Carbon 43 (2005) 786–795

www.elsevier.com/locate/carbon

KOH and NaOH activation mechanisms of multiwalled

carbon nanotubes with different structural organisation
a,b,*
E. Raymundo-Piñero , P. Azaı̈s a, T. Cacciaguerra a, D. Cazorla-Amorós b,
A. Linares-Solano b, F. Béguin a,*
a
CRMD, CNRS-University, 1b Rue de la Férollerie, 45071 Orléans Cedex 02, France
b
Departamento Quimica Inorganica, Universidad de Alicante, Apartado 99, E-03080 Alicante, Spain

Received 23 June 2004; accepted 2 November 2004

Available online 9 December 2004

Abstract

New information was obtained on the mechanism of porosity development during chemical activation by KOH and NaOH using
various multiwalled nanotubes (MWNTs) of different structural organization. The high purity MWNTs were prepared by acetylene
decomposition on a cobalt-based catalyst at different temperatures. The obtained samples ranged from MWNTs with well organised
graphitic walls to nanotubes with disorganised layers mixed with some pyrolytic carbon when decreasing synthesis temperature. The
results of transmission electron microscopy (TEM) observations were linked with gas adsorption measurements and X-ray diffrac-
tion data. They show that NaOH is only effective with disordered materials whereas KOH is effective whatever the structural order.
After reaction of the poorly ordered precursor with KOH, the nanotubular morphology is completely destroyed, whereas it is pre-
served when NaOH is used. However for the more ordered materials, the morphology remains unchanged with both reactants.
Effects of activation are only seen with KOH, which generated a large concentration of defects in the nanotubes walls. The differ-
ences found between KOH and NaOH during activation are related with an additional intercalation step of metallic K or Na pro-
duced during the redox reactions. It is shown that metallic K has the ability to be intercalated in all materials in contrast with Na
which can only intercalate in the very disorganised ones. The conclusions obtained from the study on ordered nanotubes were con-
firmed with an ordered carbon black, demonstrating that the structural organization of the carbon precursor is an important param-
eter which must be taken into account when alkali reactants are used for the activation.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: A. Carbon nanotubes; B. Activation; C. Adsorption, Transmission electron microscopy, X-ray diffraction

1. Introduction from the performance point of view, allowing activated

Chemical activation has been shown as a very effi-
cient method to obtain carbons with high surface area
and narrow micropore distribution. Among all the
chemical activation agents, alkaline hydroxides as
KOH or NaOH are reported to be highly interesting
*
Corresponding authors. Tel.: +34 965 903 946; fax: +34 965 903
454 (E. Raymundo-Piñero).
E-mail addresses: raymundo@ua.es (E. Raymundo-Piñero),
beguin@cnrs-orleans.fr (F. Béguin).
carbons to be prepared from many kinds of carbona-
ceous precursors (coals, chars, fibres, etc) [1–18].
Although it is a frequently used process to prepare acti-
vated carbons, the general mechanism of chemical acti-
vation is not well understood, and the various
interpretations found in literature underline the process
complexity [2,5–17]. In general terms, chemical activa-
tion by alkalis consists in solid–solid or solid–liquid
reactions involving the hydroxide reduction and carbon
oxidation to generate porosity. During the reactions,
CO, CO2 and H2 evolution is observed, and additional

