Thermal treatments of activated carbon

catalysts under N
2
O
Jose de Jesu s D az Velasquez
a,
*
, Luis M. Carballo Suarez
b
,
Jose Luis Figueiredo
c
a
Laboratorio de Combustibles, Departamento de Qumica, Facultad de Ciencias, Universidad Nacional de Colombia, Bogota , DC, Colombia
b
Departamento de Ingeniera Qumica, Facultad de Ingeniera, Universidad Nacional de Colombia, Bogota , DC, Colombia
c
Laborato rio de Cata lise e Materiais, Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do Porto, 4200-465 Porto, Portugal
Received 9 November 2005; accepted 20 September 2006
Available online 16 October 2006
Activated carbon is a very versatile material, and the
control of its surface chemistry allows to design truly uni-
que catalysts for applications in dierent industrial reac-
tions and processes [1,2]; therefore, a systematic study of
the carbon surface oxygen groups is needed in the context
of the oxidative dehydrogenation of hydrocarbons in gen-
eral [3,4] and of isobutane in particular, from which little
is known using activated carbon as catalyst. In this work,
we report on the textural and chemical modications
induced by treating an activated carbon under nitrous
oxide. These materials are to be tested in the oxidative
dehydrogenation of isobutane, and their activities corre-
lated with the types and amounts of surface functional
groups.
An activated carbon Norit ROX 0.8 (CORIG) was used
in the present study, which was subsequently exposed to
treatments with 20% nitrous oxide at 773 K during 180,
360 and 600 min (samples CN/180, CN/360, and CN/
600). To selectively remove some groups, the sample CN/
360 was subjected to a thermal treatment in a nitrogen
atmosphere during 60 min at 873, 1023 and 1373 K (CN/
360/600, CN/360/750 and CN/360/1100). The burn o, de-
ned as the ratio between the mass lost during the treat-
ment and the initial dry mass, was determined for each
sample. The activated carbon samples were characterized
by elemental and proximate analyses, nitrogen adsorption
at 77 K, Temperature Programmed Oxidation (TPO),
Temperature Programmed Desorption (TPD) and XPS as
described elsewhere [5].
Table 1 shows the results of the carbons characteriza-
tion. An increase in volatile matter content was observed
for oxidative treatment, which indicates an increase in sur-
face functional groups. Also, a slight increase in nitrogen
content with increasing residence times was observed,
which may imply some nitrogen incorporation into the
carbon matrix or in nitrogen surface groups. Samples
CN/360/600, CN/360/750 and CN/360/1100 show a
decrease in volatile matter content due to the decomposi-
tion of surface groups. The oxygen content of these
carbons also decreases, corresponding to the removal of
oxygen surface groups.
The nitrogen adsorption isotherms at 77 K were ana-
lysed by the t-method and by the BET and DubininRad-
ushkevich (DR) equations; the results obtained are
included in Table 1. The dierent treatments produce tex-
tural changes in the carbons. In general, the BET surface
area, the mesopore surface area, and the micropore volume
and size increase with the burn o for all the treatments.
These changes are due to carbon gasication produced
by oxidation, opening up and enlarging existing pores, or
creating new micropores [6].
Table 2 shows the characteristic peak maxima tempera-
tures in TPO spectra (T
max
). The carbons present a small
increase in the T
max
at higher burn os which could be ex-
plained by the formation of more stable supercial groups.
These more stable groups could be associated with the
incorporation of nitrogen into the surface, as suggested
by several authors [7,8] who observed an inhibition eect
from the nitrogen content in carbons on its oxidation
behaviour.
The surface oxygen complexes formed during the prep-
