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Synthesis and characteristic of silica aerogels

Marek Stolarski, Jerzy Walendziewski


*
, Mieczysaw Steininger Barbara Pniak
Institute of Chemistry and Technology of Petroleum and Coal, Technical University of Wrocaw, ul. Gdanska 7/9, 50-310 Wrocaw, Poland
Abstract
The synthesis of silica aerogels had been carried out by hydrolysis of tetraethoxysilane (TEOS) as an aerogel precursor in
ethanol solution, followed by gelation of the sols obtained and drying under supercritical conditions. The inuence of
concentration of TEOS, pH of hydrolysis and pH of gelation on the bulk density, specic surface area and porosity of silica
aerogels were investigated. # 1999 Elsevier Science B.V. All rights reserved.
Keywords: Silica; Silica aerogel; Gelation; Synthesis
1. Introduction
The aerogels are, as the name suggests, the gels with
air constituting one of its components. Since this
denition is good for most porous materials, the term
aerogels became reserved for the porous gels obtained
by removing solvent from highly swollen gels at the
conditions that no or minimal collapse occurs, most
conveniently at temperature and under pressure above
the critical point of the solvent. The no collapse
requirement distinguishes aerogels from xerogels.
Kistler [1,2] is regarded the father of aerogels. He
formulated the idea of replacing the liquid phase by
gas with only a slight shrinkage of the gel back in the
1930s. His attempts, however, with aqueous silica or
alumina gels (hydrogels) from which water was
removed at above critical conditions (3708C,
22.1 MPa) did not produce satisfactory results. Even-
tually, he obtained silica aerogels by:
1. the preparation of a hydrogel in reaction of
sodium silicate with hydrochloric acid,
2. careful removal of sodium and chlorine ions,
3. converting the hydrogel into alcogel by replacing
water with ethyl alcohol in a lengthy process of
multifold solvent replacement, and
4. drying at above critical conditions for ethyl alco-
hol.
The properties of silica aerogels were quite remark-
able.
Specic surface area was up to 1400 m
2
/g, bulk
density 80240 g/dm
3
, heat conductivity below
0.02 W/mK, excellent sound damping, etc. Later,
Fricke [3,4] obtained aerogels from alumina, tungsten,
tin, and iron oxides, as well as from organic gels:
gellatine, proteins, and cellulose.
Rediscovery of aerogels took place in the 1960s.
The Teichner et al. [5] at the Claude Bernard
University in Lyon substantially simplied the
procedure by carrying out the solgel transition
in the very solvent which was then removed at
supercritical conditions. The substrates were tetra-
Applied Catalysis A: General 177 (1999) 139148
*Corresponding author. Tel.: +48-71-320-35-51; fax: +48-71-
320-35-51; e-mail: walendziewski@nafta1.nw1.pwr.wroc.pl
0926-860X/99/$ see front matter # 1999 Elsevier Science B.V. All rights reserved.
PII: S0926-860X(98)00296-8
methoxysilane, triisopropylaluminium, iron acetyl-
acetate, nickel acetate, etc.
The inorganic aerogels were expected to be efcient
supporting media for catalysts in various chemical
processes [6]. They seem to become rather special
materials, very light and transparent.
Silicate gels are most often synthesized by hydro-
lyzing of monomeric tetrafunctional alkoxide precur-
sors employing a mineral acid (e.g. HCl) or base (e.g.
NH
3
) as a catalyst. At the functional group level, three
reactions are generally used to describe the solgel
process [7]:

