Carbon 39 (2001) 19451953

Surface characterization of polyethyleneterephthalate (PET)

based activated carbon and the effect of pH on its adsorption
capacity from aqueous phenol and 2,3,4-trichlorophenol
solutions
*, Andras
Krisztina Laszlo Szucs
U
Department of Physical Chemistry, Budapest University of Technology and Economics, H-1521 Budapest, Hungary
Received 5 September 2000; accepted 19 December 2000

Abstract

A predominantly microporous activated carbon produced from polyethyleneterephthalate (PET) by physical activation
(burn-off 50%) has a BET surface area of 1170 m 2 / g and a total pore volume of 0.625 cm 3 / g. Its surface possesses an
amphoteric nature due to the oxygen functionalities present, however, the majority of the groups are basic. The adsorption of
phenol and 2,3,4-trichlorophenol has been studied from aqueous solution of different pH (pH53, 11 and unbuffered) on this
carbon. The adsorption mechanism depends both on the pH of the solutions and the pKa of the phenols, as the former
influences the surface chemistry of the carbon as well. In the case of the phenol, a competitive adsorption takes place, as the
interactions are weak in all three media investigated. The triple chlorine substitution in the 2,3,4-trichlorophenol significantly
increases the strength of the interactions in comparison with phenol. Due to its smaller pKa value, in unbuffered medium
ionic interaction occurs, as has been concluded from the shape of the isotherm and the outstandingly high value of the
adsorption equilibrium constant. Competitive adsorption takes place only in the basic media, where the adsorption of the
2,3,4-trichlorophenol is hindered by electrostatic repulsion. 2001 Elsevier Science Ltd. All rights reserved.

Keywords: A. Activated carbon; C. Adsorption; X-ray photoelectron spectroscopy; D. Functional groups; Surface properties

1. Introduction developed, however, adsorption by activated carbon is the

Phenol and its derivatives are among the most frequent
contaminants of water, for they are widely used as
intermediates in the synthesis of dyes, pesticides, insec-
ticides, explosives, etc. [1]. In aqueous solutions, they
cause an unpleasant taste and odor already in low con-
centration. Besides being carcinogenic, a very undesirable
feature of phenol is that in the chlorinating process applied
very often in a further purification step of drinking water, it
reacts with the chlorine and produces carcinogenic (poly)-
chlorinated compounds. Phenols are weak acids. The
chlorine substitution(s) increase(s) the acidity of the
phenol, i.e. result(s) in lower pKa values. Various pro-
cedures designed to remove phenols from water have been
*Corresponding author. Tel.: 136-1-463-1893; fax: 136-1-
463-3767.
E-mail address: klaszlo.fkt@chem.bme.hu (K. Laszlo).
most frequently applied [15].
Activated carbons have been widely used as adsorbents
in municipal water supply and environmental control, due
to their outstanding adsorption capacity derived from the
high surface area, tailor-made pore structure and surface
chemistry [610]. The latter traces back to the presence of
heteroatoms, such as oxygen, nitrogen, hydrogen, phos-
phorus, sulfur, etc. The amount and the chemical forms of
these heteroatoms depend on the origin of carbon and the
history of its preparation and treatment conditions.
The most frequent heteroatom in the carbon matrices is
oxygen which is generally bonded along the edges of the
turbostratic graphite crystallites. Oxygen may be present in
various forms, such as carboxyls, carbonyls, phenols,
lactones, aldehydes, ketones, quinones, hydroquinones,
anhydrides or ethereal structures [4,1114,46]. These
groups may also interact with each other, therefore, their
properties might be different from those of their individual

0008-6223 / 01 / $ see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S0008-6223( 01 )00005-7
1946 , A. Szucs
K. Laszlo U / Carbon 39 (2001) 1945 1953

