PERGAMON Carbon 38 (2000) 19651976

Comparative adsorption study on carbons from polymer

precursors
*, Attila Bota,
Krisztina Laszlo Lajos Gyorgy
Nagy 1
Department of Physical Chemistry, Budapest University of Technology and Economics, H-1521 Budapest, Hungary
Received 4 November 1998; accepted 10 February 2000

Abstract

The effect of the precursor polymer on nitrogen adsorption properties, pore size distribution and the hydrophilic /
hydrophobic character of both the pyrolyzed char and the activated carbon was studied in the case of three basically different
polymers, i.e. polyacrylonitrile, polyethyleneterephthalate and cellulose. Pyrolyzed samples were produced from these
polymers and activated by steam at 9008C. After a 50% burn-off, the pore volume and the specific surface area increase
significantly and the pore size distribution is determined by that of the pyrolyzed char, i.e. the starting polymer. The activated
sample derived from polyacrylonitrile is microporous, while the other two carbons contain both micro- and mesopores.
Activation creates pores which are equally available for methanol and benzene and the heterogeneous surfaces become more
benzophilic in all three polymers. The N-content has limited effect on the surface properties studied. 2000 Elsevier
Science Ltd. All rights reserved.

Keywords: A. Porous carbon; B. Pyrolysis, Activation; C. Adsorption; D. Surface properties

1. Introduction structure spectroscopy (XANES) [14] studies. The trans-

Activated carbons with high surface area and pore
volumes can be produced from a variety of carbonaceous
materials. Polymer precursors are especially preferred
when carbon with low inorganic impurities is needed.
Specially developed polymers are used for the fabrication
of monolithic carbon, or for carbon fibers [15]. The most
well studied polymer representatives are the polyacryloni-
trile and the derivatives of cellulose. Polyacrylonitrile-
based activated carbons have attracted increasing attention
because of their excellent surface properties and adsorption
capacity, due to the nitrogen atoms contained in the basal
plane structure [610]. The distribution of pyridinic,
pyrrolic and quaternary nitrogen in carbons has been
studied in detail. The inclusion of nitrogen within the
graphene layers in quaternary form was originally pro-
posed on the basis of temperature controlled combustion
studies [11] and confirmed by X-ray photoelectron spec-
troscopy (XPS) [12,13] and X-ray absorption near edge
formation of nitrogen functionalities in gasification pro-
cesses were recently studied in model chars [1517].
Cellulose is most often applied in the form of various
lignocellulosic materials, such as coconut shells, olive
stones, cherry stone, apricot pit, wood, etc. [1823]. In this
paper, the pore structures and the surface properties of
pyrolyzed chars and activated carbons from three different
polymer precursors, i.e. the already mentioned polyacryl-
onitrile, cellulose, and polyethyleneterephthalate are com-
pared. Polyethyleneterephthalate (PET) might be a promis-
ing precursor. For its wide commercial application, its
conversion to activated carbon also offers a way of
recycling. Polyacrylonitrile (PAN) and cellulose (CEL)
were studied for comparison.
2. Experimental
2.1. Precursors and sample preparation

*Corresponding author. Tel.: 136-1463-1893; fax: 136- Cellulose sheets prepared from pine (Pinus silveris)
1463-3767. were obtained from the Paper Research Institute, Hungary

E-mail address: klaszlo@ch.bme.hu (K. Laszlo). (a-cellulose 88.3% w / w, hemicellulose 9.6% w / w,
1
Recently deceased. ash 0.5% w / w). Granulated polyethyleneterephthalate

0008-6223 / 00 / $ see front matter 2000 Elsevier Science Ltd. All rights reserved.
PII: S0008-6223( 00 )00038-5
1966 et al. / Carbon 38 (2000) 1965 1976
K. Laszlo