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

concentration results in lowering in hydrolysis


rate. Then the samples were brought to pH=7 and
the time was measured until they lost uidity. The time
of gelation was again the longer the higher was the
hydrolysis pH (91168 min, for pH 23.6, respec-
tively.)
The effect of pH at which TEOS was hydrolyzed on
the texture of aerogels is shown in Fig. 4. All samples
had high specic surface area (640980 m
2
/g) and
large pore volumes. The bulk density of the samples
was slightly diminishing from 0.095 to 0.083 g/cm
3
as
pH of hydrolysis increased from 2 to 3.6. It seems
worth noticing that by using weak acids, such as
aqueous acetic acid, instead of hydrochloric acid
the hydrolysis reaction was difcult to control. The
problems with control of TEOS hydrolysis with the
use of acetic acid were caused by its chelating proper-
ties. The surface area of the samples obtained with
acetic acid did not exceed above 100 m
2
/g, although
the porosity was above 10 cm
3
/g.
Table 1
The effect of preparation conditions on the texture of silica aerogels
TEOS concentration
(wt%)
Water/TEOS
(mol/mol)
Hydrolysis
pH
Hydroloysis
time (min)
Gelation
pH
Gelation
time (min)
Bulk density
(g/cm
3
)
Surface area
(m
2
/g)
Pore volume
(cm
3
/g)
a
25 4
b
2 50 7 91 0.095 638 11.1/5.7
25 4 2.4 180 7 96 0.089 981
25 4 3 330 7 128 0.083 935 8.6/4.9
25 4 3.6 1440 7 168 0.083 862 10.2/5.7
5 4 3 330 7 960 0.015 782 8.6/4.8
15 4 3 330 7 190 0.043 1150
25 4 3 330 7 128 0.083 935 8.6/4.9
35 4 3 330 7 41 0.104 808 5.6/2.7
45 4 3 330 7 16 0.162 713
25 20
c
3 330 7 180 0.085 737 8.2/4.4
25 0
c
3 330 7 128 0.083 935 8.6/4.9
25 10
c
3 330 7 100 0.084 734
25 20
c
3 330 7 41 0.082 695 14.3/7.9
25 30
c
3 330 7 16 0.074 651 7.7/5.6
25 4 3 330 5.9 1080 0.071 428 8.1/3.8
25 4 3 330 6.6 175 0.076 868
25 4 3 330 7 128 0.083 935 8.6/4.9
25 4 3 330 7.3 50 0.082 1082 10.9/5.7
25 4 3 330 7.7 17 0.083 897 12.2/6.0
25 4 3 330 8.1 8 0.087 881
25 4 3 330 8.6 5 0.090 812 7.4/4.2
25 4 1.4 1.4 6
d
0.131 934 5.4/3.1
25 4 2.6 2.6 5
d
0.104 953 5.9/3.7
25 4 2.9 2.9 4
d
0.101 1079
25 4 3.6 3.6 4
d
0.076 715 7.5/4.6
25
e
4 3.0 7.0 50 0.036 88 14.2/7.5
a
Total pore/volume of pores with radii >50 nm.
b
Stoichiometric amount.
c
Water overplus, wt% in relation to stoichiometric water demand.
d
Months.
e
Hydrolysis in the presence of acetic acid.
144 M. Stolarski et al. / Applied Catalysis A: General 177 (1999) 139148
It is worthy further to notice that the properties of
hydrolyzed precursor affects gelation time and aerogel
surface area and pore volume. It means that in the
course of hydrolysis some chemical processes, con-
nected with gelation, are initiated. Under very low pH
(ca. 2) rate of hydrolysis is high but because of low
condensation rate probably very large part of uncon-
densed monomers is subjected to condensation at
pH=7. Totally hydrolyzed precursor molecules
(monomers) quickly condense forming large, three-
dimensional structures of very high volume. Increase
in hydrolysis pH results in lowering of hydrolysis rate
and increase in hydrolysis time and next increase in
condensation rate. Then product of hydrolysis at pH
ca. 2.4 is partially condensed when it is submitted to
gelation at pH=7. Presumably under these conditions
Fig. 5. Influence of TEOS concentration on specific surface area and specific pore volume of the prepared silica aerogels.
Fig. 6. Influence of water quantity introduced to hydrolysis reaction mixture on pore volume and specific surface area of the prepared silica
aerogels.
M. Stolarski et al. / Applied Catalysis A: General 177 (1999) 139148 145
condensation type clustercluster growth model takes
place [7], resulting in linear polymeric complexes with
high surface area and lowspecic pore volume. Above
pH=2.4, when rate of hydrolysis reaction is further
lowering and rate of condensation is increasing, addi-
tionally new monomers as a result of dissolution,
hydrolysis of siloxane are formed. These phenomena
probably causes that predominant growth mechanism
changes from clustercluster to monomercluster. As
a result more branched structures characterized by
increasing pore volume and lowering specic surface
area are formed.
3.4. Precursor concentration
To establish the effect of precursor concentration,
we changed its starting from 5 to 45 wt%. All samples
were treated in the same way, i.e. hydrolysis pH was
3.0, water was added at stoichiometric amount, and
gelation pH was set to 7.0. As expected, both specic
surface area and pore volume dropped down sharply
passing concentration of 1525 wt% (cf. Fig. 5).
Simultaneously, the time of gelation decreased
from 960 to 16 min and bulk density increased
from 0.015 and 0.162 g/cm
3
. It is the result of more
compact aerogel structure: The obtained aerogel
structures were characterized by particles of smaller
size with low pore volume and probably partly closed
pores resulting in relatively small specic surface
area measured by nitrogen adsorptiondesorption
method.
3.5. Water concentration
The amount of water used at hydrolysis step was
found to have a signicant effect on the texture of
aerogels. The effect of water concentrations was