organic analogues. Thus, the functional groups may be 2. Experimental

better characterized by a bond polarity distribution than a
discrete polarity value, which plays an intrinsic role in the
surface heterogeneity of carbons [12]. These groups and
the delocalized electrons of the graphitic structure de-
termine the apparent acid / base character of the activated
carbon surface [12]. Carbonyl, carboxyl, phenolic hydroxyl
and lactonic groups are acidic, while pyrone, chromene
and quinone are basic [11,1521]. In aqueous solutions
with the presence of these acidic and basic functional
groups, the surface properties of carbon depend on the pH.
Thus, the distribution of surface functionalities is fun-
damental in activated-carbon-based water treatment pro-
cesses [1,2225].
In carbon manufacturing polymer precursors are used
when carbon of low inorganic impurity content is needed.
Polyethyleneterephthalate (PET) might be a promising
precursor containing a high percent of carbon (about
62.5% wt.). For its wide commercial application (e.g.
replacing glass in soft drink bottles and containers), its
conversion to activated carbon offers a way to reduce solid
polymer waste as well.
The objective of the present study is to characterize the
surface properties of the activated carbon prepared from
PET and describe its capacity for phenol adsorption from
aqueous solutions. Phenol and one of the potential chlori-
nated products, 2,3,4-trichlorophenol have been applied as
model compounds in unbuffered, acidic (pH53) and basic
(pH511) aqueous solutions. In unbuffered solutions the
adsorption is governed by the chemical character of the
surface sites and the phenols. By setting the pH of the
solution, the protonation of both the surface and the
phenols may be controlled (Table 1) [26]. At the acidic pH
applied in our experiments, the dissociation of both
phenols is suppressed and all the surface sites are proton-
ated. At pH511, due to the low concentration of hydrogen
ions in the aqueous phase, the surface functional groups
are in deprotonated and the phenols in dissociated state,
respectively.
2.1. Preparation of the activated carbon
Granulated polyethyleneterephthalate (PET) (Qualon)
obtained from Mitsubishi (Singapore) was carbonized as
received at 7508C in nitrogen atmosphere for 30 min. After
cooling to room temperature, the pyrolyzed material was
ground and sieved. Particles in the range of 0.82.0 mm
were activated at 9008C, up to a burn-off of ca. 50% in a
steam / nitrogen flow (molar ratio 1:1), for 90 min. The
yield relative to the starting polymer was 912% [30]. The
activated product obtained was used without further treat-
ment.
2.2. Characterization of the activated carbon
2.2.1. N2 adsorption
The surface area and the pore size distribution of the
activated sample was determined from nitrogen adsorp-
tion / desorption isotherms measured at 77 K by an AU-
TOSORB (Quantachrome, Boynton Beach, FL, USA)
computer-controlled surface analyzer. Samples were out-
gassed for 24 h at 3008C in a vacuum ( p,3310 24 mbar).
The apparent surface area was derived according to the
BET model. The Gurvitsch volume [31], the micropore
volume derived from the t-method and the pore size
distribution calculated from the desorption branch accord-
ing to Barrett, Joyner and Halenda were used to character-
ize the pore structure [32].
2.2.2. XPS
The surface chemical composition of the samples was
determined by X-ray photoelectron spectroscopy (XPS)
using an XR3E2 (VG Microtech) twin anode X-ray source
and a Clam2 (X-ray photoelectron spectroscopy) hemis-
pherical electron energy analyzer. The base pressure of the
analysis chamber was 5310 29 mbar. The Mg K a radiation

Table 1
Selected properties of phenol and 2,3,4-trichlorophenol
Molecular pKa a Solubility a Cross sectional area Ref.
weight g/l nm 2 / molecule
Phenol 94.11 9.89 82 0.42 [30]
0.30 [25]
0.522 [22]
0.437 [28]
0.437 [5]
0.43 [29]
2,3,4-Trichlorophenol 197.45 7.59 0.4 0.72 [27]
0.6310.649 [29]
a
At ambient temperature.
 , A. Szucs
K. Laszlo U / Carbon 39 (2001) 1945 1953 1947

used (1253.6 eV) was non-monochromatized. Wide scan

spectra in the 10000 eV binding energy range were
recorded with a pass energy of 50 eV for all samples. High
resolution spectra of the O 1s and C 1s signals were recorded
in 0.05 eV steps with a pass energy of 20 eV. After the
linear baseline was subtracted, the curve-fitting was per-
formed assuming a Gaussian peak shape.

2.2.3. pH
One gram of carbon was shaken with 35 ml bidistilled
water in a sealed glass bottle for 72 h, at ambient
temperature. At the end of this period the pH of the
aqueous phase was detected by an ORION 720A
(INOVATA, Broma, Sweden) pH-meter. Each determi-
nation was performed in triplicate, along with the bidistil-
led water blank.