(Qualon) was obtained from Mitsubishi (Singapore). Poly- Table 2

acrylonitrile fiber was purchased from Zoltek-Magyar Yield of the heat treatment processes a
Viscosa, Hungary. Polymers as received were carbonized Precursor Carbonization Activation
at 7508C for 30 min in a steel reactor, flushed with
Polyacrylonitrile 4852% (w / w) 2631% (w / w)
nitrogen gas (50 dm 3 / h). After cooling down to room
Polyethyleneterephthalate 1721% (w / w) 912% (w / w)
temperature, the pyrolyzed materials were ground and Cellulose 1722% (w / w) 1114% (w / w)
sieved. Particles in the range of 0.8 to 2.0 mm were a
characterized (KPAN, KPET, KCEL) and used for further Related to the mass of the starting polymer.
treatments. The carbonized char samples were activated in
a steam flow of 18 g / h at 9008C in a rotary quartz reactor mixtures were measured in order to characterize the
[24]. The steam was diluted with nitrogen in a molar ratio chemical heterogeneity of the carbon surfaces. Isotherms
of 1:1. The time of activation was optimized in order to were obtained by batchwise method in the whole com-
obtain a burn-off of ca. 50% related to the mass of the position range, at ambient temperature. Methanol and
char. It took 45 min in the case of the cellulose and benzene of the above mentioned quality were used. The
polyacrylonitrile precursors and 90 min in the case of the applied solid / liquid ratio was 1:5. The contact time
polyethyleneterephthalate activation process [25]. The established from preliminary experiments was 6 h. The
activated samples were labelled as APAN, APET and concentrations were derived from the refractive index.
ACEL.

2.2. Methods
The nitrogen adsorption / desorption isotherms were
measured at the boiling point of liquid nitrogen (77 K) by
AUTOSORB (Quantachrome, Syosset, NY, USA) com-
puter controlled surface analyzer. Samples were outgassed
at 3008C in vacuum ( p,5310 25 Torr). The specific
surface area and the pore size distribution in both the
micro- and mesopore ranges were derived from the iso-
therms [26].
The enthalpy of immersional wetting was gained at
2560.018C by an LKB Sorption Microcalorimeter (Type
2107). The 40- to 125-mg carbon samples were evacuated
at ambient temperature in vacuum less than 10 23 Torr for
10 h before the experiments. The heat of immersion
values, DHmethanol and DHbenzene , respectively, were de-
termined on a g base with dry methanol and benzene of
HPLC grade (Merck) with a reproducibility of 13%. Each
value was calculated from at least five measurements.
Adsorption from benzene(1)methanol(2) binary liquid
3. Results
The starting polymers and their heat-treated derivatives
were characterized by their elementary composition given
in Table 1. The 5.4% (w / w) O content of the poly-
acrylonitrile originates from the methylmethacrylate co-
polymer. As it is well-known, the polymers degrade during
the carbonization and the majority of the heteroatoms are
eliminated in this step, resulting in a significant increase in
the carbon content of the remaining char. The activation
has only a minor effect on the carbon content of the PET-
and CEL-derived chars. It is relevant, that in the PAN-
based sample, beside the activation effect, an intensive
evolution of N 2 starts above 7508C [27], increasing the
ratio of carbon as well. The yield of the carbonization and
activation is very similar in the case of PET- and CEL-
derived samples, according to the data summarized in
Table 2. Overall yields are much higher in the case of
PAN, though the weight loss in the activation step is about

Table 1
Elementary composition of the precursor polymers and the derivatives a
Polymer C, %(w / w) H, %(w / w) O b , %(w / w) N, %(w / w)
60.5 60.2 60.2
Polyacrylonitrile Raw 65.8 5.8 5.460.36 21.3
Carbonized 74.22 1.24 7.46 17.08
Activated 86.15 0.45 5.42 7.98
Polyethylene- Raw 61.3 4.1 34.060.1 0.4
terephthalate Carbonized 95.41 3.04 1.49 0.06
Activated 93.09 0.42 6.47 0.02
Cellulose Raw 41.7 6.3 50.660.2 0.2
Carbonized 93.72 1.27 4.84 0.17
Activated 96.35 0.45 3.08 0.12
a
Data were obtained from elementary analysis.
b
The O content was calculated as 1002(C%1H%1N%), except the precursors. In the polymers the O content was measured as well.
 et al. / Carbon 38 (2000) 1965 1976
K. Laszlo 1967

twice as much in PAN char, than in the other two, as the

activation is accompanied by nitrogen release in the
temperature range of the activation.

