Journal of Solid State Chemistry 198 (2013) 496–505

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Journal of Solid State Chemistry

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

pH control of the structure, composition, and catalytic activity of

sulfated zirconia
Vladimir K. Ivanov a,b, Alexander Ye. Baranchikov a,c,*, Gennady P. Kopitsa d, Sergey A. Lermontov e,
Lyudmila L. Yurkova e, Nadezhda N. Gubanova a,d, Olga S. Ivanova a, Anatoly S. Lermontov a,
Marina N. Rumyantseva c, Larisa P. Vasilyeva f, Melissa Sharp g, P. Klaus Pranzas g, Yuri D. Tretyakov b
a
Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, Leninsky ave., 31, Moscow 119991, Russian Federation
b
Materials Science Department, Moscow State University, Moscow 119991, Russian Federation
c
Department of Chemistry, Moscow State University, Moscow 119991, Russian Federation
d
Petersburg Nuclear Physics Institute, Orlova Roscha, Gatchina 188300, Russian Federation
e
Institute of Physiologically Active Compounds of the Russian Academy of Sciences, Chernogolovka 142432, Russian Federation
f
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka 142432, Russian Federation
g
GKSS Forschungszentrum, Geesthacht 21502, Germany

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

Article history: We report a detailed study of structural and chemical transformations of amorphous hydrous zirconia
Received 30 July 2012 into sulfated zirconia-based superacid catalysts. Precipitation pH is shown to be the key factor
Received in revised form governing structure, composition and properties of amorphous sulfated zirconia gels and nanocrystal-
12 October 2012
line sulfated zirconia. Increase in precipitation pH leads to substantial increase of surface fractal
Accepted 18 November 2012
Available online 30 November 2012
dimension (up to  2.7) of amorphous sulfated zirconia gels, and consequently to increase in specific
surface area (up to  80 m2/g) and simultaneously to decrease in sulfate content and total acidity of
Keywords: zirconia catalysts. Complete conversion of hexene-1 over as synthesized sulfated zirconia catalysts was
Sulfated zirconia observed even under ambient conditions.
Small-angle neutron scattering
& 2012 Published by Elsevier Inc.
Mesostructure
Fractal properties

1. Introduction The most common route to prepare fine zirconia powders

includes precipitation of amorphous hydrous zirconia from aqu-
Superacids including sulfated titania, zirconia, and stannia are eous or alcoholic solutions and its further treatment (e.g., drying,
among the most promising heterogeneous catalysts [1]. Their milling and annealing). Typical procedure for a sulfated zirconia
acidity is much higher even than that of concentrated H2SO4, with catalyst synthesis includes impregnation of thus obtained amor-
their surface sulfate groups acting as Lewis and Brønsted sites [2]. phous ZrO2  xH2O or crystalline ZrO2 with sulfate-containing
The main advantages of solid superacid oxide catalysts include compounds (e.g., sulfuric acid, ammonium persulfate) [3,6]. Thus
high stability at elevated temperatures, resistance to deactivation, characteristics of nanocrystalline zirconia-based materials should
and easy regeneration. The SO4/ZrO2 is the most comprehensively depend on the composition and structure of intermediate amor-
studied system because its acidity is one of the highest among the phous phases formed during hydrolysis of Zr(IV) compounds.
sulfated oxides [2,3]. The Hammett acidity functions H0 for SO4/ Recently [7] we have demonstrated that variation in the pre-
ZrO2 and SO4/SnO2 fall within the range from  16 to  18; SO4/ cipitation pH indeed considerably changes the mesostructure,
TiO2 has a slightly lower value of  14.6 [4]. The above indicated fractal dimension and specific surface area of hydrous zirconia
values can vary because of the lack of common procedures for and hafnia gels. Thermal decomposition of these gels actually
analysis of the properties of sulfated oxides [5]. Reproducibility of gives rise to ZrO2 and HfO2 nanopowders having considerably
synthetic procedures used to prepare sulfated oxides is still also different particle sizes and specific surface areas.
rather poor [1]. In this paper, we aimed at establishing the probable interrela-
tion between the composition and the mesostructure of amor-
*
phous zirconia gels and phase composition, structure and
Corresponding author at: Kurnakov Institute of General and Inorganic
Chemistry of Russian Academy of Sciences, Leninsky ave., 31, Moscow 119991,
catalytic activity of sulfated zirconia prepared thereof. To synthe-
Russian Federation. Fax: þ 7 495 9541279. size sulfated zirconia we have used a simple procedure which
E-mail address: [email protected] (A.Ye. Baranchikov). includes only two steps: one-pot precipitation of sulfated hydrous

0022-4596/$ - see front matter & 2012 Published by Elsevier Inc.

http://dx.doi.org/10.1016/j.jssc.2012.11.022
 V.K. Ivanov et al. / Journal of Solid State Chemistry 198 (2013) 496–505 497

