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1 s2.0 S0926860X98002968 Main
1 s2.0 S0926860X98002968 Main
Si OR H
2
O
hydrolysis
esterification
Si OH ROH (1)
SiOR HOSi
alcohol condensation
alcoholysis
SiOSi
ROH (2)
SiOH HOSi
water condensation
hydrolysis
SiOSi
H
2
O (3)
where R is an alkyl group, C
x
H
2x1
. The hydrolysis
reaction replaces alkoxide groups (OR) with hydroxyl
groups (OH). Subsequent condensation reactions
involving the silanol groups produce siloxane bonds
(SiOSi) plus the by-products alkohol (ROH) or
water. Because water and alkoxysilanes are immisci-
ble, a mutual solvent such as alcohol is normally used
as a homogenizing agent.
Numerous investigations have shown that variations
in synthesis conditions (for example, ratio H
2
O:Si, the
catalyst type and concentrations, the solvent, tempera-
ture and pressure) cause modications in the structure
and properties of the polysilicate products [7]. Synth-
esis parameters, including medium pH, appreciably
inuence both hydrolysis and condensation rate then
on kinetics and mechanism of solgel process, invol-
ving forming of gels of various three-dimensional
structure.
Thus, porous structure of silica aerogels strongly
depends on preparation and drying parameters
[817].
In this paper we present detailed description of the
conditions at which silica aerogels are prepared and
the inuence of this conditions on the textural proper-
ties of silica aerogels that may be applied as catalyst
supports.
2. Experimental
2.1. Preparation of aerogels
2.1.1. Materials
Tetraethoxysilane (Fluka) (TEOS) was used as
precursor. Its purity was above 98% (GC), so it was
used as supplied. Other materials were: anhydrous
ethanol (critical temperature 2438C, critical pressure:
6.46 MPa), demineralized water, hydrochloric acid,
pa. and ammonia, pa. both in the form of solutions in
demineralized water.
2.1.2. Procedure
The aerogels were prepared in four steps: (i) hydro-
lysis of TEOS, (ii) gelation and aging, (iii) drying, and
(iv) calcination. The hydrolysis and aging of gels was
carried out in a constant temperature chamber (208C)
in at bottomed 50 cm
3
glass test tubes. The solutions
of TEOS in alcohol were brought to desired pH by
introducing the catalyst (HCl or NH
3
solution) with a
micropipette. pH of reaction mixture during of TEOS
hydrolysis (TEOS, ethanol, water and HCl solution)
from 1.3 to 3.6 was tested. The hydrolysis extent was
monitored by 1H NMR. The gelation was carried out
at different value of pH (5.98.6) by using ammonia
water solution as the gelation agent and obtained
alcogels were aged during 1416 h. In order to control
the reproducibility, at least two samples were prepared
at identical conditions.
The gels were dried in a small vessel (100 cm
3
) at
supercritical conditions (temperature at 2808C under
pressure 14.2 MPa). To prevent the gels from a col-
lapse at the heating up stage, the reactor was lled with
nitrogen at a pressure of ca. 5 MPa (close to the critical
pressure of alcohol). The excess pressure that built up
was carefully removed during heating up stage. The
rate of heating was ca. 508C/h. The samples were kept
in the reactor (dried) for one more hour after reaching
the predetermined conditions. Then the pressure was
reduced and the reactor was brought to room tem-
perature. The schematical view of the apparatus is
shown in Fig. 1.
The dried aerogels were calcined at 5008C for 5 h in
air. All measurements of physicochemical properties
were made for calcined samples. The characterization
of the samples included measurements of bulk density,
specic surface area by thermal desorption of nitro-
140 M. Stolarski et al. / Applied Catalysis A: General 177 (1999) 139148
gen, and total pore volume by mercury porosimetry
(porosimeter Carlo Erba 1500).
The samples having good physical properties
were further characterized by measuring the
sorption of carbon dioxide or benzene vapors in a
gravimetric sorption apparatus, wide angle X-ray
analysis (DRU-6 diffractometer) and microscopic
examination by using an electron scanning micro-
scope (TESLA 360).
3. Results and discussion
3.1. The hydrolysis and gelation stages
Tetraethoxysilan (TEOS) easily hydrolyzes in
the presence of water with the rate depending on
pH of the solution [7]
Si(C
2
H
5
O)
4
4H
2
O Si(OH)
4
4C
2
H
5
OH
The alcohol solution of the monomer was diluted
with demineralized water and brought to desired pH in
the range 13 with hydrochloric acid against the
standard glasscalomel electrode. No correction for
nonaqueous medium was taken into account. The
extent of hydrolysis was measured by the ratio, the
area of methylene groups linked to Si and sum the
area of methylene groups linked to Si or ethanol in
1
H NMR spectra of TEOS solution. Fig. 2 shows
example of the region of the methylene groups linked
to Si in the
1
H NMR spectrum for different hydrolysis
time: 1, 20 and 90 min, for experiments carried out
at pH=2.7.