0008-6223/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2004.11.005
 E. Raymundo-Piñero et al. / Carbon 43 (2005) 786–795
reactions between active intermediates produced on the
surface and the constituents of the gas phase are possi-
ble. A recent study suggests that the carbon/MOH
(M = Na or K) reaction mechanism is independent of
the hydroxide used and consists in the overlapping of re-
dox processes [15,16]. The hydroxide reduction leads to
H2 and Na or K metals, and carbon is oxidised to
carbonates (Na or K) according to the global reaction
(1):
6MOH þ C $ 2M þ 3H2 þ 2M2 CO3 ð1Þ
In a previous work [18] we have used chemical activa-
tion with KOH to effectively develop the microporosity
of different kinds of multiwalled nanotubes (MWNTs),
obtaining BET specific surface areas around 1000 m2/g
and micropore volumes close to 0.5 cm3/g. The TEM
observations showed that the nanotubular morphology
is preserved after activation although a large concentra-
tion of defects appears on the nanotubes surface. Sur-
prisingly, NaOH, which is a very effective activating
agent [4], could not activate most kinds of MWNTs,
in agreement with results found with other types of car-
bonaceous precursors [14]. The common feature of all
the materials for which NaOH was not an efficient acti-
vating agent, was the presence of some organisation of
the graphene layers. Therefore, the previous statements
that carbon activation by NaOH or KOH takes place
through the same reactions [15,16] are not completely
exact. It is clear that further work is needed to explain
the different activation behaviour of NaOH and KOH
as a function of the structural/nanotextural organisation
of the carbon precursor used.
In this work, we use the advantage that MWNTs can
be prepared with different structural organizations, in
order to study the influence of structure/nanotexture
on activation by KOH and NaOH. The pristine and
activated MWNTs are analysed by TEM in a way which
is not possible with regular carbons, and linking these
data with gas adsorption and XRD measurements al-
lows to demonstrate that the activation process is partly
controlled by the structural organization of the precur-
sor. These results will help to better understand the dif-
ferent activation behaviours of NaOH and KOH
observed with coals of different ranks [16].
2. Experimental
Carbon nanotubes were prepared by catalytic decom-
position of acetylene at 450, 500 or 600 °C on a pow-
dered CoxMg1xO solid solution catalyst according to
the process described in reference [19]. After synthesis,
the catalyst precursor is eliminated by dissolution in
concentrated HCl.
Chemical activation is performed by physically mix-
ing KOH or NaOH with the MWNTs using a activating
787
agent/carbon ratio of 4/1 and a maximum heat treat-
ment temperature of 800 °C in a N2 flow (250 ml/min).
After activation the materials were extensively washed
in diluted HCl and water.
Transmission electron microscopy (TEM, Philips
CM20) was used for the observation of the materials be-
fore and after activation. For the analysis, few milli-
grams of the MWNTs were dispersed in anhydrous
ethanol and a drop of this suspension was deposited
on a TEM grid covered by a lacey amorphous carbon
film.
The porous texture of pristine and activated MWNTs
was analysed by N2 and CO2 adsorption at 77 and
273 K, respectively. Surfaces areas were calculated by
applying the BET equation to the N2 isotherm data.
The total and narrow micropore volumes were calcu-
lated with the Dubinin–Raduskevich equation from
the N2 and CO2 adsorption data, respectively. Mesopore
volume (for pore sizes between about 2–7.5 nm) was cal-
culated from the partial pressure range of the N2 iso-
therm between 0.2 < P/Po < 0.7.
The products of the KOH or NaOH/MWNTs reac-
tion at different temperatures using a 2/1 ratio under
a N2 flow of 250 ml/min were analysed by X-ray diffrac-
tion using CuKa or MoKa radiations (INEL CPS120).
Since the activation process produces alkali metals
which are extremely sensitive to air, the products were
transferred from the reaction furnace to a glove box
under Ar atmosphere and sealed in Lindeman capi-
llaries.
In order to demonstrate that an intercalation step can
occur in some cases, carbon nanotubes prepared at
600 °C were mixed with KOH or NaOH in a 1/1 ratio
and heat treated in a close vessel up to 800 °C inside a
glove box under Ar atmosphere. The same experiment
was done using a carbon soot for comparison purposes.
The products of the reactions were transferred and
sealed into Lindeman capillaries for their further XRD
analysis.
For having some reference of alkali metal intercala-
