Professional Documents
Culture Documents
4386
Introduction
1971.
(4) Kinoshita, K. Carbon: Electrochemical and Physicochemical
Properties; Wiley: New York, 1988.
(5) Bansal, R. C.; Donnet, J. B.; Stoeckli, H. F.Actiue Carbon;Marcel
Dekker: New York, 1988.
(6) Wen, W. W.;
Sun,S. C. Sep. Sci. Technol. 1981, 16, 1492.
(7) Lau, A. C.; Furlong, D. N.; Healy, T. W.; Grieser, F. Colloids Surf:
1986, 18, 93.
(8) Fuerstenau, D. W.; Rosenbaum, J. M.; You, Y. S. Enegy Fuels
1988,2, 241.
(9) Solar, J. M.; Le6n y Le6n, C. A,; Osseo-Asare, K.; Radovic, L. R.
Carbon 1990,28,369.
(10) Le6n y Le6n, C. A.; Radovic, L. R. In Chemistry and Physics of
Carbon;Thrower, P. A., Ed.;Marcel Dekker, Inc.: New York, 1994;Vol.
24, p 213.
%BO
% ash
A1
1.0
2.5
5.0
8.0
18.6
25.0
42.0
61.4
0.04
0.05
A2
A3
A4
Results
0.08
0.10
W=W,exp-
(Pi3"I
-
A = RT I
n
(
;
)
5 (mV) = 12.8,~~
(108m2/s*V)
(2)
(4)
(3)
(5)
Moreno-Castilla et al.
EO,
wo
WO(COrr),
sample
kJ/mol
cm3.g-1
cm3.g-1
A1
A1N
A10
A2
A2N
A20
A2S
A3
A3N
A30
A3S
A4
A4N
A40
22.8
22.6
22.6
20.9
20.9
20.9
20.8
16.3
14.2
16.3
15.8
13.4
12.4
13.5
1.96
1.86
1.95
1.74
1.68
1.78
1.83
1.63
1.12
1.39
1.42
1.41
1.09
1.29
0.270
0.259
0.278
0.330
0.275
0.324
0.368
0.520
0.414
0.580
0.576
0.723
0.561
0.737
0.270
0.259
0.278
0.330
0.275
0.324
0.368
0.509
0.335
0.567
0.562
0.497
0.204
0.503
sco*,
Sext,
SN2r
,2Lg-1
m2.g-l
712
683
733
870
725
854
970
1342
800
1495
1482
1310
538
1326
785
650
750
825
660
800
800
1290
740
1200
1060
1600
820
1400
v3,
cm3.g-1
v2 3
m2.g-1
cm3.g-1
18.3
30.7
21.5
22.5
34.6
29.8
21.1
38.2
41.4
42.4
40.5
65.9
34.8
59.1
0.063
0.097
0.071
0.078
0.105
0.089
0.068
0.119
0.128
0.132
0.127
0.225
0.114
0.200
0.068
0.089
0.061
0.078
0.116
0.115
0.074
0.155
0.164
0.166
0.131
0.309
0.194
0.243
7.00
6.02 .
5.m .
6403.
3.m
A3
1.m .
0.m
0.75
095
115
135
155
1.75
195
215
235
L (nm)
6.m
5.m
6 4.m
$3.03
2.m
1.m .
0.m
0 75
0 85
0 95
I 05
I15
I 25
I 35
t (nm)
200
6 150
100
050
om
075
A4
2.m
085
095
105
115
125
135
145
155
165
175
L (nm)
2m
A3
075
115
095
155
135
175
215
I95
235
t (nm)
A4
150
co,
coz,
sample
mmol-g-l
mmol-g-l
CO/COZ
%Oa
A1
A1N
A10
0.41
5.43
1.47
0.04
3.18
0.49
10.3
1.7
3.0
0.8
18.9
3.9
A2
A2N
A20
A2S
0.32
5.74
1.38
3.38
0.02
3.56
0.40
1.27
16.0
1.6
3.5
2.7
0.6
20.6
3.5
9.5
A3
A3N
A30
A3S
0.24
5.93
1.62
3.40
0.01
3.34
0.45
1.14
24.0
1.8
3.6
3.0
0.4
20.2
4.0
9.1
A4
A4N
A40
0.26
6.22
2.02
0.00
3.27
0.38
1.9
5.3
0.4
20.4
4.4
5 100
51
050
000
1
12
I6
16
I4
22
24
28
26
L (nm)
291:
34po
1720, I 'I
I ,
I1
,1260
300
400
500
600
700
800
900
lo00
1100
1200
900
lo00
1100
1200
T (K)
I'
51
...._.,.-...-...