aration or subsequent treatments of the activated carbon
decompose upon heating, releasing CO and CO
2
at dier-
ent temperatures. The CO and CO
2
released in TPD tests
are associated with surface oxygen groups, mainly anhy-
drides, lactones, phenols and carbonyl/quinones [5]. Table
2 shows the amounts of CO, CO
2
and the ratio CO/CO
2
re-
leased, obtained by integration of the areas under the TPD
peaks. It could be observed that the amount of CO released
increased with burn o, which indicates an increase in the
amount of the surface oxygen groups. A slight decrease
in the amount of CO
2
is observed at low burn o levels, fol-
lowed by an increase.
Figs. 1 and 2 show changes in the shape of TPD proles
which are important to stand out in relation with the treat-
ments severity. For the catalysts treated in N
2
O, the CO
0008-6223/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2006.09.024
*
Corresponding author. Tel.: +571 3165000x14468; fax: +571 3165220.
E-mail address: jddiazv@unal.edu.co (J. d. Jesu s D az Velasquez).
212 Letters to the Editor / Carbon 45 (2007) 203228
peak (Fig. 1) shows a left shoulder at lower temperature
which is more noticeable as the treatment is more severe
(larger residence time). This indicates the presence of at
least two types of functional groups: around 900 K for
the phenol groups and 1100 K for the carbonyl/quinone
groups as it was reported by Figueiredo et al. [5] for dier-
ent oxidative treatments. Regarding the CO
2
spectra
(Fig. 2), the presence of the peak at low temperatures for
the CORIG (without treatment) catalyst is observed. This
peak corresponds to carboxylic acid groups that decom-
pose at temperatures lower than 673 K, which practically
disappears for the catalysts treated at higher temperatures.
On the other hand, at temperatures higher than 673 K a
main peak is observed with a left shoulder which is more
visible for lower burn os, and practically disappears at
higher levels of oxidation. The shoulder, around 800 K,
corresponds to carboxylic anhydrides and the peak at
higher temperature to lactone groups which decompose
forming CO
2
at about 940 K [5]. Carboxylic anhydrides
also contribute to the CO peak, but the amounts are negli-
gible in comparison to phenol and carbonyl groups.
In the CO spectra, the left shoulder of the main peak is
small and practically disappears in CN/360/600, it becomes
a tail in CN/360/750 and totally disappears in CN/360/
1100. In the CO
2
spectra, a left shoulder for the main peak
is observed (around 820 K) which disappears after the ther-
mal treatments, and the main peak at higher temperature
decreases and disappears at 1373 K. The thermal treatment
for the catalyst CN/360 at 873 K removes the majority of
carboxylic anhydride groups and part of the lactone and
some of the phenol groups. At 1023 K, the lactone groups
are removed completely together with the phenol groups,
while some carbonyl groups tend to disappear with the
treatment at 1373 K. These ndings for the catalyst treated
in N
2
O and heated at dierent temperatures agree with the
results obtained by Figueiredo et al. [5] for a carbon oxi-
dized in air and thermally treated. The amounts of CO
and CO
2
decrease as well as the ratio CO/CO
2
, as can be
Table 2
Temperatures of peak maxima in TPO and amounts of CO and CO
2
released, obtained by integration of the areas under TPD peaks
Sample Burn o (%) T
max
(K) CO (lmol/g) CO
2
(lmol/g) CO/CO
2
CORIG 806.7 527 235 2.24
CN/180 10.06 803.0 1757 205 8.57
CN/360 12.83 805.5 2093 211 9.94
CN/600 22.50 808.0 2817 300 9.39
CN/360/600 14.04 805.5 1881 167 11.24
CN/360/750 18.31 800.5 1115 171 6.52
CN/360/1100 21.39 825.0 268 99 2.70
200 400 600 800 1000 1200 1400
0.0
0.2
0.4
0.6
0.8
1.0
CN/360/750
CN/360/600
CN/360/1100
Corig
CN/180
CN/360
CN/600
C
O