examined for the samples prepared at precursor con-
centrations: 25 wt%, hydrolysis pH: 3.0, and gelation
pH=7.0 (Table 1). The highest surface area (935 m
2
/
g) was obtained using stoichiometric amount of water.
Both deciency and excess of water led to a reduction
of surface area by 200300 m
2
/g (Fig. 6). With an
increase of water excess over the stoichiometric
amount, the pore volume dropped down from 8.2 to
7.7 cm
3
/g and time of gelation reduced from 180 to
56 min. The bulk density of aerogels changed at the
range 0.0740.085 g/cm
3
was effected in the least
degree by water concentration (Table 1).
3.6. pH at gelation
This parameter was found to be most important with
respect to the aerogel texture. The samples for study-
ing the effect of gelation pH contained 25 wt% of
precursor and were hydrolyzed at pH 3.0 with stoi-
chiometric amount of water. With the increase of
gelation pH from 5.9 to 8.6 the rate of gelation rapidly
Fig. 7. Influence of gelation pH on specific surface area and specific pore volume of the prepared silica aerogels.
146 M. Stolarski et al. / Applied Catalysis A: General 177 (1999) 139148
increased. The time of gelation dropped down from
1080 to 5 min, respectively. At the same time the
surface area increased from 428 m
2
/g at pH=5.9 to
1082 m
2
/g at pH 7.3. Further increase of gelation
pH to 8.6 had a reversed effect; the surface area
decreased by ca. 270 m
2
/g. The maximum of total
pore volume (12.2 cm
3
/g) was observed for gelation
pH=7.7. The bulk density was in the range 0.071
0.09 g/cm
3
(Fig. 7). It is evident on the base of the
experiments made that at the highest condensation
and redistribution reaction rates the silica aerogels
of the highest specic surface area and pore volume
are obtained.
The silica gels obtained at pH of hydrolysis in the
range 1.43.6 and left at this same pH, required a very
long time to gel: 46 months. It is known that gelation
rate at low pH is characterized by very low value. The
aerogels obtained from these gels had large surface
areas (7151079 m
2
/g), comparatively large bulk den-
sities (0.0760.1008 g/cm
3
) and pore volumes not
exceeding 7.5 cm
3
/g.
Summarizing one can state that from point of view
of the texture, the most favorable condition of their
preparation of silica aerogels are:
1. tetraethoxysilane concentration in alcohol: 15
25 wt%,
2. pH at hydrolysis stage: 2.43.0,
3. stoichiometric amount of water (1 mol/mol of
oxyethylene group),
4. pH at gelation stage: 7.07.3.
3.7. Morphology of silica aerogels
The aerogel prepared at the optimal conditions are
amorphous solids of high specic surface area (930
1150 m
2
/g) and high porosity (8.69.6 cm
3
/g). No
crystalline phase was detected by X-ray diffraction
methods. Silica aerogels are macroporous materials
and only part of pore volume, ca. 33%, is created by
pores with radii smaller than 50 nm (Table 2). The
large contribution to the total pore volume comes from
pores of radii 550 nm. Specic volume of these pores
is 2.92 cm
3
/g. On the other hand the high surface area
is related to the presence of mesopores of radii 2
50 nm, and particularly high amount of those of radii
up to 5 nm (70% of overall surface area). The pore
radii distribution for selected samples was determined
in a gravimetric sorption apparatus by the sorption of
carbon dioxide and benzene. It seems worthy to point
out that the contribution of the smallest pores radii 2
5 nm to the overall surface area and pore volume is
relatively small. For traditional silica catalyst supports
the contribution from these smallest pores usually
exceeds 50%.
4. Summary
Application of tetraethoxysilane (TEOS) as a aero-
gel precursor in ethanol solution enables to obtain
silica aerogels with high porosity and large specic
surface area. At the optimal conditions of silica aero-
gel preparation precursor concentration, tetraethoxy-
silane solved in anhydrous ethanol, have to be in the
range 1525% wt%, hydrolysis pH 2.43.0, gelation
pH 7.07.3 and stoichiometric water to aerogel pre-
cursor ratio.
Silica aerogels obtained at these parameters are
amorphic form of silica, of the following physico-
chemical properties: bulk density 0.0430.089 g/cm
3
,
specic surface area 9351150 m
2
/g overall pore
volume 8.610.9 cm
3
/g.
Silica aerogels are rather macroporous materials,
only part of pore volume, ca. 33%, is created by pores
with radii smaller than 50 nm. Large contribution to
the total pore volume, ca. 30%, comes from pores
Table 2
Pore structure of silica aerogel determined with using of CO
2
sorption
Surface area and pore volume for pore radius (nm) Total
<2 23 35 510 1050 250
Surface area (m
2
/g) 173 38.4 325.1 218.6 223.4 805.5 1082
a
Pore volume (cm
3
/g) 0.0066 0.048 0.661 0.784 2.138 3.631 10.9
b
a
By nitrogen thermodesorption.
b
By mercury porosimetry methods.
M. Stolarski et al. / Applied Catalysis A: General 177 (1999) 139148 147
of radii 550 nm. Surface area is almost exclusively
related to the presence of mesopores of radii 250 nm,
and particularly high amount of those of radii up to
5 nm (70% of overall surface area).
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