tion, reactions between MWNTs and Na or K metal
were carried out by the two-bulb technique in vapour
phase according to the conditions described in reference
[20]. Previously outgassed MWNTs are placed in one
extremity of the tube and in the other extremity an ex-
cess of the distilled metal is introduced. The tube is evac-
uated under high vacuum, then sealed and placed inside
a furnace able to create a temperature gradient between
the two extremities containing the MWNTs and the me-
tal. The temperature of the MWNTs was fixed at 300 °C
while metal was kept at lower temperature (250 °C) in
order to avoid its condensation on the nanotubes. As
the intercalation compounds are very sensitive to air,
the samples were transferred in a glove box under Ar
atmosphere and sealed into Lindeman capillaries for
XRD analysis.
788 E. Raymundo-Piñero et al. / Carbon 43 (2005) 786–795
3. Results and discussion
3.1. Chemical activation. Samples characterisation
Nanotubes were prepared by catalytic decomposition
of acetylene at 450 °C (NT450), 500 °C (NT500) and
600 °C (NT600). The TEM observations show that high
purity nanotubes are obtained at 600 °C and only few
tips are closed. Fig. 1 presents high resolution transmis-
sion electron microscopy images obtained in the 0 0 2 lat-
tice fringe mode for the different samples. It can be
observed that at 600 °C MWNTs with well organised
carbon walls are obtained (Fig. 1a). The outer surface
is less organised probably due to some deposition of
Fig. 1. TEM 0 0 2 lattice fringe images of MWNTs prepared at (a)
600 °C; (b) 500 °C; (c) 450 °C.
pyrolytic carbon. At 500 °C the MWNTs walls are not
as well ordered as in the previous case (Fig. 1b). Finally,
when the synthesis is performed at 450 °C, nanotubular
morphologies are still found, but they are not very well
organised (Fig. 1c). In addition, a high amount of pyro-
lytic carbon is also noticed either mixed with the nano-
tubes or on their surface. Hence, it is possible to produce
a tubular material with different degree of crystallinity
by modifying the synthesis temperature.
Fig. 2 contains the N2 adsorption isotherms for the
MWNTs prepared at 450 °C (Fig. 2a), 500 °C (Fig. 2b)
and 600 °C (Fig. 2c) before and after activation with
KOH and NaOH. All pristine nanotubes present similar
isotherms between type II and IV, with an hysteresis
loop typical of a mesoporous material. Mesoporosity
comes from the tubes entanglement and from the central
canal of the open tubes. Table 1 collects the BET specific
surface areas and the micropore and mesopore volumes
calculated from the N2 and CO2 adsorption isotherms.
When the synthesis temperature of MWNTs decreases,
the specific surface area slightly increases, as a conse-
quence of the increase in micropore volume. This corre-
sponds to the increase of the number of defects observed
in Fig. 1. In Fig. 2, it can be also observed that KOH is a
much more efficient activating agent than NaOH to gen-
erate porosity in MWNTs, and efficiency seems also to
depend on the structural order of the MWNTs used.
For the different materials after KOH activation, there
is an increase of N2 adsorption at low partial pressures
indicating the generation of micropores and the hyster-
esis is also more pronounced than in the pristine tubes,
confirming a wider distribution of mesopores size. Table
1 shows that the specific surface area of KOH activated
MWNTs increases with decreasing the structural/micro-
textural order of the graphene layers of the pristine
materials, i.e. increasing the materials reactivity, reach-
ing 1670 m2/g for the most disordered MWNTs. This in-
crease in specific surface area comes from the generation
of both micro- and mesopores.
On the contrary, NaOH has only some efficiency when
the pristine sample is highly disordered, as NT450. For
this material, the N2 adsorption isotherm (Fig. 2a) re-
veals some increase of N2 adsorption in the low partial
pressure region and changes in the mesoporosity region.
Table 1 shows a noticeable increase of specific surface
area when compared to the pristine material. By con-
trast, a very low increase of specific surface area was
found after activation with NaOH of the nanotubes pre-
pared at 500 and 600 °C (Fig. 2b and c, respectively). In
Table 1 it can be noticed that this small increase corre-
sponds to the generation of some mesopores, as it is also
reflected by the differences found in the hysteresis loop of
the N2 isotherms presented in Fig. 2.
These results are easily understandable after observ-
ing the TEM images from the materials after reaction
with KOH and NaOH. Fig. 3 presents, as an example,
 E. Raymundo-Piñero et al. / Carbon 43 (2005) 786–795 789

