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Microporous and Mesoporous Materials 60 (2003) 173–181

www.elsevier.com/locate/micromeso

Study of chemical activation process of a


lignocellulosic material with KOH by XPS and XRD
an a,*, D.M. Nevskaia a, J.L.G. Fierro b,
J. Dıaz-Ter
A.J. Lopez-Peinado a, A. Jerez a
a
Dpto. Quımica Inorganica, Fac. Ciencias, Universidad Nacional de Educaci
on a Distancia (UNED), C/Senda del Rey 9,
28040 Madrid, Spain
b
Instituto de Cat
alisis y Petroleoquımica (ICP), CSIC, Campus UAM, Cantoblanco, 28049 Madrid, Spain
Received 8 July 2002; received in revised form 27 March 2003; accepted 31 March 2003

Abstract

Chemical activation of carbons is currently a very common method for obtaining activated carbons with very high
surface areas. KOH is one of the most effective agents employed for this purpose. However, the reaction mechanism of
this kind of activation it is not yet completely elucidated, although some models have been proposed. In this paper, an
activated charcoal was obtained from a lignocellulosic material by impregnation with different amounts of KOH. The
activation process was studied by X-ray photoelectron spectroscopy and X-ray diffraction. These techniques point to
the formation of different potassium compounds at the carbon surface (mainly K2 CO3 and different oxides) and show
the dependence between surface area development in the carbons and the amount of K2 CO3 formed during the acti-
vation process.
Ó 2003 Elsevier Science Inc. All rights reserved.

Keywords: Activated Charcoal; Chemical Activation; X-ray diffraction; X-ray photoelectron spectroscopy

1. Introduction lored ACs with optimized properties, such as


surface area, pore size distribution and functional
Nowadays, activated carbons (ACs), due to surface groups. The carbon properties depend
their structural properties and relatively low cost mainly on the nature of the raw material and the
are among the more important industrial carbons thermal treatment leading to the final ACs [2,15].
[1,2]. They are widely used in different fields e.g., as There are many precursors from which ACs can
adsorbents [3–8], catalysts [9–11] or catalyst sup- be obtained. The use of lignocellulosic materials
ports [9,12–14]. The challenge is to prepare tai- for the manufacture of absorbents is frequent.
These materials are obtained as by-products of the
agricultural and food industries and, hence, they
*
Corresponding author. Tel.: +34-91-398-7350; fax: +34-91-
are cheap and their use contributes to the conser-
398-6697. vation of the environment. Thus, there are many
E-mail address: jaimediaz@ccia.uned.es (J. Dıaz-Teran). literature reports related to the preparation of ACs

1387-1811/03/$ - see front matter Ó 2003 Elsevier Science Inc. All rights reserved.
doi:10.1016/S1387-1811(03)00338-X
174 J. Dıaz-Teran et al. / Microporous and Mesoporous Materials 60 (2003) 173–181

