iron–manganese-doped ing of iron–manganese doped sulfated zirconia is presented in Table 1.
catalysts quantitatively, their mean crystallite sizes were obtained from Consistent with earlier reports, the iron–manganese doped samples
the broadening of the strongest peak of the samples based on Debye– showed a higher surface area as compared to the zirconia sample. The
Scherrer's equation (Table 1). The addition of sulfate was associated dispersed Fe2O3 and MnO particles along with the sulfate species
with a reduction in crystallite size to become 14.0, 9.5 and 8.0 nm prevent the agglomeration of zirconia particles leading to an enhanced
for iron–manganese doped sulfated zirconia 4% SO− 4
2
by weight surface area [19,25–27]. In the case of iron–manganese doped samples,
(FMSZ-4), iron–manganese doped sulfated zirconia 10% SO− 4
2
by an increase in sulfate content resulted in an increase of surface area.
weight (FMSZ-10) and iron–manganese doped sulfated zirconia 16% Furthermore, the pore volume of the samples also showed an increased
SO−2
4 by weight (FMSZ-16), respectively. This may be attributed to the trend with increased sulfate loading. Thus it can be assumed that the
sulfate groups that remain bounded on the surface of the samples and incorporation of iron and manganese prevents surface area loss during
inhibit the growth of zirconia crystallites, agreeing thus with the other high temperature calcinations resulting in a gradual increase in the
transition metal oxides, i.e. titania, stannia and ferria [22]. The decrease surface area of the samples FMSZ-4, FMSZ-10 and FMSZ-16 to become
in the crystallite size can be explained by the hypothesis that the 72, 139 and 149 m2/g, respectively.
 F.H. Alhassan et al. / Powder Technology 253 (2014) 809–813
3.5. Transmission electron microscope (TEM)
Fig. 5 confirms nanosized crystal shape in zirconia and iron–
manganese doped sulfated zirconia-4 catalysts as characterized by TEM.
The images of the crystals depicted in Fig. 5(a, b), were uniformly distrib-
uted at the nanometer scale having a clear shape and different size, being
approximately 50 nm with individual particles measuring 25–20.5 and
11–18 nm for zirconia and FMSZ-4, respectively, which was very well
in line with XRD data. The reproducibility of the method was established
through the triplicate preparations and triplicate analyses.
3.6. TPD-NH3
Total number of acid sites and their relative strength for the catalysts
under investigation can be measured by means of a total amount of NH3
desorbed as listed in Table 2. From these results one can conclude that
the Z sample has a low acid site density of 630.4 μmol/g. The addition
of Fe–Mn dopants and sulfate to ZrO2 can increase the acidic strength
and create very strong acid sites on the surface of ZrO2 to become
4318.4 μmol/g, 5458.0 μmol/g and 7544.0 μmol/g for the samples
FMSZ-4, FMSZ-10 and FMSZ-16, respectively.
3.7. X-ray photoelectron spectra
Both zirconia (Z) and FMSZ-4 samples showed a photoelectron
emission at 181.5 eV characteristic of Zr 3d5/2 and one at 530.0 eV
characteristic of O1s. These photoelectron peaks taken together, were
assigned to ZrO2 [28]. The peaks in Fig. 6(a, e) are assuming the presence
of two Zr(IV) components. The lower binding energy component is in
the range of Zr(IV) in ZrO2, whereas the higher binding energy compo-
nent (183.3, 185.5EV) corresponds to the formation of a Zr(IV) species
bound to a more electron-attractive species. The Zr 3d peak (Fig. 6(e))
confirms no appreciable modifications with respect to the peak of the
undoped oxide (Fig. 6(a)). The total absence of effects on the shape of
the Zr 3d peak is very interesting and indicative of the different strength
and nature of the interactions involved between sulfates and zirconia
for (NH4)2SO4 impregnation at these concentrations [29]. The S2p emis-
sion was located at about 168.6 eV (Fig. 6(c)) and suggests the presence
of S+6 in agreement with that relative to sulfur in sulfates and with pre-
vious results relative to sulfated zirconia samples [29].
Fig. 6(f) shows the XP spectrum of FMSZ-4 in the Fe 2p region. The
Fe 2p3/2 and Fe 2p1/2 emissions, located at about 711.3 and 724.0 eV, re-
spectively, support the existence of iron as an oxide at the surface of the
catalyst. This spectrum is a clear evidence of the presence of Fe+3and is
practically identical to the spectra that have been reported for Fe2O3
[30]. Mn peaks could be detected only with a rather poor noisy signal.
Fig. 6(g) displays the XPS spectrum of FMSZ-4 in the Mn 2p region. The
Mn 2p3/2 and Mn 2p1/2 photoelectron lines were observed at approxi-
mately 642.5 and 653.4 eV, respectively, which confirms the presence
of manganese oxide at the surface of the catalyst.
4. Conclusions
The obtained results show that the ZrO2 gel needs at least one mole-
cule of water to give the formula ZrO2·H2O and that the addition of ferric
and manganese as promoter and sulfate imparts a special stabilization to
the catalytically active tetragonal phase of zirconia, which decreases the
crystallite size and consequently, increases the specific surface area. The
specific surface area is increased by increasing the loading of sulfate.
Moreover, the incorporation of promoters and sulfate onto ZrO2 can in-
crease its acidity and create a strong acidic site. The XPS results indicate
the presence of the sulfate, Fe2O3, and MnO particles on the surface of
zirconia catalyst.
813
Acknowledgments
The authors acknowledge the financial support of the International
Graduate Research Fellowship (IGRF) from the Universiti Putra
Malaysia.
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