3.1. Nitrogen adsorption

Low temperature nitrogen adsorption isotherms were

measured and analyzed in order to describe the surface of
the carbonized and activated surfaces (Tables 3 and 4,
Figs. 13). The specific surface area was calculated
according to the multipoint BET method and the total pore
volume was determined at p /p0 5 0.9998. The adsorption
in the micropores was interpreted according to the pore
filling model [28,29]. In the 0 , p /p0 , 0.2 range ad-
sorption curves were approximated with the two-term D-R
equation [30]:

W 5 W1 1 W2

5 W01 exp FS RT p0
2 ] ln ]
b E1 p DG
2

1 W02 exp FS RT p0
2 ] ln ]
b E2 p DG
2
(1)

E is the energy characteristic to the adsorption occurring in

the micropores, b is the affinity coefficient, W is the
volume of the partially filled micropores and W0 is the total Fig. 1. Nitrogen adsorption / desorption isotherm of polyacryloni-
volume of the micropores, 1 and 2 relates to the two trile samples; (a) KPAN, (b) APAN.

Table 3
Nitrogen adsorption data
Carbon Specific surface Total pore
area, m 2 / g volume, cm 3 / g
Polyacrylonitrile Carbonized 6.7 0.004
Activated 544 0.278
Polyethylene- Carbonized 242 0.139
terephthalate Activated 1190 0.624
Cellulose Carbonized 415 0.212
Activated 1139 0.655