from coconut shells [16–18], olive stones and waste 2. CO2 evolution due to the reaction of K2 CO3
[15,19,20], and others [8,21–25]. with the coal or char [33] close to 750 K. This
The production of ACs from these materials gives rise to the formation of complex salts
involves pyrolysis of the raw precursor followed by (C–O–K) at the carbon surface.
the so-called ‘‘activation methods’’. These activa- 3. CO evolution above 920 K due to the reaction
tion procedures include ‘‘physical activation’’, in of K2 CO3 and K2 O with carbon:
which different gases as CO2 or water vapor are
employed [15,19,26], or ‘‘chemical activation’’, in K2 O þ C ! 2K þ CO
which different agents (KOH, H3 PO4 , ZnCl2 , . . .)
K2 CO3 þ C ! 2K þ 3CO ½32
are used to promote the carbonization and acti-
vation in a single step [15,27,28]. KOH is widely
used as an activation agent since it leads to optimal
As a consequence of these reactions, a decrease
textural and chemical properties of the carbon
in the amount of K2 CO3 is observed, which can be
[27,28]. Nevertheless, the mechanism of the acti-
accurately evaluated by HCl titration. However,
vation processes is not yet completely elucidated.
others studies [34,35] connect the CO evolution
Some models for the chemical activation of cokes
near 950 K with the destruction of different surface
or lignocellulosic materials with KOH have been
groups, such as quinones, carbonyl- or pyrone-like
suggested [17,23,27,29,30]. In the model proposed
groups, associated with carbons of acid-base
by Marsh and Yan [27] for the activation of cokes,
character. On the other hand, the activation pro-
the authors stated that, in accordance with
cess with high amounts of KOH may cause the loss
McKees considerations [31], the potassium ‘‘may
of the base character of carbons due to the
form alkalides such as –OK groups using the ox-
breakage of aromatic rings, as could be seen else-
ygen of the alkali salt’’. These compounds would
where by f-potential and pH measurements [8].
cause the separation of carbon lamellae by the
This could interfere with the determination of the
oxidation of cross-linking carbon atoms and
amount of carbonate with HCl.
the formation of surface groups in the edge of the
In the mechanism proposed by Ehrburger et al.
lamellae. They considered that these facts cause
[30], the complex salts formed at the carbon sur-
the loss of their flat form. Finally, as the washing
face could act as ‘‘active sites’’ in the gasifica-
removes these compounds, the original structure
tion process. Furthermore, no differences were
cannot be restored.
observed when K2 CO3 was employed as activat-
Ehrburger et al. [30] studied the effect of different
ing agent. For the preparation of an AC with a
amounts of KOH and NaOH on the development
very high surface area, Otawa et al. [17] pro-
of carbon porosity. Upon impregnation carbons
posed a mechanism in which the first effect of
with KOH, these authors observed the formation
KOH was the destruction of the carbon matrix,
of K2 CO3 with a simultaneous evolution of CO2
and the high specific surface area was due to the
and CO. They proposed three reactions taking
intercalation of potassium compounds. Moreover,
place during the activation process with KOH:
a large amount of potassium metal formation
was observed above 973 K. They proposed that
1. Formation of K2 CO3 [32]:
the so-called ‘‘potassium cycle’’ occurs in the ac-
4KOH þ @CH2 ! K2 CO3 þ K2 O þ 3H2 tivation:

KOH!K2 O! K
Dehydration
? !K2 O!
Reduction ? Oxidation Hydration
KOH
?
y
Structure intercalation
J. Dıaz-Teran et al. / Microporous and Mesoporous Materials 60 (2003) 173–181 175