zirconia gels at various pHs and their further annealing. We hope F1 Jupiter thermal analyzer equipped with mass-spectrometer
that such an approach would favour reproducibility of structure (heating rate 5 1C/min).
and composition of sulfated zirconia catalysts and thus their Transmission electron microscopy images were taken using
catalytic properties. Leo 912 AB Omega electron microscope operating at 100 kV.
Microstructure of the samples was also studied using Carl Zeiss
NVision 40 scanning electron microscope (micrographs were
2. Experimental obtained at 1 kV acceleration voltage) equipped with Oxford
Instruments X-MAX energy-dispersive X-ray (EDX) analyzer oper-
2.1. Synthesis of samples ating at 30 kV acceleration voltage. The samples were not spe-
cially prepared (e.g., coated with conducting material) for TEM
All starting materials used in the experiments were of analy- and SEM measurements. Before EDX analysis samples were
tical grade. Zirconium oxynitrate hydrate (ZrO(NO3)2  xH2O, 99% coated with  5 nm Au/Pd.
Aldrich) was dissolved in distilled water and then ammonium Low temperature nitrogen adsorption measurements were con-
sulfate (99%, Chimmed, Russia) was added so that the final ducted using ATX-6 analyzer (Katakon, Russia) at 196 1C. Before
concentrations of ZrO(NO3)2 and (NH4)2SO4 were 0.25 M and measurements the samples were outgased at 200 1C for 30 min
1.0 M, respectively. The resulting solution was kept overnight under dry helium flow. Determination of the surface area was
and then filtered. To obtain hydrous sulfated zirconia, aqueous carried out by 8-point Brunauer–Emmett–Teller (BET) method.
ammonia (2.7 M, 99%, Chimmed, Russia) was added dropwise to To study the influence of precipitation conditions on the
the starting zirconium-containing solution under vigorous stir- mesostructure of amorphous zirconia xerogels a small angle
ring until the desired pH value was reached (3.98, 6.98 or 8.98). neutron scattering (SANS) technique was used. SANS measure-
pH measurements were made using Crison GLP-22 pH-meter. ments were performed on SANS-2 setup (FRG-1 neutron reactor,
Obtained suspensions were additionally stirred for 30 min in GKSS Research Centre, Geesthacht, Germany). The experiments
mother liquor while pH value was carefully adjusted with aqu- were performed at neutron wavelength l ¼5.8 Å with Dl/l ¼10%
eous ammonia. The resultant white precipitates were washed and for four sample-detector distances SD¼1 m, 3 m, 7 m, and
four times by redispersion in distilled water followed by centri- 20.7 m, which allowed to perform the measurements of the
fugation (8000 min  1). All the samples were further dried in an neutron scattering intensity for momentum transfers in the range
oven under air flow at 50 1C overnight and carefully grounded in 2.5  10  3 oqo2.6  10  1 Å  1. The scattered neutrons were
an agate mortar. Hereafter the as-synthesized sulfated hydrous detected by a two-dimensional position-sensitive 3He detector.
zirconia xerogels precipitated at pH 3.98, 6.98 or 8.98 are named The samples of amorphous xerogels of sulfated hydrous ZrO2
Z-4S, Z-7S and Z-9S, respectively. were placed in a 1 mm thick quartz cells. Apparent density rH of
Thermal decomposition of the xerogels was conducted in a each sample was calculated as a weight of a powder divided by its
muffle furnace in air at 500 1C, 550 1C, 600 1C and 700 1C for 5 h. volume. The initial spectra for each q range were corrected using
Heating rate was 10 1C/min. After the annealing samples were the standard procedure [9] taking into account the scattering
cooled down to ambient temperature within the furnace. Result- from the setup equipment and cell, as well as background from
ing sulfated zirconia powders are named hereafter Z-4S–T, Z-7S– incoherent scattering of neutrons on hydrogen atoms which are
T, Z-9S–T (here T is a temperature of thermal treatment—500 1C, present in samples in the form of physically and chemically
550 1C, 600 1C or 700 1C), respectively. bounded water. Resulting 2D isotropic spectra were averaged
Throughout this paper the characteristics of sulfated zirconia azimuthally and their absolute values were determined by nor-
are compared with the properties of zirconia samples synthesized malizing to the incoherent scattering cross section from vana-
using the same procedure but without addition of ammonium dium with inclusion of the detector efficiency and apparent
sulfate to the starting solution [7]. density (rH) for each sample. All measurements were done at
room temperature.
2.2. Methods of analysis The SANS intensity analyzed hereafter was defined as
IS ðqÞ ¼ IðqÞT  I0 ðqÞ, ð2Þ
X-ray powder diffractograms (XRD) were obtained using
Rigaku D/MAX 2500 diffractometer (Cu Ka radiation) over a 2y where I(q) and I0(q) are the momentum-transfer distributions of
range of 10–851 with an increment 0.021/step at the rate 2 1/min. scattered neutrons behind the sample and beam without the
Particle size was estimated using Scherrer equation sample, respectively. T¼I/I0 ¼exp(  S  L) is the transmission
coefficient of the neutrons passing through the sample, where
Kl
D¼ ð1Þ S ¼ ss þ sa is the integral scattering cross section which includes
½bð2yÞscosy0
nuclear scattering ss and absorption sa, and L is the sample
Here, y0 is the peak position, l is the Cu Ka radiation thickness. The setup resolution function was approximated by a
wavelength (0.154,056 nm), bhkl(2y) is the FWHM of a corre- Gaussian and was calculated separately for each SD distance with
sponding peak, s is the instrumental broadening (is equal to 0.11). the use of the standard procedure [10].
The value of K (shape factor) was set equal to 1. The b value was Adsorption of NH3 for temperature-programmed desorption
determined by subtraction of background followed by fitting experiments (NH3-TPD) was performed using Chemisorb 2750
profiles of (1 1 1) and (1 1 1) reflections of monoclinic zirconia (Micromeritics) in NH3:N2 ¼5:95 (v/v) gas mixture. Before the
and (1 1 1) reflection of tetragonal zirconia to the Voigt pseudo- experiments, the samples were pretreated for 1 h at 300 1C under
functions. Volume fractions of monoclinic (m-ZrO2) and tetra- helium flow (30 ml/min), then for 1 h at 300 1C under
gonal (t-ZrO2) phases in zirconia samples were estimated using O2:N2 ¼20:80 (v/v) gas mixture (30 ml/min) and finally for
relations proposed by Toraya et al. [8]. 30 min at room temperature under O2:N2 ¼20:80 (v/v) gas mix-
Thermal analysis (TGA/DTA) of the samples was performed in ture (30 ml/min). NH3-TPD was carried out under helium flow
air using Pyris Diamond thermoanalyzer (Perkin–Elmer) in the after purging the sample at 50 1C for 20 min to decrease the
temperature range 20–1100 1C (heating rate 10 1C/min). Chemical amount of physisorbed ammonia.
composition of gases evolved during thermal decomposition Studies of catalytic activity of Z-4S-600, Z-7S-600, Z-9S-600
under argon flow was established by means of Netzsch STA 449 samples in hexene-1 oligomerization were performed as follows.
498 V.K. Ivanov et al. / Journal of Solid State Chemistry 198 (2013) 496–505