1400 1400

1200 NT450 1200 NT500

NT450KOH NT500KOH
NT450NaOH NT500NaOH
1000
V(cm3/g,STP)

1000

V(cm3/g,STP)
800 800

600 600

400 400

200 200

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
(a) P/Po (b) P/Po

1400

1200 NT600
NT600KOH
NT600NaOH
1000
V(cm3/g,STP)

800

600

400

200

0
0 0.2 0.4 0.6 0.8 1

(c) P/Po

Fig. 2. N2 adsorption isotherms at 77 K for the pristine and activated MWNTs.

Table 1 a mesoporous material, the isotherm of KOH activated

Porous texture characteristics of the pristine and activated MWNTs NT450 is almost type I, typical of a microporous mate-
SBET V microðN2 Þ V microðCO2 Þ Vmeso rial (Fig. 2). By contrast, Fig. 3b shows that when the
(m2/g) (cm3/g) (cm3/g) (cm3/g) same low temperature MWNTs are activated with
NT 450 °C 345 0.14 0.06 0.13 NaOH, the material keeps now the nanotubular mor-
NT 450 °C KOH 1670 0.62 0.39 0.43 phology after the reaction. However, the high resolution
NT 450 °C NaOH 562 0.22 0.14 0.19 images show that many defects have been generated in
NT 500 °C 330 0.13 0.05 0.13 the tubes walls and now all tips are open. These are
NT 500 °C KOH 1220 0.46 0.29 0.41 the reasons for the increase of the micropore and meso-
NT 500 °C NaOH 386 0.14 0.09 0.17
pore volumes of this material after NaOH activation
NT 600 °C 326 0.13 0.03 0.13 (Table 1).
NT 600 °C KOH 868 0.32 0.22 0.29 The transmission electron microscopy characterisa-
NT 600 °C NaOH 377 0.14 0.07 0.16
tions on the more ordered material, NT600, after reac-
tion with KOH and NaOH are presented in Fig. 3c
and d, respectively. In both cases, the nanotubular mor-
the 0 0 2 lattice fringe images for the MWNTs NT450 phology is preserved. The high magnification picture
and NT600 activated with KOH or NaOH. Fig. 3a after KOH activation reveals that the process generates
shows that after reaction of the poorly ordered precur- a large concentration of defects in the nanotubes walls,
sor (NT450) with KOH, the nanotubular morphology giving rise to micropores. In addition, the few nanotube
is completely destroyed. The high magnification image tips which were closed are now open and contribute to
resembles to that of an activated carbon with graphene the mesopore volume accessible for N2 (Table 1). After
layers fully misoriented. These results are in agreement NaOH reaction, the wall structure is preserved and de-
with the differences found between the isotherms of fects are not observed even when a weight loss of
the pristine and activated materials. Whereas the pris- 40 wt% was measured. The tips of all the tubes are now
tine tubes present a type II and IV isotherm typical of open (Fig. 3d), fitting well with the slight mesoporosity
790 E. Raymundo-Piñero et al. / Carbon 43 (2005) 786–795