0
300
400
500
600
700
800
T (K)
3600
3200
2SOo
2400
2000
1600
izoo
aoo
cm-l
Figure 6. FTIR spectra of activated carbonsfrom the A3 series.
potential a t the shear plane which is adjacent to the
external surface. Therefore these measurements yield
false information on the overall surface characteristics of
granular activated carbons, whereas mass titration measurements involve the transfer of Hf and OH- ions
between the bulk phase and the surface. These two types
of measurements have been used in carbon surface
Moreno-Castilla et al.
Discussion
Surface areas and pore textures of all samples used are
given in Table 2 and Figures 1-5, which show the
calculated micropore size distributions. From the results
obtained on the surface characterization the following
points can be deduced. First, for the original activated
carbons (from A1 to A4), the increase in the degree of
activation (%BO in Table 1) brings about an increase in
the S Nand
~ Sextvalues. Sco2also increases but only up to
about 40%BO (sample A3). The mean micropore width,
Lo,is shifted to higher values (Figure 11, and there is a n
increase in Vz and V3 values. All these results indicate
that an increase in %BO produces an increase in micropore
volume up to 40% BO, a widening of the microporosity,
and also a n increase in the meso- and macroporosity of
the samples. At higher BO, sample A4, the microporosity
is centered in the supermicropores (higher limit of
micropores) and in the lower limit ofthe mesopores which
makes this the only sample in which S N>~Sco2,due to
capillary condensation of Nz into the supermicropores. In
the other cases, Sco2 is always similar or quite close to
."I
>ti
sc02
SN2.
A2
-30
4r -40
S N Z*
- 10
o
-801
-
A2S
2 7
60
PH
2o
10
- 10
-20
-30
A3
-40
-4Oi
I
-50
-- 560
01
A3N
-70
A3S
A30
-701
9.9
2.4
4.8
1.8
A2S
10.4
2.3
4.8
1.4
2.4
nd
2.3
nd
A3
A3N
A30
A3S
10.6
2.4
4.9
1.3
3.4
nd
2.1
nd
A4
A4N
A40
11.1
2.3
4.7
4.1
A2
A2N
A20
nd = not detected.
structure^.^^
In conclusion, the FTIR technique detected, from a
qualitative point of view, that the treatment with HN03
fixed carboxyl groups and probably nitro and nitrate
groups, whereas the treatments with H202 and (NH4)&08
fixed carboxyl, ketone, and ether groups. These results
are most likely due to the drastic nature of the treatment
with HN03, which partially broke the porous texture of
the activated carbons compared with the other two
oxidizing treaments, which probably does not favor the
formation of ketone and ether groups.