2.2.4. Boehm titration

The Boehm titration method was used to determine the
number of the oxygenated surface groups [13,23,3335].
One gram of carbon sample was immersed into 35 ml 0.05
M HCl, NaHCO 3 , Na 2 CO 3 and NaOH solutions, respec-
tively. The vials were sealed and shaken for 72 h at
ambient temperature. The filtrates were titrated with NaOH
and HCl depending on the original titrant. The number of
the basic sites was calculated from the amount of HCl that
reacted with the carbon. The various free acidic groups
were derived using the assumption that NaOH neutralizes
carboxyl, lactone and phenolic groups, Na 2 CO 3 neutralizes
carboxyl and lactone and NaHCO 3 neutralizes only car-
boxyl groups, respectively.
2.3. Sorption from dilute aqueous solutions of phenols
Solutions of phenol (Merck, 99.5%) and 2,3,4-trichloro-
phenol (Fluka, 98%) were prepared using bidistilled water,
or the appropriate buffer solutions (Titrisol pH53, and
Titrisol pH511, both Merck), respectively. Carbon (0.05
g) was shaken with 560 ml of phenol (5 mmol / l) or
2,3,4-trichlorophenol (2 mmol / l) solutions for 24 h and 7
days, respectively, in sealed vials at ambient temperature.
The contact times employed were derived from prelimin-
ary kinetic measurements [36]. Initial and equilibrium
concentrations were determined by detecting the UV
absorption of the phenol ( l5265 nm) and 2,3,4-trichloro-
phenol ( l5290 nm) using a UVIKON 930 UV/ visible
spectrophotometer (Kontron, Zurich, Switzerland).
3. Results
3.1. Characterization of the activated carbon
The SEM picture of the PET-based activated carbon is
shown in Fig. 1. The BET surface area of this activated
Fig. 1. SEM picture of a 4003400 mm area of the PET carbon.
carbon, deduced from the nitrogen adsorption isotherm in
Fig. 2a, is 1170 m 2 / g, and the average pore radius is 1.07
nm. According to the pore size distribution (Fig. 2b), it
contains both micro- and mesopores. The total pore
volume is 0.625 cm 3 / g, and out of this value, 0.425 cm 3 / g
is the micropore volume [32]. The structure of this carbon
has been described recently [3739].
The surface of the PET carbon contains 95.7 at.% of
carbon and 4.3 at.% oxygen concluded from the XPS
results, giving an O / C ratio of 0.045. The atomic O / C
ratio calculated from the elemental analysis (typically 93.1
wt.% carbon, 0.4% hydrogen, 6.5% oxygen) proved to
vary between 0.047 and 0.052. This means, that practically
there is no difference between the O / C ratio in the bulk
and the surface, respectively. Five peaks were identified by
the deconvolution of the typically asymmetric C 1s spec-
trum (Fig. 3a) [14,16,40], and two different peaks were
distinguished in the O 1s spectrum (Fig. 3b) [40,41]. The
results of the deconvolution and fitting processes are
collected in Tables 2 and 3.
The pH of the aqueous slurry of the carbon is 6.2 (the
pH of the bidistilled water blank was measured to be 5.5),
i.e. this carbon can be classified as basic (Type H), since it
exhibits a pH value higher than that of the blank [23].
Aqueous extraction of the carbon shifted the pH of the
carbon dispersion toward higher pH values. The extraction
was performed in a Soxhlet apparatus. Ten grams of
carbon were treated with 250 ml of distilled water for 8 h.
The distribution of the surface functional groups de-
termined by Boehm titration is listed in Table 4. In
1948 , A. Szucs
K. Laszlo U / Carbon 39 (2001) 1945 1953
Fig. 2. (a) Nitrogen adsorption / desorption isotherm of the PET
carbon, 77 K; (b) differential pore size distribution derived from
the desorption branch of the isotherm in (a).
accordance with the pH shift experienced in aqueous
solution, 81.6% of the functional groups are basic.
3.2. Adsorption from aqueous phenol solutions
The dependence of the equilibrium adsorption isotherms
of phenol and 2,3,4-trichlorophenol on solution pH is
illustrated in Figs. 4 and 5, respectively. The saturation
capacity was derived from the plateau of the isotherms.
The curves were fitted according to the Langmuir model:
K 3 nm 3 ce
n a 5 ]]]
1 1 K 3 ce
where n a is the phenol or 2,3,4-trichlorophenol adsorbed
by 1 g of carbon, c e is the equilibrium concentration in the
aqueous phase, n m is the monolayer capacity and K is the
adsorption equilibrium constant. The adsorption capacities
read from the plateau as well as the fitted parameters of the
Langmuir equation are collected in Table 5. As a com-
parison, the adsorption capacities of a commercial carbon
(F200, Calgon Carbon Corp., Pittsburg, PA, USA) mea-
sured from unbuffered solution were found to be 2.05 and
2.09 mmol / g from phenol and trichlorophenol, respective-
ly.
Fig. 3. (a) XPS C 1s spectrum of the PET carbon. I, CC, CH; II,
CO; III, C=O, OCO; IV, O=CO; V, shake-up satellite peaks
due to pp* transitions in aromatic rings. (b) XPS O 1s spectrum
of the PET carbon. I, C=O; II, CO.
4. Discussion
Owing to its high BET surface area and pore structure,
the carbon derived from PET might be a suitable adsorbent
in waste-water treatment. Of its porosity, 68% derives
from the micropores and it also contains a sufficient
amount of mesopores promoting the diffusion of the
contaminants, which is essential in water treatment pro-
cesses.
The surface of the PET-derived carbon is amphoteric,
yet the majority of the functional groups are basic,
according to both the pH measurement and the titration
results. However, there is no direct relation between the
numbers of the titrated acidic / basic groups and the pH
value [23]. Part of the basic character traces back to the
delocalized electrons of the graphitic structure. According
to the C 1s spectrum most of the surface carbon atoms are
present in the form of graphitic carbon. A possible
explanation of the elevation of pH following the aqueous
extraction could be the retention of phthalic acid monomer
units from the degradation of the polymer, even after the
activation process. However, in the temperature pro-
grammed desorption mass spectrum of the activated sam-
 , A. Szucs
K. Laszlo U / Carbon 39 (2001) 1945 1953 1949

