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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-


formation of nitrogen functionalities in gasification pro-
Activated carbons with high surface area and pore cesses were recently studied in model chars [1517].
volumes can be produced from a variety of carbonaceous Cellulose is most often applied in the form of various
materials. Polymer precursors are especially preferred lignocellulosic materials, such as coconut shells, olive
when carbon with low inorganic impurities is needed. stones, cherry stone, apricot pit, wood, etc. [1823]. In this
Specially developed polymers are used for the fabrication paper, the pore structures and the surface properties of
of monolithic carbon, or for carbon fibers [15]. The most pyrolyzed chars and activated carbons from three different
well studied polymer representatives are the polyacryloni- polymer precursors, i.e. the already mentioned polyacryl-
trile and the derivatives of cellulose. Polyacrylonitrile- onitrile, cellulose, and polyethyleneterephthalate are com-
based activated carbons have attracted increasing attention pared. Polyethyleneterephthalate (PET) might be a promis-
because of their excellent surface properties and adsorption ing precursor. For its wide commercial application, its
capacity, due to the nitrogen atoms contained in the basal conversion to activated carbon also offers a way of
plane structure [610]. The distribution of pyridinic, recycling. Polyacrylonitrile (PAN) and cellulose (CEL)
pyrrolic and quaternary nitrogen in carbons has been were studied for comparison.
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 2. Experimental
studies [11] and confirmed by X-ray photoelectron spec-
troscopy (XPS) [12,13] and X-ray absorption near edge 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
3. Results
The nitrogen adsorption / desorption isotherms were
measured at the boiling point of liquid nitrogen (77 K) by The starting polymers and their heat-treated derivatives
AUTOSORB (Quantachrome, Syosset, NY, USA) com- were characterized by their elementary composition given
puter controlled surface analyzer. Samples were outgassed in Table 1. The 5.4% (w / w) O content of the poly-
at 3008C in vacuum ( p,5310 25 Torr). The specific acrylonitrile originates from the methylmethacrylate co-
surface area and the pore size distribution in both the polymer. As it is well-known, the polymers degrade during
micro- and mesopore ranges were derived from the iso- the carbonization and the majority of the heteroatoms are
therms [26]. eliminated in this step, resulting in a significant increase in
The enthalpy of immersional wetting was gained at the carbon content of the remaining char. The activation
2560.018C by an LKB Sorption Microcalorimeter (Type has only a minor effect on the carbon content of the PET-
2107). The 40- to 125-mg carbon samples were evacuated and CEL-derived chars. It is relevant, that in the PAN-
at ambient temperature in vacuum less than 10 23 Torr for based sample, beside the activation effect, an intensive
10 h before the experiments. The heat of immersion evolution of N 2 starts above 7508C [27], increasing the
values, DHmethanol and DHbenzene , respectively, were de- ratio of carbon as well. The yield of the carbonization and
termined on a g base with dry methanol and benzene of activation is very similar in the case of PET- and CEL-
HPLC grade (Merck) with a reproducibility of 13%. Each derived samples, according to the data summarized in
value was calculated from at least five measurements. Table 2. Overall yields are much higher in the case of
Adsorption from benzene(1)methanol(2) binary liquid 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- Fig. 3. Nitrogen adsorption / desorption isotherm of cellulose
ethyleneterephthalate samples; (a) KPET, (b) APET. samples; (a) KCEL, (b) ACEL.