Table 4
Parameters derived from the two-term D-R equation
Carbon W0,1 W0,2 E1 E2
cm 3 / g cm 3 / g kJ / mol kJ / mol
Polyacrylonitrile Carbonized 2.07310 23 1.16310 23 28.76 7.65
Activated 154.4310 23 112.2310 23 61.47 7.87
Polyethylene- Carbonized 79.7310 23 45.9310 23 13.59 9.24
terephthalate Activated 449.9310 23 174.1310 23 26.45 8.65
Cellulose Carbonized 188.5310 23 13.0310 23 29.61 8.46
Activated 458.2310 23 112.7310 23 29.98 8.57
1968 et al. / Carbon 38 (2000) 1965 1976
K. Laszlo
Fig. 2. Nitrogen adsorption / desorption isotherm of poly-
ethyleneterephthalate samples; (a) KPET, (b) APET.
different micropore ranges. For nitrogen b 50.33 was used
[31,32]. In order to derive the characteristic dimensions of
micropores from E, from among the numerous semi-em-
pirical methods the D-R method modified by Spitzer et al.
[33] was applied. Details were published recently [34].
For a larger pore diameter range, in the mesopore size
calculations can be made assuming cylindrical pore geom-
etry by the Kelvin equation, considering the thickness of
the adsorbed layer. For the swelling, the desorption branch
may give a misleading picture of the pore structure [35],
the pore size distribution was computed from the ad-
sorption branch in the cases of carbonized chars and from
the desorption branch in the cases of activated carbons,
using the method proposed by Barrett et al. [36].
The isotherms of the carbonized samples are of type I,
according to the IUPAC classification (Figs. 1a3a).
Although the shape of the adsorption branches is similar,
the maximum specific adsorption is very different. By
p /p0 5 0.1 more than 90% of the total adsorption is
achieved in cellulose-derived char, but only ca. 80% in the
other two chars. The heat treatment of 7508C yields porous
chars in the cases of PET and CEL, as it is illustrated by
the total pore volumes in Table 3. The porosity developing
during the first heat treatment process strongly depends on
the oxygen content of the raw material. Thus, the total
Fig. 3. Nitrogen adsorption / desorption isotherm of cellulose
samples; (a) KCEL, (b) ACEL.
specific pore volume formed in the oxygen-rich cellulose is
about 40 times higher than in the case of the poly-
acrylonitrile of low oxygen content. The pore volume of
KPET is about 65% of that of the KCEL, according to the
ratio of the O content of the starting polymers. The total
pore volume was found to be proportional to the analyzed
oxygen content. It may be supposed that the O-containing
small pyrolysis products, e.g. CO, CO 2 , H 2 O, etc., behave
as self-activating agents and even in oxygen free atmos-
phere they help to develop a pore structure in the polymer
matrix. In PAN the source of oxygen is limited by the few
percent of the copolymer, therefore only a very low
porosity has been achieved in the pyrolysis step. The same
tendency has been concluded from the BET specific
surface area of the chars yielded at 7508C (Table 3). The
high oxygen content of cellulose results in a specific
surface area of two magnitudes higher than that of the
polyacrylonitrile-derived char at the same temperature.
The low pressure hysteresis (LPH) is basically con-
nected with retarded adsorption, where the adsorbing and
desorbing molecules have to overcome a definite energy
barrier. This barrier can arise due to the presence of narrow
pores, penetration into which is difficult due to steric
considerations. Deformations can occur simultaneously:
the adsorbing nitrogen molecules prize apart weak junc-
 et al. / Carbon 38 (2000) 1965 1976
K. Laszlo
tions and open up cavities, which are inaccessible to the
gas molecules at lower pressures, along the adsorption
process. Some of these molecules become either irrever-
sibly trapped and unable to desorb, especially if the
intercalation takes place within pores of molecular dimen-
sions, or their desorption proceeds very slowly. These
processes might be superimposed on each other [3741].
The LPH is the least expressed in the KCEL char, for the
chemical structure and the high oxygen content of the
cellulose promote the formation of gaseous pyrolysis
products. In the case of the PAN-derived pyrolyzed
sample, the adsorption and desorption branches run paral-
lel almost in the entire pressure range, i.e. in the case of
the PAN sample there is a more or less constant amount of
nitrogen of hindered desorption. The KPET sample ex-
hibits a permanently widening hysteresis, as in the ca.
0.11 relative pressure range the desorption branch does
not decrease, the desorption is almost completely hindered
at 77 K. Repeated adsorption / desorption cycles were run
on this char (Fig. 4). The pressure during the evacuation
cycles was below 5310 25 Torr, and the evacuation was
repeated at 473, 293, 473 and 293 K, respectively, for 70 h
every time. The total pore volumes deduced from the final
section of the isotherms of the successive runs are 84.63
Fig. 4. Cyclic low temperature nitrogen adsorption / desorption
isotherms on KPET. Evacuation parameters: 5310 25 Torr; 70 h;
runs 1 and 3: 473 K; runs 2 and 4: 293 K.
1969
10 23 , 14.0310 23 , 65.7310 23 and 8.1310 23 cm 3 / g,