Table 2
Distribution of carbon structures (at.%) from the XP C 1s spectrum
Peak Binding energy, eV Carbon structure At.%
Refs. [14,40] Fitted value
I 284.0284.3 284.0 CC, CH 60.0
II 285.3285.7 285.2 CO 18.1
III 286.8287.4 286.7 C=O, 8.1
OCO
IV 288.5289.2 288.6 O=CO 5.3
V 290.2291.1 290.3 Shake-up satellite peaks 4.2
due to pp* transitions
in aromatic rings

Table 3 phenolic, alcoholic or ethereal groups is 57%. Similarly, in

Distribution of oxygen structures (at.%) from the XP O 1s spectrum
Peak Binding energy, eV Oxygen structure At.%
Refs. [40,41] Fitted value
I 530.7531.0 531.3 C=O 1.2
II 532.2533.0 533.1 CO 3.1
ple phthalic acid appears only at elevated temperature and
can be attributed to the degradation of the carbon matrix
[42]. In case of polyacrylonitrile-based carbon fibers an
acidic shift of pH was experienced after aqueous Soxhlet
extraction, which was attributed to chemical reaction of
surface functional groups with water, most probably of
anhydrides by formation of strongly and weakly acidic
carboxyl groups [14]. It was also found that in oxygen-free
medium the aqueous extraction does not affect or only
slightly decreases the value of pH [43]. In our case,
oxygen was not removed when pH was detected, thus
several redox processes resulting in a basic shift of pH
might occur [44].
Carboxylic groups were not detected within the ex-
perimental error of the Boehm titration method [35]. The
acidic character arises from the phenolic (81.1%) and
lactonic (18.9%) groups. This is consistent with the ratio
of the deconvoluted peaks of the C 1s spectrum, whereas,
from among the carbon atoms related to oxygen (peaks II,
III and IV), the ratio of peak II derived from carbons in
the O 1s spectrum, the ratio of the single CO bonds is
dominant (72%). The information obtained from the XPS
analysis characterizes the upper (ca. 10 nm) layer of the
sample. The discrepancy of the surface and bulk regions is
obvious from the deviation of the O / C proportions derived
from the XPS and elemental analysis, respectively.
The phenol adsorption isotherms shown in Fig. 4 belong
to Type L according to Giles classification [45], except for
the unbuffered 2,3,4-trichlorophenol curve. The L- or
Langmuir type means that the aromatic ring adsorbs
parallel to the graphitic surface, and there is no strong
competition between the adsorbent and the solvent to
occupy the surface sites. The trichlorophenol adsorption
isotherm from buffered solutions can also be classified as
Type L, but from unbuffered medium we obtained an
isotherm of Type H which is typical when a few very
strong sorption sites are present on the surface. The
monolayer capacities derived from the trichlorophenol data
are higher in any medium studied than those detected in
the case of phenol solutions. If the sorption were governed
only by the porosity of the carbon, the monolayer capacity
expressed in moles per gram should be a decreasing
function of adsorbate molecular size, i.e. the phenol
adsorption capacities should exceed those derived from
trichlorophenol isotherms. Such a regular molecular siev-
ing trend was experienced when comparing the monolayer
capacities from phenol and 2,4-dichlorophenol solutions at
pH.13, on olive stone-based carbons of low burn-off

Table 4
Results of Boehm titration of PET carbon
Functional group Concentration, Group / 100 nm 2 a
mmol / g
Carboxylic Below the detection limit
Lactonic 17.7 0.91
Phenolic OH 76.0 3.85
Total acidic groups 93.7 4.76
Total basic groups 416.8 21
Total functional groups 510.5 26
a
Calculated as 100 3 concentration 3 (NA /a S,BET ), applying the corresponding unit conversions; NA is Avogadros number.
1950 , A. Szucs
K. Laszlo U / Carbon 39 (2001) 1945 1953