Hu and Vansant considered the same cycle in the tractor first with HCl solution and then with
preparation of an AC obtained from coconut bidistilled water until complete HCl elimination.
shells [23] and pointed out the importance of the The samples are denoted by E followed by the
pre-treatment of samples, in which a partial de- agent name, the ratio of impregnation and the
struction of the carbon matrix had occurred, with pyrolysis temperature in Kelvin. The non-impreg-
the subsequent loss of mechanical strength upon nated samples were denoted as E-0 (temperature).
dehydroxylation. Nevertheless, no K2 CO3 forma- The sample prepared at a similar temperature but
tion was considered in the reaction mechanism, at a total pressure at <104 mbar, was denoted as
which agrees with the above reaction scheme. In- ‘‘V’’ before the name.
deed, the enhancement in surface area and poros- Specific surface areas were determined by N2
ity is explained by the formation of different adsorption isotherms at 77 K applying the BET
K-compounds in the carbon matrix, which leads to method [36] in a Micromeritics ASAP 2010 Volu-
a separation of the lamellae or destruction. The metric System. Pore size distributions were calcu-
structure does not return to the original form after lated by the Density Functional Theory (DFT)
elimination of these compounds, the new structure method [37,38] by means of the DFTplus software.
is permanent. By mean of this method, the volume and area of
To provide additional information for under- micropores (Vmic and Smic ), the total pore volume
standing the mechanism of chemical activation, (Vtot ) and the external surface area (Sext ) were cal-
the effect of KOH impregnation on the surface culated. With the aim to compare these results, we
area and porosity of a lignocellulosic material recalculated the micropore surface area (Smic ) by
(Stipa Tenacissima) was studied by means of X-ray means of the Dubinin–Radushkevich equation
diffraction (XRD) and photoelectron spectroscopy [39], and the macro and mesopore surface area
(XPS). (Sext ) was calculated as the difference between the
total and the micropore surface areas.
X-ray photoelectron spectra were recorded in a
Fisons Escalab 200R spectrometer equipped with
2. Experimental a hemispherical electron analyzer and an MgKa
(1253.6 eV) X-ray exciting source. The samples
The ACs were obtained from an esparto-grass were pre-treated under high vacuum at 423 K for 2
(Stipa Tenacissima) substrate. Esparto-grass is a h with the aim to remove adsorbed contami-
very common grass from southern Spain which nants. Peak intensities were estimated by calcu-
has currently no industrial uses. A detailed prep- lating the integral of each peak, after smoothing,
aration method was reported earlier [8]. Briefly, subtraction of an S-shaped background and fit-
the precursor was impregnated with aqueous so- ting the experimental curve to a combination of
lutions of KOH (analysis grade) at different ratios Gaussian and Lorenztian lines of variable pro-
(0%, 20%, 50%, 100% (1:1) and 400% (4:1) by portion (Fig. 1). All binding energies were refe-
weight) in a rotary evaporator. Another sample, renced to the C 1s line at 284.9 eV. This reference
taken as reference, was impregnated with K2 CO3 gave binding energy values with an accuracy of
with a ratio 1:1. After impregnation, the pyrolysis 0.1 eV.
was carried out under N2 atmosphere (100 XRD patterns were recorded in a Rayflex
ml min1 ) in a tubular furnace at different tem- XRD3100 equipment using CuKa X-rays
peratures (673, 873 and 1073 K), keeping the (k ¼ 1:54 A ) and a Ni filter. Steps of 0.02° were
maximum temperature for 30 min. The heating employed with a time of 1s per step. A high-tem-
rate employed was 10 K min1 in all cases. Car- perature chamber was coupled to the equipment
bons were allowed to cool down under N2 atmo- with the aim to follow the activation process ‘‘in
sphere up to room temperature. With the aim to situ’’. Several scans were carried out at different
remove the K-compounds from the carbon sur- temperatures under the same furnace conditions,
face, the samples were washed in a Soxhlet ex- both under N2 atmosphere and vacuum.
176 J. Dıaz-Teran et al. / Microporous and Mesoporous Materials 60 (2003) 173–181

3. Results and discussion

It has been demonstrated that very high surface


area ACs (near 2000 m2 g1 ) can be obtained from
this lignocellulosic material using KOH as im-
pregnating agent [8]. The surface area depends on
three different parameters, namely the pyrolysis
temperature, the mass ratio of KOH and the raw
material. Table 1 shows the surface characteriza-
tion data of carbons obtained at different tem-
peratures and mass ratios. High values of the
specific surface area (SBET ) were obtained at 1073
K (maximum temperature). At this temperature,
the pore size distribution depends on the KOH:
raw material ratio. Evolution of the carbon po-
rosity was studied by the DFT method and the
Dubinin–Radushkevich equation (Table 1).
It is well known that the basis of both methods
are absolutely different. The DR equation is less
accurate (presents a smaller range of linearity)
when it is employed to solids with a contribution
of mesopores. Due to the limited range of linearity
of the DR equation in carbons with a high con-
tribution of mesopores [39], the DFT method was
employed, allowing us to obtain a reliable evalu-
ation of the pore size distribution, although several
kinds of pores were present in the carbon struc-
Fig. 1. C 1s XPS spectra of impregnated samples. ture, as in E-KOH 4:1 (1073 K).