different micropore ranges. For nitrogen b 50.33 was used specific pore volume formed in the oxygen-rich cellulose is
[31,32]. In order to derive the characteristic dimensions of about 40 times higher than in the case of the poly-
micropores from E, from among the numerous semi-em- acrylonitrile of low oxygen content. The pore volume of
pirical methods the D-R method modified by Spitzer et al. KPET is about 65% of that of the KCEL, according to the
[33] was applied. Details were published recently [34]. ratio of the O content of the starting polymers. The total
For a larger pore diameter range, in the mesopore size pore volume was found to be proportional to the analyzed
calculations can be made assuming cylindrical pore geom- oxygen content. It may be supposed that the O-containing
etry by the Kelvin equation, considering the thickness of small pyrolysis products, e.g. CO, CO 2 , H 2 O, etc., behave
the adsorbed layer. For the swelling, the desorption branch as self-activating agents and even in oxygen free atmos-
may give a misleading picture of the pore structure [35], phere they help to develop a pore structure in the polymer
the pore size distribution was computed from the ad- matrix. In PAN the source of oxygen is limited by the few
sorption branch in the cases of carbonized chars and from percent of the copolymer, therefore only a very low
the desorption branch in the cases of activated carbons, porosity has been achieved in the pyrolysis step. The same
using the method proposed by Barrett et al. [36]. tendency has been concluded from the BET specific
The isotherms of the carbonized samples are of type I, surface area of the chars yielded at 7508C (Table 3). The
according to the IUPAC classification (Figs. 1a3a). high oxygen content of cellulose results in a specific
Although the shape of the adsorption branches is similar, surface area of two magnitudes higher than that of the
the maximum specific adsorption is very different. By polyacrylonitrile-derived char at the same temperature.
p /p0 5 0.1 more than 90% of the total adsorption is The low pressure hysteresis (LPH) is basically con-
achieved in cellulose-derived char, but only ca. 80% in the nected with retarded adsorption, where the adsorbing and
other two chars. The heat treatment of 7508C yields porous desorbing molecules have to overcome a definite energy
chars in the cases of PET and CEL, as it is illustrated by barrier. This barrier can arise due to the presence of narrow
the total pore volumes in Table 3. The porosity developing pores, penetration into which is difficult due to steric
during the first heat treatment process strongly depends on considerations. Deformations can occur simultaneously:
the oxygen content of the raw material. Thus, the total the adsorbing nitrogen molecules prize apart weak junc-
et al. / Carbon 38 (2000) 1965 1976
K. Laszlo 1969

tions and open up cavities, which are inaccessible to the 10 23 , 14.0310 23 , 65.7310 23 and 8.1310 23 cm 3 / g,
gas molecules at lower pressures, along the adsorption respectively. Comparing the total pore volumes obtained
process. Some of these molecules become either irrever- from the adsorption isotherm of runs 1 and 2, it can be
sibly trapped and unable to desorb, especially if the concluded that almost 85% of the nitrogen adsorbed in the
intercalation takes place within pores of molecular dimen- first run was retarded, when the evacuation between the
sions, or their desorption proceeds very slowly. These two runs took place at ambient temperature. At elevated
processes might be superimposed on each other [3741]. temperature (473 K, run 3) this retention is only ca. 22%.
The LPH is the least expressed in the KCEL char, for the The repeated evacuation at ambient temperature does not
chemical structure and the high oxygen content of the yield a reproducible isotherm (runs 2 and 4). The dis-
cellulose promote the formation of gaseous pyrolysis crepancy of the isotherms is the most significant in the
products. In the case of the PAN-derived pyrolyzed very low pressure range of the adsorption branch. In all the
sample, the adsorption and desorption branches run paral- four runs, the desorption branches are parallel with each
lel almost in the entire pressure range, i.e. in the case of other and practically horizontal, i.e. the nitrogen molecules
the PAN sample there is a more or less constant amount of became trapped and their desorption is very slow or totally
nitrogen of hindered desorption. The KPET sample ex- hindered. The elevated evacuation temperature partly
hibits a permanently widening hysteresis, as in the ca. overcomes this hindrance: a higher total pore volume is
0.11 relative pressure range the desorption branch does obtained, however, it is smaller than the one experienced
not decrease, the desorption is almost completely hindered in the first run. From these observations it has been
at 77 K. Repeated adsorption / desorption cycles were run concluded that distortion of the pores is very probable, in
on this char (Fig. 4). The pressure during the evacuation which the micropore structure is irreversibly modified.
cycles was below 5310 25 Torr, and the evacuation was In the micropore range, for the low porosity of the
repeated at 473, 293, 473 and 293 K, respectively, for 70 h KPAN sample, only the PET- and the CEL-derived chars
every time. The total pore volumes deduced from the final can be characterized by a pore size distribution, which
section of the isotherms of the successive runs are 84.63 proved to be a bimodal function (Figs. 5a and 6a). The