Fig. 4. Adsorption isotherms (ambient temperature) from aqueous phenol solutions of various pH. Symbols are the measured values, the
solid lines were fitted by the Langmuir equation.

levels, but at a burn-off exceeding 50% an inverse trend
was detected [5]. Similarly, in the case of our carbon of
50% burn-off an inverse deviation of 3378%, depend-
ing on the pH of the solution, was observed.
The L-type isotherms obey the Langmuir model (Figs. 4
and 5). However, it should be noted that the surface
homogeneity, which is one of the basic conditions applied
in this model, is hardly fulfilled in these systems. In the
case of the H-type isotherm this model gives a poor fit. In
phenol adsorption the order of the monolayer capacities is:
unbuffered.pH53.pH511, while in the case of tri-
chlorophenol the sequence is: pH53unbuffered.pH5
11. It is in accordance to the observations that in the pH
range of 912 the increasing pH results in a decreasing
adsorption capacity [47]. In the case of phenol adsorption,
the values of the K parameter derived from the Langmuir
fit are practically similar in the buffered solutions but it
exhibits a higher value when the system is not buffered.
The sequence of K values from trichlorophenol isotherms
is: unbuffered4pH511.pH53, and the numerical val-
ues are one or two orders of magnitude higher than in
phenolic systems. This phenomenon can be explained by
the significantly different solubility of the adsorbates. The
electron withdrawing effect of the chlorine atoms reduces