Before a reaction each sample was heated in air at 600 1C for 2 h The exponent n value for the Z-4S sample found from the slope
and then cooled in dry atmosphere. A 1 g portion of catalyst and of the straight-line section of the experimental dS(q)/dO plotted
5 ml (3.4 g) of hexene-1 were placed into a thermostated glass in log–log scale is equal to 3.68. Thus scattering from the sample
flask and kept at constant temperature in 20–60 1C range under occured on the fractal surface with the dimension 2rDS ¼ 6
vigorous stirring. Samples of the reaction mixtures (0.2 ml) were n¼2.32 o3. In the q4qc1 region, the scattering curve exhibits a
taken for 1H–NMR and GC–MS analyses. 1H NMR spectra were shoulder indicating the presence of small inhomogeneities with
recorded using a Bruker DPX-200 spectrometer in CDCl3. NMR the effective gyration radius rg ¼3372 Å.
spectra gave a possibility to monitor a vinyl group protons Thus, the Z-4S xerogel contains two types of scattering
disappearance. Gas chromatography (GC) and GC–MS were per- inhomogeneities with strongly different characteristic sizes
formed using a LHM-2000 chromatograph (3% Dexsil 300—Chrom which correspond to relatively large aggregates with a fractal
W–AW column) and Perkin–Elmer Clarus 500 (SE-30 column) surface and small monomer particles.
spectrometer, respectively. These data were used to determine The absence of the Guinier region on the scattering curve for
oligomers content in reaction mixtures. low q-values means that the gyration radius rg or, for the fractal
systems, the upper self-similarity boundary is larger than the
maximum size Rmax of the inhomogeneities that can be detected
in the experiment with a given resolution. In turn, the lower self-
3. Results and discussion similarity boundary is likely to be determined by the size rc of
small inhomogeneities, which usually lies in the range from 2rg to
Fig. 1 shows the experimental curves of differential neutron cross 3rg (approximately 2.6rg for spherical particles) [12].
section dS(q)/dO for amorphous sulfated zirconia xerogels precipi- SANS cross-section for the samples Z-7S and Z-9S as distin-
tated at different pHs. According to these data, increase in the guished from Z-4S has higher intensity and possesses an extra
precipitation pH from 3.98 to 8.98 leads to notable (approximately region in the range of small q-values (qoqc2 E0.005 Å  1), where
two orders of magnitude) increase in SANS intensity as well as to the deviation of dS(q)/dO from power-law q  n is observed. This
changes in scattering pattern. This clearly indicates that the nuclear deviation is due to the transition to Guinier regime, where cross-
density homogeneity of xerogels in the range 10–1000 Å is section is governed by relatively large scattering inhomogeneities
decreased with the increase in the precipitation pH. with characteristic size rc (aggregates). As for the region q4qc1,
Sample synthesized in acidic media (Z-4S) shows two various the scattering curves also exhibit a shoulder due to the scattering
q ranges which significantly differ by the behavior of the on small inhomogeneities, while this shoulder appears at larger q-
SANS cross section dS(q)/dO. For low values qoqc1 (where values compared to the spectrum of Z-4S sample. This indicates
qc1 E0.06 Å  1 is the transition point between one scattering that precipitation of sulfated hydrous zirconia at higher pH leads
regime and another), the scattering cross-section dS(q)/dO satis- to decrease in the primary particles size rc. Moreover, despite we
fies the power law q  n. Such a power-law dependence is typical cannot estimate the upper limit of self-similarity range for all the
for systems with a wide size distribution (Rmax cRmin) if the samples, the widest self-similarity range can be ascribed to the
condition xerogel synthesized at the lowest pH. Values of n parameter as
calculated from linear slopes of spectra for samples Z-7S and Z-9S
max o o qo oRmin
R1 1
ð3Þ are equal to 3.43 and 3.17, respectively.
SANS from sulfated hydrous zirconia xerogels is in a good
is satisfied. In addition, the power scattering law means that
accordance with our previously reported data [7,13] indicating
inhomogeneities making the dominant contribution to scattering
that scattering from non-sulfated zirconia precipitated at pH46
are sufficiently large (qmin  Rc 1). Bale and Schmidt [11] pro-
can be described within the model of porous structure with
posed a more exact criterion for determination of a certain
fractal surface.
characteristic size of inhomogeneities, qmin  R E3.5. In our case,
In view of this circumstance, to analyze scattering from Z-7S
qmin ¼2.5  10  3 Å  1 and consequently the characteristic size of
and Z-9S amorphous xerogels over the entire q range, we used the
the inhomogeneities is RE1250 Å.
expression [13,14]:
! !
dSðqÞ q2 R2g A2 ðDS Þ q2 r 2g
¼ A1  exp  þ  n þA3  exp  ð4Þ
dO 3 q^ 3

Here,
 
q^ ¼ q=½erf q  Rg =61=2 3 ð5Þ

is the momentum q transferred, normalized to an error function

erf(x). Such a procedure allows the cross-section of scattering
dS(q)/dO to be described correctly in the intermediate region
between q  R0 o1 (Guinier approximation) and q  R0c 4 41
(q  n asymptotics), where scattering from both surfaces and
aggregates of characteristic size R0 contributes [14]. The values
of A1 and A3 are directly proportional to the number and the
volume of inhomogeneities (aggregates and monomers, respec-
tively) as well as to the density of their neutron scattering
amplitudes [15]. Amplitude A2(DS) depends on the fractal dimen-
sion of the system [11] as
Fig. 1. SANS differential cross-section dS(q)/dO for amorphous sulfated zirconia,
precipitated at pH ¼8.98 (1), 6.98 (2), and 3.98 (3) versus momentum transfer q.  
Continuous lines represent results of experimental data fitting. A2 ðDS Þ ¼ pr2 Gð5DS Þsin½ðDS 1Þ p=2 N0 ð6Þ
 V.K. Ivanov et al. / Journal of Solid State Chemistry 198 (2013) 496–505 499