Fig. 4. Cyclic low temperature nitrogen adsorption / desorption


isotherms on KPET. Evacuation parameters: 5310 25 Torr; 70 h; Fig. 5. Micropore distribution of polyethyleneterephthalate sam-
runs 1 and 3: 473 K; runs 2 and 4: 293 K. ples; (a) KPET, (b) APET; narrow; - - - wide; ? ? ? total.
1970 et al. / Carbon 38 (2000) 1965 1976
K. Laszlo

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
Fig. 6. Micropore distribution of cellulose samples; (a) KCEL, (b) the other two carbons.
ACEL; narrow; - - - wide; ? ? ? total. 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
computed functions have the first maximum at 0.36 and low pressure hysteresis. At the same time, the higher
0.28 nm in the case of KPET and KCEL, respectively, and temperature promotes the extension of the condensed ring
the other one at 0.41 nm in both cases. According to these system. The increase of the crystalline region is reflected
values, the derived characteristic layer distances are 0.72 by the sharpening of the micropore size distribution
and 0.82 nm in KPET, and 0.56 and 0.82 in KCEL chars. functions (Figs. 5b, 6b and 7). The intensity and the ratio
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 Fig. 7. Micropore distribution of APAN; narrow; - - - wide;
extensive low pressure hysteresis in both the PET- and ? ? ? 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). Fig. 8. Mesopore distribution of polyacrylonitrile samples; (a)
Heats of immersion of the carbonized PET and CEL KPAN, (b) APAN.
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 carbonized samples the exclusion of benzene is ex-
partly due to the increased specific surface area. In both perienced to some extent. In all cases, pores become
cases the heat in benzene showed a more extensive slit-shaped in the size range of the methanol and benzene
elevation, a sign of increased benzophilic behavior. Thus, after the activation, giving almost equal heat of immersion-
it reflects an increased non-polar character, as the heat al wetting values on a J / g basis.
effects are almost equal when APET and ACEL are
immersed either in benzene or methanol. Carbonized PAN 3.3. Adsorption from benzene(1) methanol(2) binary
gave similar effects in both solvents, only slightly higher liquid mixture
heat was measured in methanol. Activation practically
quintupled both heat values. As a result of the activation The heterogeneity of carbon surfaces was determined
process, the surface character of all the three polymer from adsorption studies of organic molecules from solu-
carbons became more alike, as can be concluded from the tions. The binary mixture of benzene and methanol is very
similar values of the wetting enthalpies calculated on a often used to describe the overall surface character of
J / m 2 basis, both in methanol and benzene. The trans- carbons, as these two solvents are miscible in the entire
formation of the pore shapes during the heat treatment can concentration range in spite of their significantly different
also be explored from the heats of immersion [44,45]. s(n)
polarities. Excess isotherms (n 1 vs. x 1 functions) com-
Methanol and benzene were used, as from the same set of puted from the primary experimental data were used to
experimental data we were able to estimate a possible evaluate the character of the surface:
molecular sieve effect for the liquid adsorption measure-
s (n) s s s
ments. The methanol and the flat benzene molecule have n1 ; n 0 (x 1,0 2 x 1 ) 5 n x 1 2 n x 1 (2)
the same minimum dimension of about 0.35 nm [46,47].
s (n)
According to the calorimetric data, the shape of the pores where n 1 is the specific surface excess amount (mmol /
is formed diversely in the three polymers. The pores in the g) of benzene in the interfacial layer, n 0 is the specific
KPAN are practically slit-shaped, as the heat of immersion amount of the initial bulk liquid phase (mmol / g), x 1,0 and
both in methanol and benzene are equal. In the other two 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- Fig. 10. Mesopore distribution of cellulose samples; (a) KCEL,
ples; (a) KPET, (b) APET. (b) ACEL.