Fig. 5. Adsorption isotherms (ambient temperature) from aqueous 2,3,4-trichlorophenol solutions of various pH. Symbols are the measured
values, the solid lines were fitted by the Langmuir equation.
 , A. Szucs
K. Laszlo U / Carbon 39 (2001) 1945 1953
Table 5
Adsorption parameters of aqueous phenol and 2,3,4-trichlorophenol solutions on PET carbon
Phenol
pH53 Unbuffered
a
n m (mmol / g) 1.79 2.36
n m b (mmol / g) 2.14 2.49
K (mmol / l)21 2.12 5.94
Adsorbed molecule / 100 nm 2 b,c 110 128
Surface area available for 0.91 0.78
one adsorbent molecule, nm 2 b,d
a
From the plateau of the isotherm.
b
From the Langmuir model.
c
Calculated as 100 3 n m 3 (NA /a S,BET ), applying the corresponding unit conversions; NA is Avogadros number.
d
Calculated as a S,BET /(n m 3 NA ), applying the corresponding unit conversions; NA is the Avogadros number.
the electron density of the aromatic ring, which is reflected
in the lower pKa value as well.
The possible interaction between the carbon surface and
phenols is (a) dispersion effect between the aromatic ring
and the p electrons of the graphitic structure; (b) electron
donoracceptor interaction between the aromatic ring and
the basic surface oxygens; (c) electrostatic attraction and
repulsion when ions are present [2227,48]. When the
concentration of the oxygen atoms is relatively high, the
specific interaction between the water molecules and the
surface sites must also be considered, since it results in the
depletion of the phenol adsorption sites [22]. Comparing
the number of functional groups / 100 nm 2 from the
titration and the number of adsorbed phenols / 100 nm 2
listed in Tables 4 and 5, respectively, it is clear that
adsorption takes place not only on the titrated function-
alities, as the number of the adsorbed molecules sig-
nificantly exceeds that of the oxygen-containing surface
sites. According to model calculations, the theoretical
maximum of the number of surface functional groups may
be 6 or 12 groups / 100 A 2 , depending on the model applied
[49]. If all the edge sites were functional groups, the
proportion of the lateral plane vs. basal plane (i.e. edge /
sheet) surface area would be 4.3 or 2.1% in the PET-
derived carbon.
At pH53 both the functional groups on the carbon
surface and the phenolic compounds are in non-ionized
form, that is, the surface groups are either neutral or
positively charged. As can be deduced from the K values,
the interaction between the carbon surface and the phenolic
compounds is the weakest in this case and can be
attributed to dispersion effect. The enhanced interaction in
the case of the trichlorophenol adsorbate is due to the
electron withdrawing phenomenon of the three chlorine
substituents. The weak interaction in the case of the phenol
results in the competitive adsorption of the water mole-
cules, yielding a reduced surface concentration in com-
parison with trichlorophenol. The calculated area occupied
by a single trichlorophenol molecule is less than its cross
sectional area (Table 1). For the stronger interaction, the
1951
2,3,4-Trichlorophenol
pH511 pH53 Unbuffered pH511
1.18 3.18 3.15 1.8
1.25 3.42 3.01 1.84
2.67 19.17 809.25 58.6
64 176 155 95
1.55 0.57 0.64 1.06
trichlorophenol may adsorb exclusively. Moreover, part of
the molecules interacts via hydrogen bond formation
between the protonated functional groups along the edge of
graphitic layers and the phenolic OH groups, resulting in a
reduced average surface demand.
At pH511 the phenols dissociate, forming phenolate
anions, while the surface functional groups are either
neutral or negatively charged. The electrostatic repulsion
between the alike charges lowers the adsorption capacities
in the case of both phenols. The deprotonated acidic
groups along the graphitic layers repel the deprotonated
phenolate ions, reducing the access of the phenolate ions
into the space between the graphite sheets. However, some
dispersion interaction may occur. Besides that, the oxygen
atoms of the nondissociated basic groups may form a
donoracceptor relation, stronger than the pp interaction,
as it can be deduced from the elevated value of K,
especially in the case of the trichlorophenol. The competi-
tive adsorption of water molecules must also be consid-
ered: the surface area related to a single adsorbed unit
shows the highest value at pH511 in the case of both
phenols.
When the adsorption occurs from unbuffered solutions,
both the phenols and the surface groups coexist in their
protonated and deprotonated forms, depending on their pKa
values. Moreover, as phenols are weak acids, the pH of the
equilibrium solution is a function of its concentration. All
three types of surfacephenol interactions may occur
simultaneously. In the case of the phenol, based on the
shape of the isotherm and the value of K, ionic interaction
may be excluded, i.e. the dissociation of the phenol
molecules is negligible. In spite of the somewhat stronger
interaction deduced from the value of K, the competition
with water molecules still takes place, according to the
relatively high molecular area value derived from the
isotherm. The lower pKa value of the 2,3,4-trichlorophenol
results in dissociated trichlorophenolate ions of consider-