Fig. 3. TEM 0 0 2 lattice fringe images of MWNTs prepared at 450 °C and activated with (a) KOH and (b) NaOH; and of MWNTs prepared at
600 °C and activated with (c) KOH and (d) NaOH.
development observed by gas adsorption when com-
paring the pristine and the activated materials (Table 1,
Fig. 2).
The results presented above demonstrate a different
behaviour between KOH and NaOH during activation,
which is related with the structural organisation of the
pristine material. In summary, there are clear evidences
to state that KOH can be used as activating agent for
samples with different degree of crystallinity, being more
efficient with decreasing crystallinity. By contrast,
NaOH is only acting as activating agent when the mate-
rial structural order is not so high, reacting only where it
exists a high concentration of defects as in the low tem-
perature MWNTs or at the tips of highly ordered
MWNTs. The reasons of such a behaviour can be found
by deep analysis of the mechanism of chemical activa-
tion.
3.2. About reaction mechanism
X-ray diffraction (XRD) analyses were performed
with the objective of determining the reaction products
formed by the redox reactions between KOH or NaOH
with carbon during the pyrolysis of the mixture. For this
purpose, mixtures of KOH or NaOH/NT600 in a 2/1
mass ratio were treated up to 400, 600, 700 or 800 °C
in N2 atmosphere and further analysed by XRD, while
avoiding the contact with air. Fig. 4a presents the
XRD patterns for the pristine MWNTs (NT600), the
physical mixture MWNTs/KOH and the mixture after
reaction at different temperatures. From these XRD re-
sults, it can be observed that the redox reaction (carbon
oxidation) starts at around 400 °C, forming K2CO3. At
600 °C, the KOH peaks are no longer visible, indicating
that all KOH has been transformed into K2CO3 and if
the reaction temperature is increased up to 700 °C some
K2O can be detected. Finally, at 800 °C the only potas-
sium species which remain after the reaction is K2O. It
was also found that K2O is converted into KHCO3 after
contact with air, which is given as the main product of
the reaction for all the previous studies where the
XRD analysis was performed in air atmosphere [17].
However, the above observations agree with previous
results [15,16], proposing that the first step in the chem-
ical activation with KOH is a redox reaction which
could be summarized by the global reaction (1). When
the reaction temperature is higher than 700 °C, the fol-
lowing plausible reactions could explain the generation
of K2O:
K2 CO3 þ C $ K2 O þ 2CO ð2Þ
K2 CO3 $ K2 O þ CO2 ð3Þ
2K þ CO2 $ K2 O þ CO ð4Þ
 E. Raymundo-Piñero et al. / Carbon 43 (2005) 786–795 791