where G is the gamma function, and r for a compound containing further increase in pH will result in formation of hydrous zirconia
several elements is defined as samples possessing even higher surface fractal dimension.
Fig. 2 shows SANS data for amorphous sulfated zirconia in
X rh NA
r¼ bi N i : ð7Þ comparison with our recent data for hydrous zirconia xerogels
i
M synthesized using precisely the same procedure excluding addi-
tion of ammonium sulfate to the starting solution [7]. Surface
Here, NA is the Avogadro constant, M is the molar mass, bi is fractal dimension for both sulfated and non-sulfated zirconia
the scattering length for the ith element in the compound, Ni is xerogels increases with the increase in the precipitation pH
the number of atoms of this element, and rH is the solid-phase (Fig. 2A). These data are in line with our earlier supposition that
density. The constant N0 is related to the specific surface of the precipitation conditions influence strongly the mesostructure of
surface fractal as S0 ¼N0  r2  Ds, where r2  Ds is determined by the zirconia xerogels and this effect is due to change in colloid
length of the yardstick. For smooth surfaces, DS ¼2 and N0 ¼ S0. particles aggregation mechanism upon change of acidity of the
Taking into account that for the Z-4S sample no deviation of media and surface charge of colloid particles. On the other hand,
scattering spectrum from power-law dependence in small q range DS of sulfated zirconia is notably higher than DS of non-sulfated
was observed, expression (4) was simplified to: zirconia within the whole pH range. This difference is probably
! due to the presence of doubly charged sulfate ions, which strongly
dSðqÞ A 2 ð DS Þ q2 r 2g adsorb onto the surface of colloid ZrO2  xH2O particles, while
¼ þ A3  exp  ð8Þ
dO qn 3 nitrate ions have less sorption ability.
It is worth saying that reproducibility of structural parameters
To obtain the final results, expressions (4, 8) were convolved of hydrated zirconia gels as derived from small-angle neutron
with the setup resolution function. The experimental curves of scattering data is very high. For instance, the fractal dimension of
the differential cross section dS(q)/dO versus q were processed by amorphous zirconia gels precipitated at given pH is always the
the least mean squares method over the entire q range under same (namely, variation of DS value is less then 0.02 from one
investigation. The results of this analysis are given in Table 1. experiment to another). In fact, from our point of view, such a
These data evidently show that both surface fractal dimension reproducibility is a very amazing phenomenon. It clearly demon-
and A2(DS) values increase with the increase in the precipitation strates that the ‘‘soft matter’’ is in fact not so ‘‘soft’’.
pH. The value of DS for the sample Z-4S is the lowest, i.e., in this
case monomer particles form fractal aggregates with the smooth-
est surface. Upon precipitation from neutral (pH¼6.98) and
alkaline (pH¼8.98) media the values of surface fractal dimension
are higher (2.6 and 2.8, respectively). In other words, increase in
the precipitation pH results in notable changes in monomer
aggregation behavior.
Formation of zirconia surface fractal aggregates and increase in
their surface fractal dimension upon increase in pH can be
explained using well known data on the mechanism of condensa-
tion of hydrous silica monomers [16]. Under acidic conditions
condensation occurs mainly between silanol groups located at the
ends of polymeric chains leading to the formation of linear
polymers. Contrariwise, under basic conditions, the condensation
reaction occurs preferentially between the ends and the interior
of polymeric chains thus leading to formation of ramified aggre-
gates with a higher fractal dimension. Such an approach explains
the increase in the surface fractal dimension value of hydrous
zirconia upon gradual increase in the precipitation pH from 4 to 9.
These suppositions are also in agreement with well established
Clearfield theory [17], which states that slow hydrolysis of
zirconyl salts leads to formation of regular sheets consisting of
tetrameric [Zr4(OH)8] units, while fast hydrolysis (for instance,
under basic conditions) promotes rapid polymerization occurring
in many directions at once. The degree of polymerization
increases with an increase in pH [18]. Such a mechanism of
polymerization can be also the main reason of fractal formation in
course of hydrous sulfated zirconia precipitation. In this case,

Table 1
Parameters of mesostructure of amorphous sulfated zirconia according to SANS
measurements.

Zr-4S Zr-7S Zr-9S

A1  10  6 (cm2 g  1) – 31,400 72000 25,4007 2,000

R0 (Å) Z 1,250 710 770 6907 100
A2  10  6 (cm2 g  1) 0.87 0.1 100 725 2107 60
DS ¼ 6  n 2.32 70.09 2.57 70.08 2.837 0.08
A3  10  1 (cm2 g  1) 0.577 0.05 4.08 70.07 5.37 0.08 Fig. 2. Surface fractal dimension, DS (A) and primary particle size, rc (B) of
rg (Å) 337 2 17.3 70.8 15.17 0.9 amorphous zirconia xerogels versus precipitation pH. 1 – non-sulfated zirconia
according to [7], 2 – sulfated zirconia synthesized in this work.
500 V.K. Ivanov et al. / Journal of Solid State Chemistry 198 (2013) 496–505