able number, while the character of the carbon surface is
similar to the one interacting with the unbuffered phenol
solution. Thus, ionic attraction acts between the trichloro-
1952 , A. Szucs
K. Laszlo U / Carbon 39 (2001) 1945 1953
phenolate anions and the surface sites positively charged in
the unbuffered medium. The few ionic interactions are
reflected by the H-type of the isotherm and the remarkable
K value of the Langmuir fit. The surface coverage in this
case is similar to that developing at pH53, which also
supports that part of the adsorbed species is in a position
other than parallel to the graphene layer.
5. Conclusions
The microporous carbon produced from PET by a two-
step physical activation shows an amphoteric surface
nature, due to the presence of oxygen-containing groups. A
total of 81.6% of the surface groups can be titrated by HCl,
i.e. the majority of the functional groups have a basic
character. The acidity derives from lactonic and phenolic
oxygens. The adsorption capacities from aqueous phenol
and 2,3,4-trichlorophenol solutions are comparable to
commercial carbon used as reference. It was concluded
from the shape of the isotherms and the parameters of the
Langmuir fit, that the adsorption mechanism fundamentally
depends on the pH of the solution applied, as (a) the
phenols are weak acids; (b) the surface is amphoteric.
The L-shape of the phenol isotherms, the relatively low
K values and the high surface area available for each
phenol molecule compared to the theoretical cross section-
al area lead to the conclusion, that in all three media
applied, the phenol adsorbs mainly by dispersion inter-
action and therefore, a competitive adsorption of the
solvent molecules may take place as well.
The introduction of the three chlorine substituents
results in a significantly different electron structure in the
case of 2,3,4-trichlorophenol. The dispersion interaction
becomes stronger than in the case of phenol, as is reflected
by the K values at pH53. (In this acidic medium neither
phenol nor 2,3,4-trichlorophenol dissociate and the surface
is in neutral or protonated state. Therefore, the characteris-
tic interaction is a dispersion effect.) At pH511 the
electrostatic repulsion existing between the negative sur-
face sites and the phenolate or 2,3,4-trichlorophenolate
ions reduces the adsorption capacities.
In unbuffered medium the lower pKa value of the
trichlorophenol results in a significant number of trichloro-
phenolate anions in comparison with the phenol itself. It
leads to ionic attraction between the trichlorophenolate
ions and the surface sites positively charged. The ionic
interaction is reflected by the H-type of the isotherm, the
remarkably high K value and a molecular area closer to the
adsorbate cross sectional area.
Acknowledgements
This research was supported by the OTKA Fund (Hun-
gary) Nos. T 017019 and T 025581. The authors wish to
express their appreciation to Ms. Katalin Josepovits for the
XP spectra and Mr. Han Liu for the SEM pictures. The
experimental work of Ms. Emese Fulop and Mr. Gyorgy
Bosznai is gratefully acknowledged.
References
[1] Salvador F, Merchan MD. Study of the desorption of phenol
and phenolic compounds from activated carbon by liquid-
phase temperature-programmed desorption. Carbon
1996;34:154351.
[2] Wood JM. Chlorinated hydrocarbons oxidation in the
biosphere. Environ Sci Technol 1982;16:2917.
[3] Cheremisinoff PN, Ellerbusch F, editors, Carbon adsorption
handbook, Ann Arbor: Ann Arbor Science, 1980.
[4] Bansal RC, Donnet J, Stoeckli F. Active carbon, New York:
Dekker, 1988.
[5] Caturla F, Martn-Martnez JM, Molina-Sabio M, Rod-
riguez-Reinoso F, Torregrosa R. Adsorption of substituted
phenols on activated carbon. J Colloid Interface Sci
1988;124:52834.
[6] Dubinin MM, Serpinski VV. Isotherm equation for water-
vapor adsorption by microporous carbonaceous adsorbents.
Carbon 1981;19:4023.
[7] Suffet IH, McGuire MJ, editors, Activated carbon adsorp-
tion, vol. 1, Ann Arbor: Ann Arbor Science, 1980.
[8] Barton SS, Evans MJB, Holland J, Koresh JE. Water and
cyclohexane vapor adsorption on oxidized porous carbon.
Carbon 1984;22:26572.
[9] Marsh H, editor, Introduction to carbon science, London:
Butterworths, 1989.
[10] Wigmans T. Industrial aspects of production and use of
activated carbons. Carbon 1989;27:1322.
[11] Puri BR. Surface complexes on carbons. In: Walker Jr. PL,
editor, Chemistry and physics of carbon, vol. 6, New York:
Dekker, 1970, pp. 191282.
[12] Leon y Leon CA, Radovic LR. Interfacial chemistry and
electrochemistry of carbon surfaces. In: Thrower PA, editor,
Chemistry and physics of carbon, vol. 24, New York:
Dekker, 1994, pp. 213310.
[13] Boehm HP. In: Eley DD, Pines H, Weisz PB, editors,
Advances in catalysis, vol. 16, New York: Academic, 1966,
pp. 179274.
[14] Zielke U, Huttinger KJ, Hoffman WP. Surface-oxidized
carbon fibers: I. Surface structure and chemistry. Carbon
1996;34:98398.
[15] Lopez-Ramon MV, Stoeckli F, Moreno-Castilla C, Carrasco-
Marin F. On the characterization of acidic and basic surface
sites on carbons by various techniques. Carbon
1999;37:121521.
[16] Kinoshita K. In: Carbon. Electrochemical and physicochemi-