KOH K2 O
+ K2CO3 * Co NaOH Na
* + Na2CO3 * Co
* MWNT:KOH 800°C
+ + +
+ + * +
* MWNT:KOH 700°C ++ + *
+ + + ++ ++ * MWNT:NaOH 800°C
+ +
++ + + ++ + * +
+ +* +* MWNT:KOH 600°C + * MWNT:NaOH 700°C
+
+ + + ++ +
+ + * ++ * MWNT:NaOH 600°C
+ +
MWNT:KOH 400°C
MWNT:NaOH 400°C
MWNT:KOH
MWNT:NaOH
MWNT MWNT
10 20 30 40 50 60 70 80 90 100 10 20 30 40 50 60 70 80 90 100
(a) 2 Theta (b) 2 Theta

Fig. 4. XRD patterns (CuKa) of MWNTs prepared at 600 °C (a) during the reaction with KOH at different temperatures; (b) during the reaction
with NaOH at different temperatures.

These reactions are very favourable for potassium, hav-
ing large negative free energies at the reaction tempera-
ture [8] and it is known that alkali metal carbonates can
decompose at temperatures below their melting point in
the presence of carbon [15,16,21]. In addition, such reac-
tions are supported by the fact that evolution of CO and
CO2 was observed from TPD experiments over KOH/C
mixtures when temperature is higher than 700 °C
[15,16]. Finally, the K2O formed could be also expected
to react with carbon by the reaction:
K2 O þ C $ 2K þ CO
which has a negative free energy change at around
800 °C [8].
The case of NaOH activation can be seen in Fig. 4b
which shows the XRD patterns for the same pristine
MWNTs, the MWNTs mixed with NaOH and the prod-
ucts of the reaction at different temperatures. In this
case, the redox reaction (Na2CO3 formation) starts at
higher temperature (600 °C) than for KOH (400 °C).
This observation is in agreement with the higher reactiv-
ity of KOH when compared with NaOH. However, con-
trarily to the case of KOH, we observe that Na2CO3 is
the only product at 700 °C, and at higher temperature
(i.e. 800 °C) important peaks of metallic Na are seen
in addition to the Na2CO3 peaks. This observation is
in agreement with the global reaction summarized by
Eq. (1).
After comparison of Fig. 4a and b, it can be noticed
that, as expected, the first step of the activation reaction
by hydroxides is a redox process. Another important re-
mark is that for the reaction with NaOH (Fig. 4b) metal-
lic Na was found on the surface of the material, whereas
metallic K was not detected after reaction with KOH.
The reason could be that at the reaction temperature
the vapour pressure of potassium is higher than that
of sodium. However, these results could be also ex-
plained considering that potassium produced by KOH
reduction is intercalated between the graphitic type lay-
ers. In the literature, the intercalation of metallic potas-
sium has been suggested as one of the steps in the
chemical activation of carbon by using KOH
[2,9,11,14]. However, only recently, Xue et al. were
showing a direct evidence of the formation of graph-
ite–potassium intercalation compounds during the acti-
vation of MCMB with KOH [17].
In order to have some references to demonstrate any
metal intercalation during the activation by KOH or
NaOH, in a first step, we have checked if the pure metals
ð5Þ
(K or Na) are able to be intercalated into the different
MWNTs precursors (NT450, NT500 and NT600). For
this purpose, vapour phase reactions were carried out
between the distilled metal and the MWNTs by the
two-bulb technique according to the conditions de-
scribed in the experimental part.
Fig. 5a shows the X-ray diffractograms of the pristine
nanotubes prepared at different temperatures and of
their reaction products with K. After reaction of potas-
sium with the nanotubes prepared at low temperatures
(NT450 and NT500), the broad d002 peak corresponding
to the interplanar distance of the pristine materials
(d  0.35 nm) shifts to a higher value at d  0.4 nm. This
result indicates that K insertion/intercalation took place
resulting in the separation of the graphene layers. In the
case of the MWNTs prepared at higher temperature
(NT600), the (0 0 2) line of pristine MWNTs completely
disappears. A new peak at ca. 0.55 nm corresponds to
the 1st stage intercalation compound, whereas two other
peak at ca. 0.4 nm and 0.28 nm are attributed to higher
stage derivatives [22,23].
Fig. 5b shows the results after Na reaction with the
same materials. The 0 0 2 line of the most disordered
MWNTs (NT450) is shifted to higher interlayer distance
from d002  0.35 nm to d002  0.4 nm, indicating Na
insertion and separation of the graphene layers. By con-
trast, the XRD pattern of MWNTs prepared at higher
792 E. Raymundo-Piñero et al. / Carbon 43 (2005) 786–795