The rise of the precipitation pH from 3.98 to 8.98 leads to These data are also in a good agreement with our recent results
approximately twofold decrease in the characteristic size rc (for on thermal decomposition of non-sulfated hydrous zirconia [7].
spheres, rc ¼ (5/3)1/2rg) of primary sulfated ZrO2  xH2O particles It is well known that hydrous oxides generally possess extremely
(from 43 Å to  20 Å, see Fig. 2B). For non-sulfated zirconia high sorption capacity. Below the point of zero charge (pHpzc)
synthesized under the same conditions a slight increase in their surface is positively charged and this charge is compensated
primary particle size (from  18 to 22 Å) is observed upon the by preferential adsorption of negatively charged ions. Thus
rise of pH. sedimentation of hydrous zirconia under acidic conditions is
According to XRD data (see Fig. S1 in the Supporting Informa- accompanied by considerable adsorption of NO3 and SO2 4 ions
tion) all the initial xerogels are completely amorphous giving two which are present in mother liquor. However, higher bonding
extremely broad peaks at  30 and  50–6012y. Basing on short- strength of sulfate ions results in preferred adsorption of SO2
4 . These
range structural model proposed by Southon et al. [19], repro- species cannot be removed completely even by repeated washing.
ducible extremely broadened peaks on diffractograms of hydrous Temperature corresponding to maximum rate of sulfates
zirconia xerogels can be caused by short range ordered zirconium decomposition decreases with the increase in the precipitation
hydroxide polymers consisting of cyclic tetramer species. Accord- pH and is equal to 715–725 1C, 685–695 1C, 650–660 1C for Z-4S,
ing to Moroz et al. hydrous zirconia gels precipitated at pH 7 and Z-7S and Z-9S samples, respectively. This effect is probably caused
pH 9 are indeed X-ray amorphous [20] but possess short-range by the stronger bonding between SO24  -ions and hydrous zirconia
ordering [21]. Amorphous nature of sulphated zirconia xerogels particles when precipitation is conducted under acidic conditions.
was also confirmed by TEM and SAED patterns of the samples. Differential TGA curve of Z-4S sample shown in Fig. 3B exhibits
According to TGA (Fig. 3A) and TGA–MS (see Fig. S2 in the a distinct decomposition stage at 430–500 1C which is absent for
Supporting Information) data the first stage of thermal decom- the other samples. According to TGA–MS data this stage corre-
position of sulfated zirconia xerogels at temperatures up to sponds to decomposition of nitrate-containing zirconium com-
approximately 200 1C corresponds to elimination of physisorbed pounds. Thus, hydrous zirconia precipitated under acidic
water, and the second one (at 600–750 1C) corresponds to conditions contains not only high amount of sulfate species, but
decomposition of sulfates. also a certain amount of NO3 ions. Two peaks in the range of
Thermal analysis shows that precipitation conditions substan- 600–750 1C are attributed to two-stage decomposition of sulfate
tially affect the chemical composition and thermal behavior of groups. This evidences the presence of at least two types of
sulfated zirconia gels. Weight loss at high temperature decom- surface sulfate species.
position stage decreases notably with the increase in the xerogel The body of TGA–MS and differential TGA data gave us the
precipitation pH. This effect is obviously due to the less content possibility to estimate the chemical composition of sulfated
of sulfates in hydrous zirconia samples precipitated at higher zirconia xerogels: Zr-4S—ZrO1.46(NO3)0.12(SO4)0.48  2.2H2O; Zr-
pH values and corresponds well to observations made in [22]. 7S—ZrO1.76(SO4)0.24  2.6H2O; Zr-9S—ZrO1.88(SO4)0.12  2.7H2O.
Mass spectroscopy data shows no signal corresponding to sulfur
oxides at temperatures below 500–550 1C since SO24  groups are
chemically bonded to zirconia particles and no other sulfur-
containing compounds (like ammonium sulfates or sulfuric acid)
are present in samples.
DTA data are presented in Fig. 4. Strong endothermic peak
below 200 1C which is observed for all the samples corresponds
to elimination of physisorbed water from zirconia xerogels. At
higher temperatures a notable difference in samples behavior is
observed. An exothermic peak (maximum at 590–600 1C) for Z-9S
sample does not correspond to release of any gaseous products
and so it is probably caused by crystallization of zirconia from

Fig. 3. Thermal analysis (A) and differential thermal analysis (B) curves of sulfated Fig. 4. Differential thermal analysis of sulfated zirconia xerogels (1—Z-4S, 2—Z-7S,
zirconia xerogels precipitated at different pH (1—Z-4S, 2—Z-7S, 3—Z-9S). 3—Z-9S).
 V.K. Ivanov et al. / Journal of Solid State Chemistry 198 (2013) 496–505 501

X-ray amorphous state. In turn, non-sulfated zirconia synthesized because of superposition of two opposite sign thermal effects
under the same conditions crystallizes at 415–435 1C. Thus, caused by decomposition of sulfates and crystallization of ZrO2.
introduction of sulfate ions favors additional stabilization of Stabilization of amorphous zirconia by sulfate species was
amorphous zirconia and inhibits crystallization process. This confirmed by X-ray diffraction of ZrO2  xH2O samples subjected to
conclusion is also in line with [22]. long term (5 h) annealing at 500–700 1C (Fig. 5). While Z-9S
DTA curves for Z-7S and Z-4S samples show no evident xerogel which contains minimum amount of sulfates crystallizes
exothermic effects corresponding to crystallization of ZrO2. On upon annealing at 500 1C, Z-4S and Z-7S samples treated under
the contrary, DTA curve for Z-7S sample shows endothermic the same conditions remain completely or almost completely
effect at 700–705 1C which corresponds to decomposition of amorphous (Z-4S-500 sample contains trace amounts of crystal-
sulfates, while Zr-4S sample exhibits two close endothermic line zirconia in addition to amorphous phase). Increase in anneal-
effects with maxima at 630–635 and 720–725 1C which are also ing temperature to 550 1C results in notable decrease in the
due to the elimination of sulfur oxides. The absence of exothermic amount of amorphous phase in the samples. Further temperature
crystallization peaks for Z-4S and Z-7S xerogels is probably rise up to 600 1C results in formation of crystalline ZrO2 in all the

Fig. 5. X-ray diffraction patterns of sulfated zirconia xerogels upon thermal treatment at (a) 500 1C, (b) 550 1C, (c) 600 1C, (d) 700 1C during 5 h (1—pH 4, 2—pH 7, 3—pH 9).
Solid black vertical lines correspond to tetragonal zirconia, dotted red ones—to monoclinic zirconia.
502 V.K. Ivanov et al. / Journal of Solid State Chemistry 198 (2013) 496–505