benzene, respectively, in the bulk phase, n s is the specific methanol takes place on the hydrophilic functional groups
amount of the adsorbed liquid in the interfacial layer and as well as arm-chair and zig-zag sites of the basal planes.
x s1 is its composition in equilibrium. The adsorption of benzene is attributed to the interaction
The intersection of the linear section with the x 1 axis between p-electrons in the benzene ring and the carbon
when it exists is called the adsorption azeotropic surface [51]. The behavior in which both components in
composition, x 1,a , and is a measure of the hydrophobic / the binary mixture adsorb, depending on the relative
hydrophilic character of the surface. The adsorbed amount concentration of each component, is ascribed to the acidic
of both components in the linear range, n s1 and n s2 were CO 2 complexes on the carbon surface. Part of the oxygen
determined by the SchayNagy extrapolation method. In present in CO 2 complexes is thought to render the surface
the linear section the composition of the interfacial layer is benzophilic, while part of the oxygen renders the surface
practically constant [4850] and equals to x 1,a . The polar and enhances its interaction with the polar com-
number of sorbed layers was calculated as ponent (methanol) in the binary mixture. The presence of
CO complexes also promotes the preference of the carbon
n s1 n s2 surface for benzene [52,53].
] 1 ] 5 t, (3)
n s1,m n s2,m The adsorption azeotropic compositions as well as the
number of sorbed layers are listed in Table 6. The
where n s1,m and n s2,m mean the number of moles of isotherms of both the carbonized and activated carbons
components 1 and 2, respectively, which form a monolayer (Figs. 1113) are of type IV according to the SchayNagy
on 1 g carbon. Their values were derived from the BET classification [48], i.e. the isotherms display an S-shape
surface by applying 180 m 2 / mmol and 94 m 2 / mmol as with a relatively long linear section. The S-shape means
molar surface area for benzene and methanol, respectively that the surface contains both hydrophilic and hydrophobic
[46]. surface sites, as it was also concluded from calorimetric
The preferential adsorption of both methanol and ben- results. The preferentially adsorbing component depends
zene is a result of structural and chemical phenomena. In on the bulk concentration. In each sample below x 1,a the
the case of carbon surfaces the preferential adsorption of 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

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
Fig. 13. Adsorption of benzene(1)methanol(2) binary liquid the PET-derived carbons, while in the other two pyrolyzed
mixture on cellulose samples; (a) KCEL, (b) ACEL. samples the decrease of the concentration of O and N
heteroatoms is significant.
x 1 ,1 range the adsorption of the polar methanol is It should be mentioned that the surface characterization
preferred. methods applied in this paper give overall information
In the PAN- and CEL-derived char the interval of the about the hydrophilic / hydrophobic state of the surface.
preferred adsorption of benzene is wider, while in the Therefore, the contribution of any of the heteroatoms
KPET char the adsorption of methanol is preferred in a cannot be pointed out unambiguously, as there is no direct
wider range. The unreal number of the layers in the cases relation between the measured parameters and the con-
of KPAN and KPET samples can be attributed to special centration of O and N respectively. The surface con-
interactions between the tarry amorphous part and the centration of the heteroatoms (Table 7) was deduced from
solvent molecules, which might result in swelling of the the elementary composition and the specific surface area
chars in the organic media. Similar behavior of these values, collected in Tables 1 and 3, respectively. The high
samples was also experienced in the nitrogen adsorption heat of immersion values (J / m 2 ) experienced in the case of
experiments. KPAN may be explained with the high concentration of the
Activation shifts the azeotropic composition towards heteroatoms. Nevertheless, it is obvious, that the nitrogen
higher benzene mole fractions in all the three activated content does not affect the benzene immersion, as all the
samples, in accordance with the results of the immersional three activated samples provided the same DHbenzene (J /
wetting measurements. The shift is 0.11 and 0.13 in the m 2 ) value. In the APAN carbon the DHbenzene /DHmethanol
case of the CEL and PAN, respectively. The PET exhibits ratio is 0.87, while in the other two carbons it is 0.940.95.
a much greater shift of 0.42. The modification of the The O concentrations of the APAN and KCEL surfaces are
adsorption azeotropic composition derives from the struc- similar. In spite of the large difference in their nitrogen
tural and chemical changes taking place during the higher concentration, they gave similar DHbenzene values in J / m 2 ,
temperature heat treatment in the presence of the activating but there is a 45% deviation in the DHmethanol values.
agent. This complex treatment removes the frozen, py- In spite of the similar oxygen concentration of activated
rolyzed amorphous carbon and increases the porosity [54]. PAN and carbonized CEL, the x 1,a values show a remark-
The higher temperature also promotes the further develop- able difference. The value of t shows a significant dis-
ment of graphitic regions. By the evolution of the slit-like crepancy when APAN is compared to the practically
pores the size exclusion of the benzene molecules, existing 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 carbon. The more preferential adsorption of benzene is the
the case of APAN the adsorbed layer is much thicker, result of the extension of the graphite-like region and / or
t53.8. 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.
5. Conclusions The N content seems not to effect the immersion enthalpy
in benzene. In contradiction to the monolayer being
The properties of polymer carbons prepared from the formed on the nitrogen-free surfaces, a multilayer ad-
different precursors depend on the starting polymer. The sorption takes place on the APAN surface from benzene
behaviour of PET during the manufacturing is similar to methanol mixtures.
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-
Acknowledgements
cally eliminated during the activation. The activation
significantly increases the surfaces. The highest improve-
The research described in this paper was supported by
ment is achieved in the case of PAN of low oxygen
the OTKA Funds (Hungary) No. T017019 and T025581.
content, but its surface is still far beyond the other two
The authors wish to express their appreciation to Ms.
carbons made of polymers with high oxygen content. The and Mr. Gyorgy