Table 1
Surface characterization of carbons
Sample SBET DFT method Dubinin–Radushkevich equation
(m2 g1 ) Vmic Smic Vtot Sext W0 E0 Smic Sext
(cm3 g1 ) (m2 g1 ) (cm3 g1 ) (m2 g1 ) (cm3 g1 ) (kJ mol1 ) (m2 g1 ) (m2 g1 )
E-0 (673 K) 2 – – – – – – – –
E-0 (873 K) 456 0.176 – 0.186 – – – – –
E-0 (1073 K) 254 0.082 – 0.090 – – – – –
E-KOH 4:1 (673 K) 7 – – – – – – – –
E-KOH 20% (873 K) 260 0.093 204 0.101 9 0.082 26.4 227 17
E-KOH 1:1 (873 K) 620 0.214 524 0.233 17 0.231 25.2 590 23
E-KOH 4:1 (873 K) 815 0.264 673 0.287 11 0.297 23.7 677 31
E-KOH 20% (1073 K) 820 0.270 677 0.278 3 0.291 26.3 800 30
E-KOH 1:1 (1073 K) 1625 0.477 1243 0.642 107 0.567 25.7 1495 217
VE-KOH 1:1 (1073 K) 718 0.237 657 0.271 21 – – – –
E-KOH 4:1 (1073 K) 1960 0.496 1124 1.01 345 0.653 18.8 900 860
E-K2 CO3 1:1 (1043 K) 545 0.213 227 0.250 1 – – – –
The surface area was calculated by the BET method, using N2 at 77 K. The volume of nitrogen adsorbed in the micropores (Vmic ) and
the total volume adsorbed (Vtot ) were calculated by DFT. The surface area due to micropores (Smic ), the surface area due to mesopores
(Sext ), the limiting micropore volume (W0 ) and characteristic energy (E0 ) were calculated by the Dubinin–Radushkevich method.
J. Dıaz-Teran et al. / Microporous and Mesoporous Materials 60 (2003) 173–181 177

As can be seen from Table 1, although the values the aim to study changes in the surface chemical
obtained by the DR equation are higher than those structure of the impregnated samples. XPS is a
obtained by the DFT method, both methods show surface method and, therefore, gives information
the same trends in the development surface area concerning the outermost 3–4 nm surface layer
and porosity. That is, the maximal micropore sur- carbon surface (surface groups, metal content,
face area (Smic ) obtained by both methods corre- metal distribution and chemical state of the ele-
sponds to E-KOH 1:1 (1073 K), although a higher ments [40,41]). Table 2 shows the binding energy
SBET was observed with a 4:1 ratio. This is due to of the C 1s, O 1s and K 2p3=2 core-levels. These
the very low amount of micropores present in the energies allow the identification of different com-
two samples (slightly larger in the sample with a 1:1 pounds. Thus, from a deconvolution of C 1s (Fig.
ratio), but in E-KOH 4:1 (1073 K), the develop- 1), the component at 284.9 eV is associated with
ment of mesopores increases dramatically. C–C bonds, the component at 286–287 eV
These pores and the surface area evolution are with ˜C@O and the component at 288–289 eV
due to the activation process and, therefore, can be with O@C–O bonds in carbonates [42].
explained following the evolution of KOH. With Deconvolution of the O 1s spectra is complex
this purpose, XPS and XRD studies were carried due to the broadness of the peak and the difficulty
out. in deciding whether when heteroatoms are present
It is important to point out that, when other [34,40,41,43,44]. In the deconvoluted of O 1s
activating agents, such as K2 CO3 were employed, a spectra, the component at 531–532 eV is related to
lower surface area was obtained (only 545 m2 g1 ). both ˜C@O bonds and K–O bonds (531–33 eV),
The carbonized samples were analyzed by XPS whereas that at 534 eV and even higher binding
before washing. This technique was employed with energies is associated to strongly adsorbed water

Table 2
Results of XPS
Sample C 1s K 2P3=2 O 1s K/C O/C K/CO2
3 K/O
E-0 1073 284.9 (65) 531.2 (39)
286.2 (25) – 533.1 (46) – 0.117 – –
288.8 (9) 534.5 (15)
E-0 873 284.9 (70) 531.1 (20)
286.2 (22) – 533.1 (56) – 0.118 – –
288.6 (8) 534.7 (24)
E-0 673 284.9 (51)
286.1 (38) – 531.4 (35) – 0.141 – –
287.7 (11) 533.4 (65)
E-KOH 4:1 1073 284.9 (80) 292. 8 531.1 (59) 2.20 3.53 11.0 0.62
288.9 (20) 533.1 (41)
E-KOH 4:1 1073 (Washed) 284.9 (75)
286.6 (15) n.d. 532.3 (65) – 0.09 – –
288.7 (10) 534.3 (26)
E-KOH 4:1 873 284.9 (69) 531.6 (74)
289.2 (31) 293.2 533.5 (26) 1.03 1.65 3.32 0.62
E-KOH 1:1 1073 284.9 (86) 293.2 531.5 (73) 0.886 1.41 6.36 0.63
289.9 (14) 532.8 (27)
E-KOH 1:1 873 284.9 (54)
287.2 (18) 293.2 531.5 (80) 0.80 1.27 4.44 0.63
289.5 (28) 533.1 (20)
E-KOH 1:1 573 284.9 (81) 292.8 531.2 (80) 0.26 0.45 1.37 0.58
288.1 (19) 533.0 (20)
Binding energies (eV) and surface elements ratios of samples carbonized at different temperatures.
nd: Not detected.
178 J. Dıaz-Teran et al. / Microporous and Mesoporous Materials 60 (2003) 173–181