cases while small amounts of amorphous zirconia still remain in media [7]. In turn, to explain unusual behavior of sulfated zirconia
Z-4-600 and Z-7-600 samples. Complete crystallization occurs we had to take into consideration the second possible stabiliza-
only after 5 h treatment at 700 1C. tion mechanism of tetragonal ZrO2 described elsewhere [24]
Phase composition (content of metastable tetragonal and which deals with surface excess energy of sub-30 nm zirconia
stable monoclinic zirconia) depends on a number of factors particles.
including chemical composition of zirconium-containing amor- Actually, mean particle size calculated using Scherrer formula
phous precursors. Thermal treatment of Z-7S and Z-9S samples notably depends on the precipitation pH. Particle size of tetra-
leads to formation of metastable tetragonal zirconia with no gonal zirconia obtained upon thermal treatment of sulfated
marked traces of monoclinic phase. On the contrary, powders zirconia xerogels precipitated at low pH values (23–28 nm) is
obtained upon annealing of Z-4S sample at 500–700 1C contain notably higher compared with particle size of t-ZrO2 synthesized
notable amount of monoclinic zirconia (tetragonal to monoclinic in neutral and alkaline media (14–16 nm). This effect is in a good
zirconia volume fraction ratio is 1:3–1:4). accordance with transmission electron microscopy data (Fig. 7).
Phase composition of sulfated and non-sulfated zirconia Upon the rise of the temperature from 500 1C to 700 1C the
obtained under the same conditions differs dramatically. An particle size of tetragonal zirconia does not change significantly.
illustration of this difference is given in Fig. 6 and in Table 4. The same effect is observed for monoclinic ZrO2 forming upon
In non-sulfated samples tetragonal zirconia content decreases thermal decomposition of Z-4S xerogel—particle size of mono-
with increase in the precipitation pH, while sulfated ones show an clinic ZrO2 is always about 15–18 nm (see Table 4).
opposite tendency. The decrease in particle size of t-ZrO2 with the increase in the
This result is quite unusual. It is well known that stabilization precursor xerogels precipitation pH is in line with our previously
of tetragonal zirconia is caused by the presence of various anionic reported data [7,25]. As far as thermal decomposition of hydrous
and cationic impurities [23]. ZrO2  xH2O precipitated in acid sulfated zirconia can be judged as a topochemical process,
media (below the point of zero charge) indeed contains the structure of initial xerogel should affect the structure and proper-
highest amount of impurities. Thus products of the thermal ties of the product of its thermal decomposition. In particular,
decomposition of hydrous zirconia precipitated in acid media in xerogel precipitated in acid media has higher apparent density
the absence of sulfate species contain higher fraction of tetragonal compared to xerogels precipitated in neutral and alkaline media.
zirconia in comparison with zirconia precipitated in alkaline This was also the case for non-sulfated zirconia. Denser xerogels
precipitated at low pH values transform into larger ZrO2 particles
while xerogels possessing more ramified structure decompose
upon annealing with formation of relatively small ZrO2 particles.
Thermal behavior of Z-4S-600, Z-7S-600, and Z-9S-600 samples
(Fig. S3 in the Supporting Information) is in line with the above
outputs. Weight loss corresponding to elimination of sulfur oxides
decreases with increase in the precipitation pH of initial xerogel.
Furthermore, the temperature corresponding to the maximum rate
of sulfate decomposition falls with the increase in the precipitation
pH and is equal to 695–700 1C, 655–665 1C, and 625–635 1C for
Z-4S-600, Z-7S-600, and Z-9S-600, respectively.
Chemical composition of xerogels upon annealing at 500 1C
and 600 1C according to energy dispersive X-ray spectroscopy
data is given in Table 2 and in Table 4. These data also confirm

Table 2
Sulfur content (wt% S) in sulfated zirconia samples.

Precipitation pH Temperature

500 1C 600 1C

3.98 8.1 7.7

Fig. 6. Relative content of tetragonal zirconia in ZrO2 samples precipitated at 6.98 8.5 5.0
various pH and then annealed at 600 1C for 5 h. 1 – non-sulfated zirconia 8.98 4.7 2.8
according to [7], 2 – sulfated zirconia synthesized in this work.

Fig. 7. TEM images of sulfated zirconia samples Z-4S-600 (a), Z-7S-600 (b), Z-9S-600 (c).
 V.K. Ivanov et al. / Journal of Solid State Chemistry 198 (2013) 496–505 503

that sulfur content in sulfated nanocrystalline zirconia decreases Table 4. Specific surface area rises with the increase in the
with the rise of hydrous zirconia precipitation pH and agree with precipitation pH as well as with the raise of the temperature of
the thermal analysis data presented in Fig. 3 and S3. Temperature thermal treatment. Close results on the influence of pH on the
rise from 500 1C to 600 1C does not substantially affect the sulfur amount of sulfate sorbed as well as effect of calcination temperature
content in powders derived from Z-4S, while lead to 1.5 and 2.0- on surface area of sulfated zirconia was reported earlier by [26].
fold decrease in sulfur content in ZrO2 powders derived from Z-7S Actually specific surface area (SBET) of samples originated from Z-4S
and Z-9S samples, respectively. This is in a good agreement with xerogel is very low and do not exceed 20 m2/g. At the same time
the above conclusion that raise in the precipitation pH facilitates increase in the precipitation pH up to the point of zero charge and
sulfates decomposition and lowers the temperature of sulfur higher leads to dramatic increase in corresponding specific surface
oxides elimination. area values. These data give additional evidence that initial amor-
Specific surface area values of Z-4S, Z-7S, and Z-9S xerogels phous hydrous zirconia mesostructure influences the microstructure
treated at 500 1C, 550 1C, and 600 1C are given in Fig. 8 and in of nanocrystalline sulfated zirconia. The highest surface area of
zirconia can be reached when starting hydrous zirconia is precipi-
tated under alkaline conditions (pH4pHpzc). These data correlates
well with the Arata’s pioneering work [26]. Increase in specific
Table 3 surface area values with the raise of annealing temperature is
Catalytic isomerization and oligomerization of hexene-1 over sulfated zirconia.
presumably caused by elimination of gaseous products from sul-
Run Catalyst t, 1C/t, h Conversion, % Products content, % fated zirconia causing formation of microcracks. SEM images
(see Fig. 9) support surface area measurements and vividly present
C6 C12 C18 C24 C30 the difference between dense glass-like structure of Z-4S-600
sample and porous structure of Z-7S-600 and Z-9S-600 samples.
1 Z-4S-600 20/1 6
2 20/24 54
Fig. 10 represents NH3 temperature-programmed desorption
3 40/1 60 (TPD) spectra normalized per 1 m2 surface area for sulfated
4 60/1 67 78a 16 6 0 0 zirconia samples annealed at 600 1C for 5 h. The surface of all
5 Z-7S-600 20/1 58 samples contains acid sites of two different types. Low tempera-
6 20/24 100
ture peaks at 150–200 1C in NH3-TPD spectra correspond to weak
7 40/1 100 18b 49 24 7 2
8 60/1 100 acid centers. Extended shoulders with no pronounced maxima
9 Z-9S-600 20/1 74 which appear at 250–600 1C correspond to strong acid sites.
10 20/24 100 Increase in initial xerogel precipitation pH leads to the raise of
11 40/1 100 13b 45 26 10 4 the ratio between weak and strong acid centers. As weak acid
12 60/1 100
sites are commonly assigned to the surface hydroxyl groups, the
a
 30% of hexene-1. surface of sulfated zirconia remains hydroxylated even upon
b
Only hexene-2þ hexene-3. annealing at 600 1C. Distribution of weak acid sites over ammo-
nium desorption activation energy becomes narrower in a row of
Z-4S-600, Z-7S-600, and Z-9S-600. This can be explained by
higher phase uniformity of samples obtained upon annealing of
xerogels precipitated at higher pH (see Fig. 5c). Note that Z-4S-
600 sample possesses the highest concentration of strong acid
sites. When adsorbed on oxide surfaces sulfate species generate
strong acidity [3,4] through both Lewis and Brønsted superacid
centers [2]. Accordingly sulfated zirconia synthesized from xer-
ogel precipitated at the lowest pH possess the highest sulfur to
zirconium molar ratio.
Surface concentration of acid sites can be determined by
integrating the NH3-TPD curves, supposing that each NH3 mole-
cule desorbs from one site. Z-4S-600 sample showed the highest
specific concentration of acid sites (18.6 mmol/m2), while the
values for Z-7S-600 and Z-9S-600 are quite close and are equal
to 6.5 and 8.9 mmol/m2, respectively (see Table 4).
To estimate the catalytic activity of sulfated zirconia we have
studied hexene-1 oligomerization catalyzed by Z-4S-600, Z-7S-
600, and Z-9S-600 samples. During each experiment a portion of
pure hexene-1 was stirred with a catalyst at a predetermined
Fig. 8. Specific surface area of sulfated zirconia against precipitation pH and temperature. Analysis of reaction mixtures was performed by 1H
temperature of thermal treatment (1–500 1C, 2–550 1C, 3–600 1C). NMR and GC–MS methods. The catalytic transformation of