respectively. Comparing the total pore volumes obtained
from the adsorption isotherm of runs 1 and 2, it can be
concluded that almost 85% of the nitrogen adsorbed in the
first run was retarded, when the evacuation between the
two runs took place at ambient temperature. At elevated
temperature (473 K, run 3) this retention is only ca. 22%.
The repeated evacuation at ambient temperature does not
yield a reproducible isotherm (runs 2 and 4). The dis-
crepancy of the isotherms is the most significant in the
very low pressure range of the adsorption branch. In all the
four runs, the desorption branches are parallel with each
other and practically horizontal, i.e. the nitrogen molecules
became trapped and their desorption is very slow or totally
hindered. The elevated evacuation temperature partly
overcomes this hindrance: a higher total pore volume is
obtained, however, it is smaller than the one experienced
in the first run. From these observations it has been
concluded that distortion of the pores is very probable, in
which the micropore structure is irreversibly modified.
In the micropore range, for the low porosity of the
KPAN sample, only the PET- and the CEL-derived chars
can be characterized by a pore size distribution, which
proved to be a bimodal function (Figs. 5a and 6a). The
Fig. 5. Micropore distribution of polyethyleneterephthalate sam-
ples; (a) KPET, (b) APET; narrow; - - - wide; ? ? ? total.
1970 et al. / Carbon 38 (2000) 1965 1976
K. Laszlo
Fig. 6. Micropore distribution of cellulose samples; (a) KCEL, (b)
ACEL; narrow; - - - wide; ? ? ? total.
computed functions have the first maximum at 0.36 and
0.28 nm in the case of KPET and KCEL, respectively, and
the other one at 0.41 nm in both cases. According to these
values, the derived characteristic layer distances are 0.72
and 0.82 nm in KPET, and 0.56 and 0.82 in KCEL chars.
In graphitic structures the walls of the micropores consist
mainly of basal planes and are formed by gasification of
one or a few adjacent aromatic layers [34,42]. The diffuse
character of the distribution functions shows that the
formation and the organization of the layers is in a very
early stage. In the case of the KCEL, from the position of
the peaks, it is likely that the layer distances correspond to
the removal of a single and two adjacent layers. In the
KPET sample the positions of the two maxima are very
near to each other. The wider peak may rise from the
gasification of two adjacent layers. The peak corre-
sponding to the removal of a single layer shifts towards
larger dimensions, presumably for the highly disorganized
carbon being produced during the polymer degradation,
blocking the finer pores. Thus, closed pores and partially
plugged pores are formed. The significant share of this
amorphous carbon may be partly responsible for the lack
of microporosity in the PAN char as well as for the
extensive low pressure hysteresis in both the PET- and
PAN-derived chars. Due to the high oxygen content and
the different way of degradation, the retention of the
amorphous carbon at 7508C is less significant in KCEL.
Only the cellulose-derived sample exhibits a characteristic
pore size distribution in the mesopore range, with a
maximum of about 2 nm (Fig. 10a).
The activation significantly increases the adsorption
capacity in all the three samples by altering the pore
structure and increasing the pore volume, as it is obvious
from the nitrogen adsorption isotherms (Figs. 1b3b). The
nearly 50% burn-off triples the specific surface area of the
cellulose char, and quadruples that of the PET char. The
specific surface area of the activated PAN is increased by a
factor of ca. 80, similar to the experience of Ko et al. [7]
who used CO 2 for activation. That is, the activating agent
has a lower effect on the adsorption capacity of the
carbons from oxygen-rich precursors in the applied two-
step preparation process.
The adsorption isotherms of the activated PET and CEL
carbons belong to type IV. Despite the different pore
structure and apparent specific surface area of their carbon-
ized form, the resulting adsorption capacity in the activated
samples is almost equal, though the initial section of the
isotherms is dissimilar. The low pressure hysteresis practi-
cally disappears, but the isotherms still exhibit hysteresis
in the higher pressure range. PAN shows an isotherm of
type I characteristic to a mainly microporous pore struc-
ture. The specific adsorption of APAN is far below that of
the other two carbons.
Besides drilling new pores, the steam also gasifies the
amorphous carbon from the micropores, leaving behind a
more rigid structure, which results in the suppression of the
low pressure hysteresis. At the same time, the higher
temperature promotes the extension of the condensed ring
system. The increase of the crystalline region is reflected
by the sharpening of the micropore size distribution
functions (Figs. 5b, 6b and 7). The intensity and the ratio
Fig. 7. Micropore distribution of APAN; narrow; - - - wide;
? ? ? total.
 et al. / Carbon 38 (2000) 1965 1976
K. Laszlo 1971