cal properties, New York: Wiley, 1988, pp. 86173.
[17] Bansal RC, Donnet J, Stoeckli F. Active carbon, New York:
Dekker, 1988.
[18] Papirer E, Li S, Donnet JB. Contribution to the study of
basic surface groups on carbons. Carbon 1987;25:2437.
[19] Papirer E, Dentzer J, Li S, Donnet JB. Surface groups on
nitric acid oxidized carbon black samples determined by
chemical and thermodesorption analyses. Carbon
1991;29:6972.
 , A. Szucs
K. Laszlo U / Carbon 39 (2001) 1945 1953
[20] Bismarck A, Wuertz C, Springer J. Basic surface oxides on
carbon fibers. Carbon 1999;37:101927.
[21] Suarez
D, Menendez JA, Fuente E, Montes-Moran MA. [37]
Contribution of pyrone-type structures to carbon basicity: an
ab initio study. Langmuir 1999;15:3897904.
[22] Nevskaia DM, Santianes A, Munoz V, Guerrero-Ruz A. [38]
Interaction of aqueous solutions of phenol with commercial
activated carbons: an adsorption and kinetic study. Carbon
1999;37:106574.
[23] Tessmer CH, Vidic RD, Uranowski LJ. Impact of oxygen- [39]
containing surface functional groups on activated carbon
adsorption of phenols. Environ Sci Technol 1997;31:18728.
[24] Brasquet C, Le Cloirec P. Adsorption onto activated carbon
fibers: application to water and air treatments. Carbon
1997;35:130713. [40]
[25] Singh B, Madhusudhanan S, Dubey V, Nath R, Rao NBSN.
Active carbon for removal of toxic chemicals from contami-
nated water. Carbon 1996;34:32730. [41]
[26] Radovic LR. In: Schwarz JA, Contescu CI, editors, Surfaces
of nanoparticles and porous materials, New York: Dekker,
1999, pp. 52965. [42]
[27] Snyder LR. In: Principles of adsorption chromatography,
New York: Dekker, 1968, pp. 199205.
[28] Haghseresht F, Lu GQ, Whittaker AK. Carbon structure and [43]
porosity of carbonaceous adsorbents in relation to their
adsorption properties. Carbon 1999;37:14917.
[29] McClellan AL, Harnsberger HFJ. Cross-sectional areas of [44]
molecules adsorbed on solid surfaces. J Colloid Sci
1967;23:57799.
K, Bota
[30] Laszlo A, Nagy LG. Comparative adsorption study [45]
on carbons from polymer precursors. Carbon 2000;38:1965
76.
[31] Unger K, Schadow E, Fischer H. High-pressure mercury
intrusion porosimeter for determining pore structure of
porous adsorbents in pressure range 40006000 bars. Z Phys [46]
Chem NF 1976;99:24556.
[32] Gregg SJ, Sing KSW. In: Adsorption, surface area and
porosity, London: Academic, 1982, pp. 41190. [47]
[33] Tamon H, Okazaki M. Influence of acidic surface oxides of
activated carbon on gas adsorption characteristics. Carbon [48]
1996;34:7416.
[34] Otowa T, Nojima Y, Miyazaki T. Development of KOH
activated high surface area carbon and its application to
drinking water purification. Carbon 1997;35:13159.
[35] Szucs
U A. Surface properties of polymer based carbons, [49]
Budapest, Hungary: Budapest University of Technology and
Economics, 1999, Master thesis.
A, Laszlo
[36] Bota K, Nagy LG, Subklew G, Schlimper H,
1953
Schwuger MJ. Adsorbents from waste materials. Adsorption
1996;2:8191.
A, Laszlo
Bota K, Nagy LG, Copitzky T. Comparative study
of active carbons from different precursors. Langmuir
1997;13:65029.
K, Bota
Laszlo A, Cabasso I, Dekany
I. Comparative study
of carbon surfaces from polymer precursors. In: Abstracts,
216th Meeting of ACS, Boston (Massachusetts, USA),
American Chemical Society, 1998, p. 103.
K, Nagy LG, Cabasso I. Effect of heat treatment on
Laszlo
the properties of polymer derived carbons. In: Abstracts, 7th
European Symposium on Thermal Analysis and Calorimetry
(ESTAC), Balatonfured, Hungary: Hungarian Academy of
Sciences, 1998, p. 269.
Biniak S, Szymanski G, Siedlewski J, Swiatkowski A. The
characterization of activated carbons with oxygen and nitro-
gen surface groups. Carbon 1997;35:1799810.
Yue ZR, Jiang W, Wang L, Gardner SD, Pittman Jr. CU.
Surface characterization of electrochemically oxidized car-
bon fibers. Carbon 1999;37:178596.
K, Cabasso I. MS characterization of carbons
Liu H, Laszlo
from polymer precursors. In: Abstracts, EUROCARBON
2000, Berlin, Germany, 2000, p. 49.
Contescu A, Vass M, Contescu C, Putyera K, Schwarz JA.
Acid buffering capacity of basic carbons revealed by their
continuous pK distribution. Carbon 1998;36:24758.
Ives DJG. In: Ives DJG, Janz GJ, editors, Reference elec-
trodes, theory and practice, New York: Academic, 1961, p.
270.
Giles CH, MacEwan TH, Nakhwa SN, Smith D. Studies in
adsorption. Part XI. A system of classification of solution
adsorption isotherms and its use in diagnosis of adsorption
mechanisms and in measurement of specific surface areas of
solids. J Chem Soc 1960;:397492.
Pittman Jr. CU, Jiang W, Yue ZR, Gardner S, Wang L,
Toghiani H et al. Surface properties of electrochemically
oxidized carbon fibers. Carbon 1999;37:1797807.
Urano K, Kano H. Adsorption of organic compounds in
basic solutions. Bull Chem Soc Jpn 1984;57:25014.
Radovic LR, Silva IF, Ume JI, Menendez JA, Leon y Leon
CA, Scaroni W. An experimental and theoretical study of the
adsorption of aromatics possessing electron-withdrawing and
electron-donating functional groups by chemically modified
activated carbons. Carbon 1997;35:133948.
Hoffman WP, Vastola FJ, Walker PL. Chemisorption of
alkanes and alkenes on carbon active sites. Carbon
1984;22:58594.