Table 4
Properties of sulfated zirconia catalysts.

Sample Surface area, Particle size (XRD), nm Volume fraction Sulfur Specific acidity, Total acidity, Conversion of hexene-1
m2/g of t-ZrO2, % content, wt% mmol/m2 mmol/g at 40/1 run (see Table 3), %
t-ZrO2 m-ZrO2

Z-4S-600 17 73 267 2 17 7 2 24 73 7.77 0.4 18.6 7 0.6 3207 50 60 7 3

Z-7S-600 45 74 157 1 – 100 5.07 0.3 6.4 7 0.4 2907 50 100
Z-9S-600 76 76 167 1 – 100 2.87 0.3 8.9 7 0.4 6807 50 100
504 V.K. Ivanov et al. / Journal of Solid State Chemistry 198 (2013) 496–505

Fig. 10. NH3-TPD data normalized per 1 m2 of surface area of sulfated zirconia
(1—Z-4S-600, 2—Z-7S-600, 3—Z-9S-600).

Scheme 1. Chemical transformations catalyzed by sulfated zirconia. .

(18.6 mmol/m2) but the lowest specific surface area (17 m2/g),
what gives the value of total acidity approx. 320 mmol/g. The
Z-9S-600 sample with 8.9 mmol/m2 specific acidity and 76 m2/g
surface area gives more than a two times higher total acidity
value—approx. 680 mmol/g. This means that 1 g of Z-9S-600
catalyst will be at least two times more active in catalytic
transformation of hexene-1 than an equivalent amount of Z-4S-
600 catalyst. The difference in catalytic activity must be even
larger because of the surface structure of the samples—glass-like
for Z-4S-600 and porous for Z-9S-600 (Fig. 9). The total acidity of
Z-7S-600 sample (approx. 290 mmol/g) is close to Z-4S-600, but
the porous surface structure makes it more active.

4. Conclusions

Fig. 9. SEM images of Z-4S-600 (a), Z-7S-600 (b), and Z-9S-600 (c) samples. In this work, we have established how mesostructure and
composition of hydrous sulfated zirconia gels precipitated from
ZrO(NO3)2/(NH4)2SO4 aqueous solutions at different pHs govern
hexene-1 under acid conditions leads to a double bond shift structure, chemical and phase composition, and catalytic activity
and/or to oligomerization resulting in formation of higher olefins. of nanocrystalline sulfated zirconia formed via thermal decom-
Catalytic reaction scheme is given in Scheme 1 and the results are position of these gels. We have shown for the first time that the
summarized in Tables 3 and 4. The influence of precipitation pH raise in precipitation pH from 4 to 9 leads to dramatic increase in
on the catalytic activity of sulfated zirconia in oligomerization as the surface fractal dimension (DS) of sulfated zirconia xerogels as
well as on side isomerisation reaction of hexene-1 can be easily well as to a decrease in the size of primary particles (rc) forming
observed. The data obtained correlate well with earlier short zirconia fractal aggregates. Sulfated nanocrystalline zirconia sam-
communication of Arata et al. devoted to catalytic isomerization ples prepared from gels precipitated in neutral and alkaline media
of n-pentane [27]. have relatively low sulfur content but they possess much higher
Table 4 summarizes properties of sulfated zirconia catalysts. catalytic activity due to the smaller particle size, higher specific
The results of catalytic experiments can be explained from the surface area and higher total acidity. We hope this paper makes a
point of view of surface acidic properties of the samples (see contribution to reproducible synthetic methods of sulfated zirco-
Table 4). Z-4S-600 sample has the highest specific acidity nia superacid catalysts preparation.
 V.K. Ivanov et al. / Journal of Solid State Chemistry 198 (2013) 496–505 505

Acknowledgments Commun. (1992) 1645;