of the narrower and wider peak areas show a significant

increase. In the APET sample, the removal of the amor-
phous plugs shifts the position of the narrower peak to
smaller size and has a maximum at 0.29 nm, while in the
ACEL sample the position of the narrower peak (0.28 nm)
is not affected by the activation. The position of the wider
peak (0.42 nm) is practically equal in both APET and
ACEL samples and is not affected by the activation.
Distribution can be calculated also in APAN, due to the
reasonable increase in the pore volume. The bimodal
distribution exhibits maxima at 0.22 and 0.43 nm. Using
CO 2 , pores with a diameter of less than 3.9 nm were
obtained [7]. Considering the 0.335 nm layer distance of
the ideal graphite layers, the graphitic organization of the
crystalline part is the highest in the APAN sample, and
similarly lower in the other two activated carbons. Similar
conclusions were obtained from X-ray scattering measure-
ments [43].
The APAN sample, in accordance with Ref. [7], has no
distinguished pore size in the mesopore range, while both
APET and ACEL show a single maximum at 2 nm (Figs.
8b10b).

3.2. Calorimetric data

Immersional wetting enthalpies were measured and

given in J / g basis in order to describe the variation of
surface heterogeneity during the heat treatment (Table 5).
Heats of immersion of the carbonized PET and CEL
samples proved to be significantly higher in methanol than
in benzene, indicating that the surfaces are heterogeneous
and strongly polar. Activation increased the heat effects
partly due to the increased specific surface area. In both
cases the heat in benzene showed a more extensive
elevation, a sign of increased benzophilic behavior. Thus,
it reflects an increased non-polar character, as the heat
effects are almost equal when APET and ACEL are
immersed either in benzene or methanol. Carbonized PAN
gave similar effects in both solvents, only slightly higher
heat was measured in methanol. Activation practically
quintupled both heat values. As a result of the activation
process, the surface character of all the three polymer
carbons became more alike, as can be concluded from the
similar values of the wetting enthalpies calculated on a
J / m 2 basis, both in methanol and benzene. The trans-
formation of the pore shapes during the heat treatment can
also be explored from the heats of immersion [44,45].
Methanol and benzene were used, as from the same set of
experimental data we were able to estimate a possible
molecular sieve effect for the liquid adsorption measure-
ments. The methanol and the flat benzene molecule have
the same minimum dimension of about 0.35 nm [46,47].
According to the calorimetric data, the shape of the pores
is formed diversely in the three polymers. The pores in the
KPAN are practically slit-shaped, as the heat of immersion
both in methanol and benzene are equal. In the other two
Fig. 8. Mesopore distribution of polyacrylonitrile samples; (a)
KPAN, (b) APAN.
carbonized samples the exclusion of benzene is ex-
perienced to some extent. In all cases, pores become
slit-shaped in the size range of the methanol and benzene
after the activation, giving almost equal heat of immersion-
al wetting values on a J / g basis.
3.3. Adsorption from benzene(1) methanol(2) binary
liquid mixture
The heterogeneity of carbon surfaces was determined
from adsorption studies of organic molecules from solu-
tions. The binary mixture of benzene and methanol is very
often used to describe the overall surface character of
carbons, as these two solvents are miscible in the entire
concentration range in spite of their significantly different
s(n)
polarities. Excess isotherms (n 1 vs. x 1 functions) com-
puted from the primary experimental data were used to
evaluate the character of the surface:
s (n) s s s
n1 ; n 0 (x 1,0 2 x 1 ) 5 n x 1 2 n x 1 (2)
s (n)
where n 1 is the specific surface excess amount (mmol /
g) of benzene in the interfacial layer, n 0 is the specific
amount of the initial bulk liquid phase (mmol / g), x 1,0 and
x 1 are the initial and the equilibrium molar fractions of the
1972 et al. / Carbon 38 (2000) 1965 1976
K. Laszlo
Fig. 9. Mesopore distribution of polyethyleneterephthalate sam-
ples; (a) KPET, (b) APET.
benzene, respectively, in the bulk phase, n s is the specific
amount of the adsorbed liquid in the interfacial layer and
x s1 is its composition in equilibrium.
The intersection of the linear section with the x 1 axis
when it exists is called the adsorption azeotropic
composition, x 1,a , and is a measure of the hydrophobic /
hydrophilic character of the surface. The adsorbed amount
of both components in the linear range, n s1 and n s2 were
determined by the SchayNagy extrapolation method. In
the linear section the composition of the interfacial layer is
practically constant [4850] and equals to x 1,a . The
number of sorbed layers was calculated as
n s1 n s2
] 1 ] 5 t, (3)
n s1,m n s2,m
where n s1,m and n s2,m mean the number of moles of
components 1 and 2, respectively, which form a monolayer
on 1 g carbon. Their values were derived from the BET
surface by applying 180 m 2 / mmol and 94 m 2 / mmol as
molar surface area for benzene and methanol, respectively
[46].
The preferential adsorption of both methanol and ben-
zene is a result of structural and chemical phenomena. In
the case of carbon surfaces the preferential adsorption of
Fig. 10. Mesopore distribution of cellulose samples; (a) KCEL,
(b) ACEL.
methanol takes place on the hydrophilic functional groups
as well as arm-chair and zig-zag sites of the basal planes.
The adsorption of benzene is attributed to the interaction
between p-electrons in the benzene ring and the carbon
surface [51]. The behavior in which both components in
the binary mixture adsorb, depending on the relative
concentration of each component, is ascribed to the acidic
CO 2 complexes on the carbon surface. Part of the oxygen
present in CO 2 complexes is thought to render the surface
benzophilic, while part of the oxygen renders the surface
polar and enhances its interaction with the polar com-
ponent (methanol) in the binary mixture. The presence of
CO complexes also promotes the preference of the carbon
surface for benzene [52,53].
The adsorption azeotropic compositions as well as the
number of sorbed layers are listed in Table 6. The
isotherms of both the carbonized and activated carbons
(Figs. 1113) are of type IV according to the SchayNagy
classification [48], i.e. the isotherms display an S-shape
with a relatively long linear section. The S-shape means
that the surface contains both hydrophilic and hydrophobic
surface sites, as it was also concluded from calorimetric
results. The preferentially adsorbing component depends
on the bulk concentration. In each sample below x 1,a the
nonpolar benzene adsorbs preferentially while in the x 1,a ,
 et al. / Carbon 38 (2000) 1965 1976
K. Laszlo 1973

