ARTICLE NO.
CS964564
AND
MIGUEL GREGORKIEWITZ 1
INTRODUCTION
About 500 silica gel samples were prepared by neutralization of sodium silicate solutions (Panreac, 6 mol/liter SiO2 ,
SiO2 /Na2O 3.3 by weight) with hydrochloric acid (Carlo
Erba p.a., 2 mol/liter HCl).
In order to conduct polycondensation at a defined pH, the
method of Ref. (10) was followed: hydrochloric acid and
silicate solution were added simultaneously to distilled water
in a polypropylene beaker, and the mixture was vigorously
stirred to avoid local changes in pH during the formation of
the precursor sol. The silicate solution was added through a
459
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Copyright q 1997 by Academic Press
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MICROPOROUS SILICA
[1]
slow
GSi{OH / 0O{SiG r
GSi{O{SiG / OH 0
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[2]
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TABLE 1
Percentage of Different Species of Silicate Tetrahedra, Qn, and Its Variation with the Reaction Time, t,
for Silica Sols Prepared at pH 1, 3, and 9 and [Si] 0.9, 0.7, and 0.3 mol/liter, Respectively
pH
12
t(h)
Q0
Q1
Q2
Q3
Q4
Q3/Q4
4
10
33
45
8
5.6
1
1
3
24
50
23
16
50
34
2.17
24
14
52
34
1.47
1.53
3
31
12
49
39
51
5
42
53
1.25
0.79
17
48
35
1.37
24
8
51
41
1.24
9
47
9
46
45
1.00
72
8
41
51
5
34
42
19
0.80
Note. The percentages have been obtained from the integrated area of the corresponding peaks in the
for comparison (as in Fig. 1), and gelation falls, in all cases, between the last two points.
2.21
24
4
41
55
0.74
48
12
13
37
38
0.97
72
99
14
43
43
1.00
9
91
0.10
29
(Fig. 3 in (18)). The corresponding results in terms of surface area, porosity, and pore radius of the different samples
are resumed in Table 2 which is divided into four parts in
order to examine the influence of the different parameters
during the polycondensation reaction.
The most important parameter is observed to be the pH:
as can be seen in Table 2 (part a), the specific surface area
is practically constant at a very high value of 650700 m2 /
g for acid-prepared gels, but it decreases steadily for pH
6. The pore volume, on the other hand, shows a maximum
at 6 pH 7 and it depends less on pH, which makes that
the pore size, as calculated from 2Vp /SBET , increases with
.
pH from r 10 until 49 A
Furthermore, it is observed (Table 2, part b) that, for pH
3, the silica concentration has little influence upon SBET ,
whereas the pore radius increases slightly with [Si]. More
important is the temperature (Table 2, part c) which causes
!) and
a considerable increase in pore size (from 5 to 15 A
3
porosity (0.150.50 cm /g) when going from 4 to 707C.
Finally, aging (Table 2, part d) is observed to cause a slight
increase of the pore size which goes from r 10.7 to r
for pH 3.
15.4 A
The pore size distribution was analyzed for gels prepared at different pH and showed an essentially monodisperse structure, although in the mesoporous samples ( pH
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MICROPOROUS SILICA
FIG. 5. Syneresis behavior of silica gels of [Si] 0.2 mol/liter prepared at different pH values. The time of aging is measured as beginning
from the moment of gelation.
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TABLE 2
Specific Surface Area SBET , Pore Volume Vp , and Pore Radius
r for Silica Xerogels and Their Dependence on Different Reaction
Parameters
a. Effect of pH during preparation of the sol
([Si] 0.41 mol/liter, T 207C)
pH
SBET (m2/g)
Vp (cm3/g)
)
r 2Vp/SBET (A
1
2
3
4
5
6
7
8
9
693
683
654
634
699
568
467
398
205
0.39
0.35
0.35
0.38
0.44
0.62
0.64
0.56
0.50
11.2
10.2
10.7
12.0
12.6
21.8
27.4
28.1
48.8
SBET (m2/g)
Vp (cm3/g)
)
r 2Vp/SBET (A
0.26
0.41
0.50
0.55
0.67
0.77
644
654
776
654
716
652
0.42
0.35
0.55
0.52
0.53
0.54
13.0
10.7
14.2
15.9
14.8
16.6
SBET (m2/g)
Vp (cm3/g)
)
r 2Vp/SBET (A
4
20
70
598
656
674
0.15
0.36
0.50
5.0
10.9
14.8
Aged
SBET (m2/g)
Vp (cm3/g)
)
r 2Vp/SBET (A
3
3
7
7
0
/
0
/
654
671
467
597
0.35
0.52
0.64
1.03
10.7
15.4
27.4
34.5
Note. All data refer to xerogels obtained from freshly prepared hydrogels
without aging, except for pH 9, where some aging was necessary to keep
the gel from dissolving in the washing step and, of course, the aged samples
cited in part d.
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REFERENCES
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