Emese Fulop Bosznai for their experimen-
pore size distribution in the micropore range if there is
tal work.
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 References
their intensity change. In PET the position of the first peak
shifts toward smaller size, but the position of the other one [1] Jenkins GM. Kawamura: polymeric carbons carbon fibre,
is not affected by the activation. The ratio of the smaller glass and char, Cambridge: Cambridge University, 1976.

[2] Burger A, Fitzer E, Heym M, Terwiesch B. Carbon
pores increases from ca. 63% to 72% by the activation. In
1975;13:149.
CEL char only the intensity and the ratio of the peaks
[3] Zippi EM, Kabalka GW. Carbon 1996;34:1539.
changes, their position is not affected. The ratio of the [4] Neely JW. Carbon 1981;19:27.
smaller pores decreases from 93% to 80% during the [5] Murakami M, Yoshimura S. Synth Metals 1987;18:509.
activation process. The finer pores show the lowest size in [6] Yoshida M, Hirai M. US Patent 4285831, 1981.
activated PAN, where the wider pores have about the same [7] Ko TH, Chiranairadul P, Lu CK, Lin CH. Carbon
size as in the other two samples. In this case the ratio of 1992;30:647.
the smaller pores is only 58%. The variation of the pore [8] McEnaney B, Mays TJ. In: Marsh H, editor, Introduction to
size during the activation supports that the pores are carbon science, Boston: Butterworth, 1989, p. 154.
formed by the outburn of forming graphite layers. Charac- [9] Wang PH, Yue ZR, Liu J. J Appl Polym Sci 1996;60:923.
teristic mesoporosity was experienced only in PET and [10] Morita K, Murata Y, Ishitani A, Murayama K, Ono T,
Nakajima A. Pure Appl Chem 1986;58:455.
CEL derivatives, especially in their activated form. Activa-
[11] Grant KA, Zhu Q, Thomas KM. Carbon 1994;32:883.
tion creates pores which are equally available for methanol
[12] Pels JR, Kaptejin F, Moulijn JA, Zhu Q, Thomas KM.
and benzene. The surface of all the samples is heteroge- Carbon 1995;33:1641.
neous, exhibiting affinity toward both methanol and ben- [13] Stanczyk K, Dziembaj R, Piwowarska Z, Witkowski S.
zene, but in different range of concentration. The regime of Carbon 1995;33:1383.
benzene affinity increases with the activation and the shift [14] Zhu Q, Money SL, Russel AE, Thomas KM. Langmuir
of the azeotropic composition is different in each polymer 1997;13:2149.
1976 et al. / Carbon 38 (2000) 1965 1976
K. Laszlo