(

m
o
l
.
g
-
1
.
s
-
1
)

Temperature, K
Fig. 1. TPD spectra before and after dierent treatments (CO evolution).
Table 1
Carbon characterization
Sample Proximate analysis
(% m/m, daf)
Elemental analysis
(% m/m, dry)
BO
(%)
Textural characterization
BET
(m
2
/g)
W
01
(cm
3
/g)
W
02
(cm
3
/g)
W
meso
(m
2
/g)
L
l
(nm) VM FC C H N S O
CORIG 8.70 91.30 93.21 0.28 0.56 0.84 5.11 1048 0.364 0.032 126 0.96
CN/180 11.80 88.20 92.73 0.23 0.23 0.67 6.14 10.06 1180 0.407 0.049 139 1.13
CN/360 12.43 87.57 90.48 0.19 0.27 0.55 8.51 12.83 1210 0.414 0.051 153 1.16
CN/600 14.03 85.97 90.02 0.31 0.94 0.68 8.05 22.50 1322 0.443 0.076 180 1.42
CN/360/
600
9.81 90.19 91.59 0.26 0.97 0.87 6.31 14.04 1201 0.411 0.053 153 1.19
CN/360/
750
8.33 91.67 93.22 0.23 0.83 0.74 4.98 18.31 1245 0.429 0.052 155 1.26
CN/360/
1100
3.70 96.30 97.53 0.17 0.48 0.59 1.23 21.39 1201 0.405 0.063 145 1.14
VM: Volatile Matter; FC: Fixed Carbon.
Letters to the Editor / Carbon 45 (2007) 203228 213
seen in Table 2. It is important to note that the catalyst that
presents the larger CO/CO
2
ratio is CN/360/600 in which
the majority of the carboxylic anhydride, some lactone,
and phenol groups have been eliminated. The results (not
shown) obtained from the deconvolution of the XPS oxy-
gen peak (O
1s
) are in agreement with these ndings, and
in particular they conrm that the nitrous oxide treatment
incorporates nitrogen into the material.
The ratio CO/CO
2
, given by the TPD, increases during
the oxidative treatments at low burn os, indicating the
development of functional groups such as carbonyl, phe-
nol, ether and quinone, which decompose into CO; the
ratio decreases at larger burn os, indicating the formation
of carboxylic anhydrides and lactones. In particular, we
have shown that oxidative treatments in oxygen could
introduce this type of sites [4,5], but the resulting catalysts
showed poor stability. In the present work, it is shown that,
upon treatment in N
2
O, the resulting materials are more
stable and the ratio CO/CO
2
is higher, for the same burn
o. It is therefore expected that these materials will exhibit
good catalytic activity and stability in the oxidative dehy-
drogenation of isobutane, which is the subject of a separate
publication.
Acknowledgements
This work was carried out in the framework of the pro-
ject ALR/B7-3011/94.04-6.0108.9, CATALISE-ALFA.
The authors thank Carlos Sa and M. Freitas for the XPS
analysis. J. D az thanks the Universidad Nacional de
Colombia for the study commission and the Universidade
do Porto for a period of training.
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200 400 600 800 1000 1200 1400
0.00
0.02
0.04
0.06
0.08
0.10
0.12
CN/360/1100
CN/360/750
CN/360/600
Corig
CN/180
CN/360
CN/600
C
O
2

(

m
o
l
.
g
-
1
.
s
-
1
)
Temperature, K
Fig. 2. TPD spectra before and after dierent treatments (CO
2
evolution).
Physisorption-induced change in the magnetism
of microporous carbon
H. Sato
a
, N. Kawatsu
a
, T. Enoki
a,
*
, M. Endo
b
,
R. Kobori
c
, S. Maruyama
c
, K. Kaneko
c
a
Department of Chemistry, Tokyo Institute of Technology, Ookayama, Megro-ku, Tokyo 152-8551, Japan
b
Department of Electrical Engineering, Shinshu University, Wakasato, Nagano, 380-8553, Japan
c
Deptartment of Chemistry, Chiba University, Yayoi-cho, Inage-ku, Chiba, 263-8522, Japan
Received 23 December 2005; accepted 18 September 2006
Available online 24 October 2006
Activated carbon bers (ACFs) are composed of a ran-
dom network of nanometer size fragments of graphite
(nanographite domains), where each nanographite domain
0008-6223/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2006.09.017
*
Corresponding author. Tel.: +81 3 5734 2242; fax: +81 3 5734 2242.
E-mail address: enoki.t.aa@m.titech.ac.jp (T. Enoki).
214 Letters to the Editor / Carbon 45 (2007) 203228