Table 5
Heat of immersion data
Carbon Benzene Methanol
2
J/g J/m J/g J / m2
Polyacrylonitrile Carbonized 12.04 1.7937 15.75 2.3617
Activated 57.53 0.1057 66.09 0.1215
Polyethylene- Carbonized 9.41 0.03885 64.97 0.2686
terephthalate Activated 118.50 0.09958 125.86 0.1058
Cellulose Carbonized 43.92 0.10577 73.13 0.1761
Activated 124.02 0.10887 129.93 0.1140

Table 6
Data derived from the benzene(1)methanol(2) excess isotherms
Carbon x 1,a n s1 n s2 t
mmol / g mmol / g
Polyacrylonitrile Carbonized 0.56 6.9 5.1 273
Activated 0.69 9.3 4.1 3.8
Polyethylene- Carbonized 0.43 5.9 6.7 4.8
terephthalate Activated 0.85 7.5 1.6 1.6
Cellulose Carbonized 0.60 8.1 4.8 17.7
Activated 0.71 8.7 3.3 1.2

Fig. 12. Adsorption of benzene(1)methanol(2) binary liquid

Fig. 11. Adsorption of benzene(1)methanol(2) binary liquid mixture on polyethyleneterephthalate samples; (a) KPET, (b)
mixture on polyacrylonitrile samples; (a) KPAN, (b) APAN. APET.
1974 et al. / Carbon 38 (2000) 1965 1976
K. Laszlo
Fig. 13. Adsorption of benzene(1)methanol(2) binary liquid
mixture on cellulose samples; (a) KCEL, (b) ACEL.
x 1 ,1 range the adsorption of the polar methanol is
preferred.
In the PAN- and CEL-derived char the interval of the
preferred adsorption of benzene is wider, while in the
KPET char the adsorption of methanol is preferred in a
wider range. The unreal number of the layers in the cases
of KPAN and KPET samples can be attributed to special
interactions between the tarry amorphous part and the
solvent molecules, which might result in swelling of the
chars in the organic media. Similar behavior of these
samples was also experienced in the nitrogen adsorption
experiments.
Activation shifts the azeotropic composition towards
higher benzene mole fractions in all the three activated
samples, in accordance with the results of the immersional
wetting measurements. The shift is 0.11 and 0.13 in the
case of the CEL and PAN, respectively. The PET exhibits
a much greater shift of 0.42. The modification of the
adsorption azeotropic composition derives from the struc-
tural and chemical changes taking place during the higher
temperature heat treatment in the presence of the activating
agent. This complex treatment removes the frozen, py-
rolyzed amorphous carbon and increases the porosity [54].
The higher temperature also promotes the further develop-
ment of graphitic regions. By the evolution of the slit-like
pores the size exclusion of the benzene molecules, existing
in the carbonized PET and CEL samples, has been
eliminated. The increased preference toward benzene in the
case of APAN can partly be attributed to this process, i.e.
the loss of nitrogen in this temperature range promotes the
extension of the graphite layers and thus the adsorption of
benzene. In the other two cases the bulk composition does
not change significantly, but the activation necessarily
alters the oxidation state of the surface, which may be one
reason for an increased benzene preference. The removal
of the amorphous matrix increases the ratio of the graphitic
region.
4. Discussion
The behaviour of PET during the manufacturing process
is similar to both CEL and PAN. KPET, like KCEL, shows
a remarkable porosity and specific surface area, due to the
oxygen content of the starting polymer. The low porosity
of KPAN is the result of the low oxygen content of PAN.
At the same time, from the LPH experienced in the
nitrogen adsorption isotherm, similar to KPAN, it can be
concluded that a highly amorphous carbon matrix has been
produced. In its activated form, the specific surface area of
APET is almost equal to that of ACEL, but the latter has a
more developed mesoporosity.
During the activation, the O % is almost unaffected in
the PET-derived carbons, while in the other two pyrolyzed
samples the decrease of the concentration of O and N
heteroatoms is significant.
It should be mentioned that the surface characterization
methods applied in this paper give overall information
about the hydrophilic / hydrophobic state of the surface.
Therefore, the contribution of any of the heteroatoms
cannot be pointed out unambiguously, as there is no direct
relation between the measured parameters and the con-
centration of O and N respectively. The surface con-
centration of the heteroatoms (Table 7) was deduced from
the elementary composition and the specific surface area
values, collected in Tables 1 and 3, respectively. The high
heat of immersion values (J / m 2 ) experienced in the case of
KPAN may be explained with the high concentration of the
heteroatoms. Nevertheless, it is obvious, that the nitrogen
content does not affect the benzene immersion, as all the
three activated samples provided the same DHbenzene (J /
m 2 ) value. In the APAN carbon the DHbenzene /DHmethanol
ratio is 0.87, while in the other two carbons it is 0.940.95.
The O concentrations of the APAN and KCEL surfaces are
similar. In spite of the large difference in their nitrogen
concentration, they gave similar DHbenzene values in J / m 2 ,
but there is a 45% deviation in the DHmethanol values.
In spite of the similar oxygen concentration of activated
PAN and carbonized CEL, the x 1,a values show a remark-
able difference. The value of t shows a significant dis-
crepancy when APAN is compared to the practically
nitrogen-free carbons. The ACEL and the APET is covered
 et al. / Carbon 38 (2000) 1965 1976
K. Laszlo 1975