Z. Yanwei, Z. Yubao, J. Colloid Interface Sci. 247 (2002) 100;
B.M. Reddy, P.M. Sreekanth, P. Lakshmanan, A. Khan, J. Mol. Catal. A 244
Authors are grateful to Dr. Tatyana I. Vetrova for technical (2006) 1;
assistance. S. Ardizzone, C.L. Bianchi, E. Grassi, Colloids Surf. 135 (1998) 41;
V.I., A.B. and G.K. would like to thank GKSS Forschungszentrum H.K. Mishra, K.M. Parida, Appl. Catal., A 224 (2002) 179.
[7] V.K. Ivanov, G.P. Kopitsa, A.E. Baranchikov, M. Sharp, K. Pranzas,
for hearty welcome. S.V. Grigoriev, Russ. J. Inorg. Chem. 54 (2009) 2091.
The work was partially supported by the Russian Ministry of [8] H. Toraya, M. Yoshimura, S. Somiya, J. Am. Ceram. Soc. 67 (1984) C–119.
Science and Education (project ]14.740.11.0281) and Russian [9] G.D. Wignall, F.S. Bates, J. Appl. Crystallogr. 20 (1986) 28.
[10] W. Schmatz, T. Springer, J. Schelten, K. Ibel, J. Appl. Crystallogr. 7 (1974) 96.
Foundation for Basic Research (projects 09-03-01067 and 11-03- [11] H.D. Bale, P.W. Schmidt, Phys. Rev. Lett. 38 (1984) 596.
00981). [12] P.W. Schmidt, Modern Aspects of Small-Angle Scattering, Kluwer Academic
Publishers, Dordrecht, 1995.
[13] G.P. Kopitsa, V.K. Ivanov, S.V. Grigoriev, P.E. Meskin, O.S. Polezhaeva,
V.M. Haramus, JETP Lett. 85 (2007) 122.
Appendix A. Supporting information
[14] G. Beaucage, J. Appl. Crystallogr. 28 (1995) 717.
[15] A. Guinier, G. Frournet, C.B. Walker, K.L. Yudowitch, Small-Angle Scattering of
Supplementary data associated with this article can be found X-rays, Wiley, New York, 1955.
in the online version at http://dx.doi.org/10.1016/j.jssc.2012.11. [16] C.J. Brinker, K.D. Keefer, D.W. Schaeffer, R.A.Q. Assink, B.D. Kay, C.S. Ashley, J.
Non-Cryst. Solids 63 (1984) 45.
022. [17] A. Clearfield, J. Mater. Res. 5 (1990) 161.
[18] T.G. Kuznetsova, V.A. Sadykov, Kinet. Catal. 49 (2008) 840.
[19] P.D. Southon, J.R. Bartlett, J.L. Woolfrey, B. Ben-Nissan, Chem. Mater. 14
References (2002) 4313.
[20] D.A. Zyuzin, E.M. Moroz, A.S. Ivanova, A.N. Shmakov, G.N. Kustova, Kinet.
Catal. 45 (2004) 739.
[1] Y. Wu, S. Liao, Front. Chem. Eng. Chin. 3 (2009) 330. [21] D.A. Zyuzin, E.M. Moroz, A.S. Ivanova, A.N. Shmakov, Crystallogr. Rep. 48
[2] J.R. Sohn, J. Ind. Eng. Chem. 10 (2004) 1. (2003) 413.
[3] M. Waqif, J. Bachelier, O. Saur, J.C. Lavalley, J. Mol. Catal. 72 (1992) 127; [22] S. Chokkaram, R. Srinivasan, D.R. Milburn, B.H. Davis, J. Colloid Interface Sci.
B.M. Reddy, M.K. Patil, Chem. Rev. 109 (2009) 2186; 165 (1994) 160.
K. Arata, Green Chem. 11 (2009) 1719; [23] S. Shukla, S. Seal, Int. Mater. Rev. 50 (2005) 1.
S.G. Ryu, B.C. Gates, Ind. Eng. Chem. Res. 37 (1998) 1786; [24] R.C. Garvie, J. Phys. Chem. 69 (1965) 1238;
S. Rezgui, R.E. Jentoft, B.C. Gates, Catal. Lett. 51 (1998) 229; E. Djurado, P. Bouvier, G. Lucazeau, J. Solid State Chem. 149 (2000) 399;
T.K. Cheung, F.C. Lange, B.C. Gates, J. Catal. 159 (1996) 99. S. Shukla, S. Seal, R. Vij, S. Bandyopadhyay, Z. Rahman, Nano Lett. 2 (2002)
[4] K. Arata, H. Matsushita, M. Hino, H. Nakamura, Catal. Today 81 (2003) 17. 989;
[5] H. Yu, H. Fang, H. Zhang, B. Li, F. Deng, Catal. Commun. 10 (2009) 920. S. Shukla, S. Seal, J. Phys. Chem. B 108 (2004) 3395;
[6] M.K. Mishra, B. Tyagi, R.V. Jasra, Ind. Eng. Chem. Res. 42 (2003) 5727; S. Shukla, S. Seal, Rev. Adv. Mater. Sci. 5 (2003) 117.
S. Wrabets, X. Yang, G. Tzolova-Müller, R. Schlögl, F.C. Jentoft, J. Catal. 269 [25] V.K. Ivanov, G.P. Kopitsa, A.E. Baranchikov, S.V. Grigor’ev, V.M. Haramus,
(2010) 351; Russ. J. Inorg. Chem. 55 (2010) 155.
A. Minesso, F. Genna, T. Finotto, A. Baldan, A. Benedetti, J. Sol–Gel Sci. Techn. [26] F.R. Chen, G. Coudurier, J.F. Joly, J.C. Vedrine, J. Catal. 143 (1993) 616;
24 (2002) 197; A. Corma, A. Martı́nez, C. Martı́nez, Appl. Catal., A 144 (1996) 249.
C.-Y. Hsu, C.R. Heimbuch, C.T. Armes, B.C. Gates, J. Chem. Soc., Chem. [27] T. Tatsumi, H. Matsuhashi, K. Arata, Bull. Chem. Soc. Jpn. 69 (1996) 1191.