KOH. By comparing this XRD pattern after KOH reac-

tion with the one presented in Fig. 5a from the same
K Na material after reaction with K vapour, it is possible to
conclude that these lines correspond to K intercalation
NT450 NT450
compounds. Hence, these data confirm that K is interca-
lated between the graphene layers during the activation
process by KOH. In addition, Fig. 6a shows that if the
KOH reacted sample is exposed to air, the new peaks
K
Na
disappear and only the carbon (0 0 2) line remains. This
is another confirmation that K intercalation compounds
NT500
NT500 were formed during the activation reaction, as it is well
known that these derivatives are unstable in air, spe-
cially due to moisture [27]. The comparative XRD pat-
terns in the region of (0 0 2) line of carbon for the
K pristine and NaOH reacted material are presented in
Na
Fig. 6b. After reaction with NaOH, we could not ob-
NT600 NT600 serve any shift of the (0 0 2) line of carbon. This result
agrees with the data presented in Fig. 5b, indicating that
0.65 0.55 0.45 0.35 0.25 0.15 0.65 0.55 0.45 0.35 0.25 0.15 Na cannot be inserted/intercalated between the graph-
(a) d (nm) (b) d (nm) ene layers of the well organised MWNTs prepared at
600 °C.
Fig. 5. XRD patterns (CuKa) in the region of the (0 0 2) line of carbon The differences found between KOH and NaOH,
for (a) the various MWNTs before and after reaction with K in the gas
phase; (b) the various MWNTs before and after reaction with Na in
regarding their activating behaviour, can be explained
the gas phase. by different intercalation ability of K and Na depending
on the structural order of the pristine material [24–26].
Metallic potassium produced during the redox reaction
temperatures (NT500 and NT600) is unchanged after between MWNTs and KOH can be intercalated into
contact with Na vapour, indicating the absence of metal the nanotubes walls, independently of the structural
insertion/intercalation. order of the material, being responsible for the separation
Hence, it is clearly demonstrated that K can be in-
serted/intercalated in all the MWNTs studied and that
its intercalation process is favoured with the increase
in crystallinity, whereas Na can be inserted/intercalated
to a much lower extent only in the MWNTs of low
structural order. These results are in agreement with
the well known fact that intercalation of alkali metals
as Na or K strongly depends on the crystallinity of the
host carbon [24–26]. In this sense, K can be intercalated Air
into graphite-like structures [24], whereas Na can be
only intercalated in low temperature carbons with
non-graphitic structure [24–26].
After documenting the intercalation behaviour of al-
kali metals (Na and K) in the different MWNTs, we
decided in a second step to check if the same phenome- KOH
non could be observed in the conditions of chemical
NaOH
activation. For this purpose, 1/1 KOH/MWNTs or
NaOH/MWNTs mixtures were heat treated in a close
NT600
vessel up to 800 °C under Ar atmosphere. The experi- NT600
ments were done with the highly ordered MWNTs
(NT600) which were showing the highest differences 0.65 0.55 0.45 0.35 0.25 0.15 0.65 0.55 0.45 0.35 0.25 0.15
during KOH and NaOH activation. Fig. 6a presents (a) d (nm) (b) d (nm)
the XRD patterns in the region of the (0 0 2) line of car-
Fig. 6. XRD patterns (CuKa) in the region of the (0 0 2) line of carbon
bon for the pristine and KOH activated materials. Addi-
for (a) MWNTs prepared at 600 °C, after reaction with KOH in static
tionally to the typical (0 0 2) peak of the pristine material Ar atmosphere and the previous sample after contact with air; (b)
at d  0.35 nm, two new lines can be observed ca. MWNTs prepared at 600 °C and after reaction with NaOH in static Ar
0.28 nm and 0.4 nm after reaction of the nanotubes with atmosphere.
 E. Raymundo-Piñero et al. / Carbon 43 (2005) 786–795
Fig. 7. TEM 0 0 2 lattice fringe images of the carbon black CS.
and degradation of the graphitic layers and thus for the
development of microporosity. On the contrary, sodium
is only able to be intercalated in highly defective materi-
als. Therefore, NaOH only activates the MWNTs pre-
pared at low temperature.
In order to determine if the same results could be ob-
tained from other materials with an ordered nanotex-
ture, a carbon black (CS) prepared by CVD (CENIM,
CSIC, Madrid, Spain) has been studied. The 0 0 2 lattice
fringe mode image presented in Fig. 7 confirms that this
material presents a highly ordered nanotexture with gra-