Table 7
Surface concentration of oxygen and nitrogen atoms
Carbon O N Total
mmol / m 2 mmol / m 2 mmol / m 2
Polyacrylonitrile Carbonized 696 1823 2519
Activated 6.2 10.5 16.7
Polyethylene- Carbonized 3.9 0.2 4.1
terephthalate Activated 3.4 |0 3.4
Cellulose Carbonized 7.3 0.3 7.6
Activated 1.7 0.1 1.8

with a monolayer (t51.2 and 1.6, respectively), while in
the case of APAN the adsorbed layer is much thicker,
t53.8.
5. Conclusions
The properties of polymer carbons prepared from the
different precursors depend on the starting polymer. The
behaviour of PET during the manufacturing is similar to
CEL as well as to PAN. The products obtained in the
carbonization process show a low pressure hysteresis
characteristic to non-rigid structures. This feature is practi-
cally eliminated during the activation. The activation
significantly increases the surfaces. The highest improve-
ment is achieved in the case of PAN of low oxygen
content, but its surface is still far beyond the other two
carbons made of polymers with high oxygen content. The
pore size distribution in the micropore range if there is
any can be described by bimodal functions. As a result
of the activation process, the distribution function can be
applied for the PAN-derived sample as well. In the other
two cases the position, the ratio of the peaks as well as
their intensity change. In PET the position of the first peak
shifts toward smaller size, but the position of the other one
is not affected by the activation. The ratio of the smaller
pores increases from ca. 63% to 72% by the activation. In
CEL char only the intensity and the ratio of the peaks
changes, their position is not affected. The ratio of the
smaller pores decreases from 93% to 80% during the
activation process. The finer pores show the lowest size in
activated PAN, where the wider pores have about the same
size as in the other two samples. In this case the ratio of
the smaller pores is only 58%. The variation of the pore
size during the activation supports that the pores are
formed by the outburn of forming graphite layers. Charac-
teristic mesoporosity was experienced only in PET and
CEL derivatives, especially in their activated form. Activa-
tion creates pores which are equally available for methanol
and benzene. The surface of all the samples is heteroge-
neous, exhibiting affinity toward both methanol and ben-
zene, but in different range of concentration. The regime of
benzene affinity increases with the activation and the shift
of the azeotropic composition is different in each polymer
carbon. The more preferential adsorption of benzene is the
result of the extension of the graphite-like region and / or
the increasing amount of benzophilic CO 2 -complexes.
No direct relation could be established between the
measured parameters and the concentration of O and N.
The N content seems not to effect the immersion enthalpy
in benzene. In contradiction to the monolayer being
formed on the nitrogen-free surfaces, a multilayer ad-
sorption takes place on the APAN surface from benzene
methanol mixtures.
Acknowledgements
The research described in this paper was supported by
the OTKA Funds (Hungary) No. T017019 and T025581.
The authors wish to express their appreciation to Ms.
and Mr. Gyorgy
Emese Fulop Bosznai for their experimen-
tal work.
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