Desorption profiles of C02, CO, and H2O are depicted
in Figure 7 for the oxidized samples from activated carbon
A3. The C02 desorption profile (Figure 7a) of sample A3N
is similar to that of other activated carbons oxidized with
HN03.14,48-51The maximum rate of COZ evolution is a t
575 K, with a shoulder a t around 700 K that tails up to
around 1200 K. This profile is indicative ofthe occurrence
of chemically different complexes and/or the same oxygen
complex existing on energetically different ~ i t e s . ~ ~
Thus,
-~O
anhydride groups which can be formed from two adjacent
carboxylgroups during the TPD runs are more stable than
carboxylic acid groups and, therefore, will evolve CO2 and
CO above 573 K. Possible evidence for the formation of
anhydride groups during the experiments is that the H 2 0
profiles (Figure 7c) present a peak a t around 500 K
inmediately after evolution of physisorbed water. The
COz desorption profile ofA3O sample presents a maximum
desorption rate at around 575 K, as for the A3N sample,
and a tail up to around 1200 Kwith no significant shoulder
a t 700 K. In the case of sample A3S, the maximum
desorption rate of the C02 profile is shifted to a lower
temperature, 525 K, than in the above cases, which
indicates that the thermal stability of the carboxyl groups
present on this sample is lower than that on samples A3N
and A30. After this maximum there is a slight shoulder
in the region of 700 K, possibly due to the presence of
carboxyl anhydride groups. These groups will be present
in a higher proportion in sample A3N due to the fact that
the HN03 treatment fixed the highest amount of oxygen
that evolved as C02. The carboxyl anhydride groups will
also yield CO, probably in the same temperature range
as C 0 2 .
With regard to the CO profiles (see Figure 7b), sample
A3N has a small maximum a t 530 K, which is shifted to
500 Kin sample A3S and does not appear in sample A30.
Sample A3N has a shoulder a t around 775 K (which can
correspond to the shoulder a t around 700 K in the COz
desorption profile due to anhydride carboxyl groups), and
the maximum desorption rate is a t 1000 K, whereas
sample A3S has a peak a t this temperature and the
maximum desorption rate is shifted to 1130 K. The CO
profile of sample A30 does not present any peak and
increases continuously from 600 up to 1170 K.
The amounts of C02 and CO evolved from all samples
are given in Table 3 and the results obtained indicate
that (i) The amount of oxygen fixed after the different
(47) Starsinic, M.;Taylor, R. L.; Walker, P. L., Jr. Carbon 1983,21,
69.
(48)Linares-Solano, A.; Salinas-Martinez de Lecea, C.; CazorlaAmor&, D.;Joly, J. P. In Fundamental Issues in Control of Carbon
Gasification Reactiuity; Lahaye, J., Ehrburger, P., Eds.; NATO/ASI
Series E192; Kluwer Academic: New York, 1991; p 409.
(49) Cazorla-Amor6s, D.;Linares-Solano, A,; Joly, J. P.; SalinasMartinez de Lecea, C. Catal. Today 1991,9, 219.
(50) Otake, Y.; Jenkins, R. G. Carbon 1993, 31, 109.
(51)Vinke, P.; Van der Eijk, M.; Verbree, M.; Voskamp, F.; Van
Bekkum, H. Carbon 1994,32, 675.
Moreno-Castilla et al.
Conclusions
In this study, the surface modifications of activated
carbons after their treatments with HN03, HzOz, and
(NH4)&08 have been analyzed. Treatment with HN03
causes a decrease in surface area and in the microporosity
ofthe activated carbons, and these effects are more drastic
with increasing degrees of activation of the original
activated carbon. However, the treatments with H2Oz
and (NH4)2S208were not as drastic, and in some samples
the oxygen surface complexes were fixed a t the entrance
of the micropores so that there was some restricted
diffusion of Nz a t 77 K.
From FTIR, carboxyl groups and probably carboxylcarbonate structures as well as nitro and nitrate groups
were detected after the HN03 treatment, whereas after
the HzOz and (NH4)&08 treatments carboxyl, ketone,
and ether groups and probably carboxyl-carbonate structures were detected. The amount of oxygen fixed after
these treatments followed the sequence HN03 (NH4)ZSz08 > HzOz, and the CO/COZ ratio followed a contrary
sequence, probably due to the higher proportion of ketone
and ether groups with respect to COz-liberatingcomplexes
on samples treated with peroxides.
Finally, the most important is that treatment with
(NH4)zSzOefixed stronger acid groups than treatment with
HN03 in spite of the fact that this latter treatment fixed
the largest amount of oxygen surface complexes evolving
as COZ. There is the added advantage that, unlike the
HN03 treatment, treatment with (NH4)~S208does not
modify the surface area and pore texture of the original
activated carbon to a great extent. These findings can be
important when using activated carbons in reactions
catalyzed by acidic solids.