molecules [42]. A precise assignment of the O 1s (K/O ¼ 0.66) or a mixture of carbonate and oxide
components can be made by looking simulta- (K2 O) as proposed by Ehrburger [30]. This fact
neously at the C 1s and O 1s profiles. Thus, in the could indicate the presence of other potassium
impregnated samples no C 1s component at 286 compounds on the carbon surface. As stated
eV was detected, whereas an O 1s peak in the 531– above, the fact that practically all oxygen is asso-
532 eV energy range was observed. Accordingly, ciated with potassium and not with surface carbon
this O 1s component can be assigned to the K–O atoms suggests the presence of undecomposed
bond. However, in K-free samples, (E-0 samples KOH or, at higher temperatures, the formation of
and washed samples) these lines may be associated KO2 , which is thermodynamically the most stable
to the presence of ˜C@O bonds on the carbon potassium oxide [47]. The formation of metallic K
surface. and K2 O, as proposed by Otawa et al. [17], may
The surface K/C and O/C atomic ratios of the enhance the K/O ratio. In any case, we emphasize
carbons obtained are compiled in Table 2. In the here that the AC samples were air-exposed prior to
impregnated samples, increasing pyrolysis tem- being analyzed by XPS. This makes it difficult to
perature at a constant impregnation ratio gives rise draw a more general conclusion.
to an enhancement of the surface oxygen and Although the analysis of the carbons by XRD,
surface metal content, which indicates a better due to their amorphous structure, is not very ac-
distribution of the K-compound(s) on the carbon curate and presents different band widths which
surface, probably due to KOH melting. For non- makes the correct assignment of the peaks difficult,
impregnated samples, the opposite behavior was XRD patterns were recorded during the activation
found (Fig. 2). The decrease of the surface oxygen process in a high-temperature chamber, under the
content with temperature seems to be due to a same conditions as in the furnace. The aim of these
destruction of different surface groups [34,45,46]. analyses was to follow the formation of different
This fact, and the very low oxygen content de- crystalline compounds during the activation pro-
tected in sample E-KOH 4:1 (1073 K) washed cess. The non-uniform dispersion of K-compounds
(lower than E-0 samples), suggest that, in im- and their formation on the carbon structure pre-
pregnated samples, practically all oxygen is asso- vented the acquisition of high-quality patterns.
ciated to potassium. However, these patterns showed that the principal
The K/O atomic ratios are similar for all the compound formed was K2 CO3 (Fig. 3), irrespec-
samples. Moreover, this ratio is lower than ex- tive of the impregnating ratio employed. The in-
pected if all potassium is present as carbonate

K 2CO3
3.5 K/C Surface ratio
O/C Surface ratio T=1073K
3.0

2.5 K 2CO3 T=873 K


2.0
K 2CO3 T=673 K
1.5

1.0 T=473 K
0.5
T=303 K
0.0
3 3 73 3 33
107
3 873 -0 673 :1 107 107 :1 8 107 1:1 87
3
:1 4 25 30 35 40
E-0 E-0 E 4 4:1 H4 1:1 H1
-K OH -KOH shed E-KO -K OH E-KOH E-KO
E E Wa E