The quartets centered at 3.55 and 3.75 ppm with
respect to tetramethylsilane are due to ethanol and
TEOS, respectively. In Turner and Franklin paper [18]
the quartets was centered at 3.59 and 3.80 ppm,
respectively, and in Brinker et al. [7] the quartets at
3.70 and 3.90 ppm were found.
Presumably this shift in the peaks quartets position
is a result of the solvent (C
6
D
6
) used for measurement
and internal standard, i.e. TMSCCl
4
. All these peaks
decreased in intensity as hydrolysis progressed
(Fig. 2).
Result of measurements of TEOS hydrolysis in time
dependence as a function of pH (1.33.6) was applied
for selecting a range of hydrolysis parameters.
Both the rate and extent of hydrolysis were found
to depend very strongly on pH value. It is shown
Fig. 1. Apparatus for drying of silica aerogels under supercritical conditions: (1) reactor, (2) water cooler, (3) pressure separator, (4) pressure
valves, (5) nitrogen gas cylinder, (6) pump, (7) CO
2
gas cylinder, (8) gas flowmeter, and (9) container.
M. Stolarski et al. / Applied Catalysis A: General 177 (1999) 139148 141
in Fig. 3. The calculated and below presented rate
constants of TEOS hydrolysis with the use of acid
catalyst (HCl solution) reects our experimental data
presented in Fig. 3. Kinetics analysis of experimental
data shows that TEOS hydrolysis reaction in the
studied pH range is rst-order reaction.
Fig. 3. Influence of pH of silica aerogel precursor on hydrolysis time.
Fig. 2. Region of the methylene groups linked to Si in
1
H NMR spectra of TEOS solutions for different hydrolysis time: 1, 20, and 90 min at
pH=2.7.
142 M. Stolarski et al. / Applied Catalysis A: General 177 (1999) 139148
k = 2X6848 10
2
min
1
for pH = 1X3Y
k = 3X3546 10
3
min
1
for pH = 2X7Y
k = 1X5582 10
3
min
1
for pH = 3X0Y
k = 0X3422 10
3
min
1
for pH = 3X6X
Very satised goodness of t (0.940.99) of experi-
mental data to the calculated regression equation was
found. For 25% initial concentration of TEOS in
ethanol with stoichiometric amount of water (these
conditions were considered the optimal concentrations
of reagents and used in further experiments), with the
increase of pH from 1.3 to 3.6 the maximum yield of
hydrolysis dropped down from 95% to 70% (Fig. 3)
and the time of reaction increased from 25 min to 20 h
(Figs. 2 and 3).
Further experiments were made for the samples
hydrolyzed at pH=3.0. The extent of hydrolysis
was 92.4% after the time of 6.5 h.
It is difcult to separate the reaction of hydrolysis
from formation of SiOSi links which leads to
gelation, because this type of measurements is possi-
ble only with using of
29
Si NMR while
1
H NMR gives
only information on hydrolysis extent. At the condi-
tions applied in this work, gelation was accompanied
by phase separation. The built up of turbidity could
therefore be used to monitor the rate of gel formation.
This rate was found to be the highest at neutral pH or
slightly above pH=7. Aqueous ammonia was used to
bring pH to a desired value.
3.2. The effect of preparation procedures on the
texture of aerogels
The parameters that were modied during prepara-
tions were the precursor (TEOS) concentration (5
45 wt%), water content (2030 wt% with respect to
the stoichiometric amount), pH of hydrolysis (2.0
3.6) and pH of gelation stage (5.98.6). For the
samples prepared at these conditions the texture
was characterized including bulk density, total surface
area, and total pore volume. All results are collected in
Table 1 and shown in Figs. 47.
3.3. pH at hydrolysis
According to the literature date, hydrolysis of
TEOS catalyzed by acids is nucleophilic reaction,
probably S
N
2 type. The reaction is an equilibrium
one what means that alcohol and =SiOR groups
remains within gel. The condensation reaction is even
more complicated, because a molecular analysis of the
growing chain or the quantitative analysis of the
particle growth steps are very difcult. But, both
Fig. 4. Influence of hydrolysis pH on specific surface area and specific pore volume of the prepared silica aerogels.
M. Stolarski et al. / Applied Catalysis A: General 177 (1999) 139148 143
hydrolysis and condensation are the main steps den-
ing the structure of the growing and nal polymer
which inuence strongly the further steps.
The hydrolysis was found to proceed depending on
pH. The time of hydrolysis was 50 and 1440 min, at
pH 2 and 3.6, respectively. This observation is in
agreement with the nding of Brinker and Scherer
([7], p. 212) which stated that up to pH=7 decrease in
H