phitic layers concentrically oriented in the spherical par-
ticles. This material has been reacted with KOH or
NaOH in the same conditions previously used for the
MWNTs (i.e. temperature: 800 °C; N2 flow of 250 ml/
min). Fig. 8 shows the N2 adsorption isotherms of the
carbon black before (CS) and after activation with either
KOH or NaOH (CSKOH and CSNaOH, respectively).
The pristine carbon black used has a negligible specific
surface area. A type I isotherm is observed in Fig. 8 after
the reaction with KOH, that demonstrates the genera-
tion of micropores, due to KOH activation. After reac-
250
CS
CSKOH
200
CSNaOH
V(cm /g,STP)
150
3
100
50
0 4. Conclusion
0 0.2 0.4 0.6 0.8
P/Po
Fig. 8. N2 adsorption isotherms at 77 K for the pristine carbon black
(CS) and for CS activated with KOH and NaOH.
793
Air
KOH
CS
0.65 0.55 0.45 0.35 0.25 0.15
d (nm)
Fig. 9. XRD patterns (CuKa) in the region of the (0 0 2) line of carbon
for the pristine CS, after reaction with KOH in static Ar atmosphere
and the previous sample after contact with air.
tion with NaOH, the increase in N2 adsorption is very
low, indicating that NaOH was not able to develop
porosity. Hence, the carbon black and the MWNTs pre-
pared at high temperatures (NT500 and NT600) have a
similar behaviour because of their ordered nanotexture.
XRD patterns of the (0 0 2) region for carbon after
performing the KOH/carbon black (CS) reaction under
a static Ar atmosphere are shown in Fig. 9. By analogy
with Fig. 6a for the KOH/MWNTs reaction, lines at
higher and lower interlayer distances than the (0 0 2) line
for carbon are appearing, corresponding to the same
intercalation potassium compound which was detected
in Figs. 5a and 6a for the case of the MWNTs. In Fig.
9 it can be also observed that if the KOH reacted sample
is exposed to air, these new lines found in the reacted
material disappear and only the (0 0 2) line for carbon
remains.
Therefore, we can confirm that all the conclusions ob-
tained before with MWNTs can be extended to other
carbonaceous materials and potassium intercalation is
a common step in the activation process of materials
with high microtextural order.
1
The mechanism of chemical activation by KOH and
NaOH has been studied in nanotube materials ranging
from high purity MWNTs with well organised graphitic
794 E. Raymundo-Piñero et al. / Carbon 43 (2005) 786–795
walls to nanotubes with disorganised layers mixed with
some pyrolytic carbon. We have demonstrated that
there is a different behaviour of NaOH and KOH as
activating agents related with the structural organisation
of the pristine material. NaOH is only effective with dis-
ordered materials whereas KOH was found effective
with all of them.
The chemical activation process starts with similar re-
dox reactions between carbon and KOH or NaOH, pro-
ducing metallic K or Na and the metal carbonate
(K2CO3 or Na2CO3). However, the reaction proceeds
further with KOH giving K2O. In addition, K metal
produced from the redox reactions is intercalated be-
tween the graphene layers of the carbon materials; the
higher the structural order, the better intercalation.
Hence, during the chemical activation with KOH, K
intercalation can be considered as a relevant step which
will have an important influence on the total reaction
mechanism. The metal intercalation favours the process
by separating the layers, that generates micropores or
even new high energy sites for the redox reactions. The
differences of efficiency found between KOH and NaOH
for the activation of MWNTs of different crystallinity
are explained by the fact that K intercalates better than
Na.
The possibility of obtaining a series of nanotubes of
various structural organisation simply by changing the
preparation temperature, was extremely useful for this
study. The uncertainty which could appear in the results
interpretation using materials from different sources is
eliminated. Moreover, HRTEM could be efficiently ap-
plied for monitoring the effects of activation, that would
not be possible with regular carbons. Hence, it is now
well demonstrated that the structural organization of
the carbon precursor is an important parameter which
must be taken into account when alkali reactants are
used for the activation.
Acknowledgments
This research was supported by a Marie Curie fellow-
ship of the European Community programme ‘‘Improv-
ing Human Research Potential and the Socio-Economic
Knowledge Base’’ under contract number HPMF-CT-
2001-01453.
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