Fig. 3. XRD patterns of samples E-KOH 1:1 under N2 atmo-


Fig. 2. Surface K/C and C/O ratios of the carbons. sphere at different temperatures.
J. Dıaz-Teran et al. / Microporous and Mesoporous Materials 60 (2003) 173–181 179

tensity of the first peak of this compound K 2CO 3


(2h ¼ 31:6°) increases with the pyrolysis tempera-
ture, both in the 1:1 and the 4:1 samples. No de- T=1073 K in N2
crease in peak intensities of this compound was
observed at temperatures above 920 K as indicated
by Ehrburger et al. [30].
It must be pointed out that in Fig. 3, second
K 2CO3
intense line of K2 CO3 at 34° was not observed.
This could be due to a preferential orientation of T=1073 K Vacuum

the K2 CO3 crystallites, since the development of


this compound occurs a preferential sites in the
carbon structure. Moreover, the only possibility for 25 30 35 40
assigning the peak at 31.6°, with the present species
and taking into account the XPS data, was K2 CO3 .
Fig. 4. XRD patterns of sample E-KOH 1:1 under N2 and
Formation of K2 CO3 occurs by the reaction of under vacuum.
KOH with CO2 evolved in the degradation of he-
micellulose and cellulose. This process may not
only occur on the outermost carbon surface, in Fig. 4, a smaller amount of carbonate was
whereby K2 CO3 forms a ‘‘shell’’ around the car- formed, which is paralleled by a lower surface area
bon and has no effect on the carbon structure, but of the sample. Nevertheless, the pore size distri-
also in the pores and cavities of the carbon where bution is very close to that of sample E-KOH 1:1.
molten KOH could be located [8]. K2 CO3 formed Only a slight shift to smaller pore sizes in the
here would cause carbon lamellae separation and carbon obtained under vacuum conditions was
deformation and at the same time protect the observed (Fig. 5). This fact provides support that
pores from a structure crumbling, as occurs in the formation of K2 CO3 is due to the reaction with
non-impregnated samples at high temperatures. evolved CO2 .
Thus, once K2 CO3 is removed by washing, a high The limitation of the XRD technique to detect
surface area and porosity are developed. crystalline structures smaller than 4 nm does not
Fig. 3 shows that K2 CO3 formation in sample allow the observation of highly dispersed potas-
E-KOH 1:1 was detected above 673 K, and its sium compounds, which were proposed by different
proportion progressively increased with tempera-
ture. The same behavior was observed in sample
E-KOH 4:1. This fact could explain the develop- 0.2
(a)
ment of the surface area with increasing pyrolysis
E-KOH 1:1 1073 K
temperature (Table 1). Thus, it appears that a 0.1
larger amount of K2 CO3 formed causes a larger
surface area development. The very low values of
0.0
surface area obtained in samples E-KOH 1:1 (673
K) and E-KOH 4:1 (673 K) are due to the fact 0.2
that, though a considerable amount of K2 CO3 was (b)
formed, porosity was not developed in the carbon
matrix at this temperature, and therefore all 0.1
VE-KOH 1:1 1073K
K2 CO3 was formed on the external surface.
When the carbon was prepared under vacuum 0.0
(VE-KOH 1:1), an important decrease in surface 1 10 100

area was observed (from 1625 to 716 m2 g1 ). This


could be due to a lesser reactivity of CO2 with Fig. 5. Pore size distribution of samples carbonized under N2
KOH under vacuum (>104 mbar). As can be seen and under vacuum.
180 J. Dıaz-Teran et al. / Microporous and Mesoporous Materials 60 (2003) 173–181

A+B ciated with potassium, which is present in the form


E-KOH 1:1 1073 K
of different surface groups (carbonates and oxides
B
A: K 2CO3 mainly). The K/O ratios obtained in all samples
B: K 2CO3H 2O were similar and lower than expected assuming
C: α KO2 that all K occurs as K2 CO3 . The main activation
D+E D: β K 2O product was K2 CO3 produced by the reaction of
E: β KO2 KOH with CO2 evolved from hemicellulose and
A
C F: KOH cellulose degradation. Moreover, a continuous in-
F A+D C
crease in the formation of this product was ob-
served within the temperature range studied. The
surface area development is directly related with
the amount of K2 CO3 formed during the activa-
20 30 40 50
tion process. A large amount of K2 CO3 formed
enhances mesopore formation.
Fig. 6. XRD patterns of sample E-KOH 1:1 1073 K after
contact with the atmosphere.
References
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