[15] Biniak S, Szymanski G, Siedlewski J, Swiatkowski A. [36] Barrett EP, Joyner LG, Halenda PP. J Am Chem Soc
Carbon 1997;35:1799. 1951;73:373.
[16] Kaptejin F, Moulijn JA, Matzner S, Boehm HP. Carbon [37] Kabanova ON, Yakubov TS, Serpinskii VV. Bull Acad Sci
1999;37:1143. USSR Div Chem Sci 1988;37:1311.
[17] Lahaye J, Nanse G, Bagreev A, Strelko V. Carbon [38] Gregg SJ, Sing KSW. In: Adsorption, surface area and
1999;37:585. porosity, London: Academic, 1982, p. 233.
[18] Marsh H. In: Figuereido JL, Moulijn J, editors, Carbon and [39] Marsh H, Wynne-Jones WFK. Carbon 1964;1:281.
coal gasification, Dordrecht: Martinus Nijhoff, 1986, p. 27. [40] Rodriguez-Reinoso F, Linares-Solano A. In: Thrower PA,
[19] Linares-Solano A, Lopez-Gonzalez JD, Molina-Sabio M, editor, Chemistry and physics of carbon, New York: Dekker,
Rodriguez-Reinoso F. J Chem Tech Biotechnol 1980;30:65. 1989, p. 1.
[20] Rodriguez-Reinoso F, Lopez-Gonzalez JD, Berenguer C. [41] Vnukov SP, Uspenskaya KS. Bull Acad Sci USSR Div Chem
Carbon 1982;20:513. Sci 1990;39:1.
[21] Lussier MG, Shull JC, Miller DJ. Carbon 1994;32:1493. [42] Ehrburger P, Pusset N, Dziedzinl P. Carbon 1992;30:1105.
A, Laszlo
[22] Bota K, Schlimper H, Nagy LG. ACH-Models
K, Bota
[43] Laszlo A, Cabasso I, Nagy LG. Abstracts 5th
Chem 1997;134:169.
Chemical Congress of North America, Concun, Mexico,
[23] Solum MS, Pugmire RJ, Jagtoyen M, Derbyshire F. Carbon
1997.
1995;33:1254.
Nagy LG. Per Polytechnica [44] Gregg SJ, Sing KSW. In: Adsorption, surface area and
[24] Noszko L, Bota A, Simay A,
porosity, London: Academic, 1982, p. 232.
1984;28:293.
[45] van Driel J. In: Capelle A, de Vooys F, editors, Activated
K, Cabasso I, Bota
[25] Laszlo A, Nagy LG. Colloids Surf A
carbon . . . a fascinating material, Amersfort: Norit, 1983, p.
1999;151:311.
40.
A, Valyon J, Laszlo
[26] Bota K, Nagy LG. Per Polytechnica
[46] McClellan AL, Harnsberger HFJ. J Colloid Sci 1967;23:577.
1997;41:25.
[27] Watanabe T, Ohtsuka Y, Nishiyama Y. Carbon 1994;32:329. [47] Webster CE, Dargo RS, Zerner MC. J Am Chem Soc
[28] Dubinin MM. Prog Surf Memb Sci 1975;9:1. 1998;120:5509.
[29] Marsh H, Rand B. J Colloid Interface Sci 1970;33:101. [48] Schay G, Nagy LG. J Chim Phys 1961;:149.
[30] Izotova TI, Dubinin MM. Zh fiz khimii 1965;39:2796. [49] Schay G, Nagy LG. Elegyadszorpcio folyadek / szilard
es
[31] Garrido J, Linares-Solano A, Martin-Martinez JM, Molina- / goz
folyadek hatarfeluleten,

Budapest: Akademiai, 1978.
Sabio M, Rodriguez-Reinoso F, Torregrosa R. Langmuir
[50] Dekany I, Zsednai A, Laszlo
K, Nagy LG. Colloids Surf
1987;3:76. 1987;23:41.
[32] Ehrburger-Dolle F, Holz M, Lahaye J. Pure Appl Chem [51] Gasser GC, Kipling JJ. In: Proceedings of the Fourth
1993;65:2223. Conference on Carbon, New York: Pergamon, 1960, p. 55.
V, Kadlec O. Carbon 1976;14:151.
[33] Spitzer Z, Bba [52] Puri BR. In: Walker Jr. PL, editor, Chemistry and physics of

[34] Bota K, Nagy LG, Copitzky T. Langmuir
A, Laszlo carbon, New York: Dekker, 1970, p. 247.
1997;13:6502. [53] Kinoshita K. In: Carbon, electrochemical and physicochemi-
[35] Everett DH. In: Gregg SJ, Sing KSW, Stoeckli HF, editors, cal properties, New York: Wiley, 1988, pp. 1445.
Characterisation of porous solids, London: Society of K, Bota
[54] Laszlo A, Nagy LG, Subklew G, Schwuger MJ.
Chemical Industries, 1979, p. 229. Colloids Surf A 1998;138:29.

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