ARTICLE IN PRESS

Water Research 38 (2004) 20432052

Adsorption of anionic and cationic dyes on activated carbons

with different surface chemistries
! ao, M.F.R. Pereira*
P.C.C. Faria, J.J.M. Orf*
!
!
Laboratorio
de Catalise
e Materiais, Departamento de Engenharia Qu!mica, Faculdade de Engenharia da Universidade do Porto,
Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
Received 20 March 2003; received in revised form 20 October 2003; accepted 27 January 2004

Abstract
The inuence of the surface chemical groups of an activated carbon on the removal of different classes of dyes is
evaluated. Starting from the same material (NORIT GAC 1240 PLUS), the following treatments were carried out in
order to produce a series of samples with different surface chemical properties but with no major differences in their
textural properties: oxidation in the liquid phase with 6 M HNO3 and 10 M H2O2 (acid materials) and heat treatment at
700
C in H2 or N2 ow (basic materials). The specic micropores volume and mesopores surface area of the materials
were obtained from N2 adsorption equilibrium isotherms at 77 K. The surface chemistry was characterised by
temperature programmed desorption , by the determination of the point of zero charge (pHpzc) and by the evaluation of
the acidity/basicity of the samples. Elemental and proximate analyses were also carried out.
Equilibrium isotherms of selected dyes (an acid, a basic and a reactive dye) on the mentioned samples were obtained
and the results discussed in relation to their surface chemistry. In general, the Langmuir model provided the best t for
the adsorption data.
It is shown that the surface chemistry of the activated carbon plays a key role in dye adsorption performance. The
basic sample obtained by thermal treatment under H2 ow at 700
C is the best material for the adsorption of all the
tested dyes.
r 2004 Elsevier Ltd. All rights reserved.
Keywords: Activated carbon; Surface chemistry; Wastewater; Decolourisation; Dyes; Adsorption

1. Introduction
The textile industry is characterised by its high water
consumption and is one of the largest industrial
producers of wastewaters. Water from spent dyebaths
and dye rinse operations contains unxed dyes and may
be highly coloured. The persisting colour and the nonbiodegradable nature of the spent dyebaths represent
serious problems to the environment. However, the
primary concern about efuent colour is its undesirable
aesthetic impact in receiving waters [1].
*Corresponding author. Tel.: +351-22-508-1468; fax: +35122-508-1449.
E-mail address: fpereira@fe.up.pt (M.F.R. Pereira).

Despite the existence of a wide range of wastewaters

treatment techniques, there is no single process capable
of adequate treatment for these efuents [2]. Thus, the
best solution for textile wastewater treatment appears as
a combination of different techniques. The conventional
association of biological and physicalchemical processes results in the removal of most of the organic
content of the textile wastewaters. However, the resulting efuent is still fairly coloured. Ideally, a nal rening
treatment is needed to remove the colour [3]. This nal
step in the treatment of textile efuents is indispensable
for a potential water reuse, since total decolourisation
and extensive elimination of organic content are
required for water recycling in the textile industry [4].
In this context, adsorption techniques appear as

0043-1354/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2004.01.034

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P.C.C. Faria et al. / Water Research 38 (2004) 20432052

2044

Nomenclature
AC
a.u.
Ce
CI
d
KF
KL
L1
n
N
pHpzc
qe

activated carbon
arbitrary units
adsorbate equilibrium liquid phase concentration (mg/dm3)
Colour Index
particle diameter
parameter in the Freundlich equation
mg=gAC dm3 =mg1=n
parameter in the Langmuir equation (dm3/
gAC)
average width of the small micropores (nm)
parameter in the Freundlich equation
number of points
point of zero charge
adsorbate equilibrium solid phase concentration (mg=gAC )

successful efcient alternatives for the removal of dyes in

wastewater. Studies involving the application of a wide
range of adsorbents in the decolourisation of wastewaters are reported in literature [5,6], adsorption on
activated carbon (AC) being one of the most studied
techniques [79].
Activated carbons have a high degree of porosity and
an extensive surface area. These materials are effective
adsorbents for several organic compounds of concern, in
water and wastewater treatment. The adsorption capacity of an AC is determined not only by the textural
properties but also by the chemical nature of its surface,
i.e., the amount and nature of oxygen-containing
functional groups [10]. The nature of an activated
carbon surface can be changed by different treatments,
which include liquid phase oxidations with HNO3 and
H2O2 and gas phase oxidations with O2 or N2O, as well
as thermal treatments at high temperatures [11]. A
thorough knowledge of AC surface chemistry enables
the preparation of adsorbents with appropriate characteristics for specic applications [10]. Yet, little
attention has been given to the role of the AC surface
chemistry in the adsorption process. Karanl et al. [12]
evaluated the uptake of two organic contaminants on a
set of commercial and treated ACs in order to study the
inuence of the surface chemistry on the adsorption of
those organic pollutants. More recently, some authors
started to study the effect of activated carbon surface
chemistry on the removal of dyes from textile efuents
[13,14]. Al-Degs et al. [13] studied the adsorption of
three reactive dyes on a Filtrasorb 400 activated carbon,
and attributed the high adsorption capacity of this
adsorbent to its net positive surface charge during the
adsorption process. In a previous work, Pereira et al.

qcalc
e

calculated adsorbate equilibrium solid phase

concentration (mg=gAC )
qm
maximum adsorption capacity determined by
the Langmuir equation (mg=gAC )
SBET
BET surface area (m2/g)
Smeso
mesopore surface area calculated by the tmethod (m2/g)
SD
standard deviation
T
temperature (
C)
Wmicro micropore volume calculated by the t-method
(cm3/g)
W01 ; W02 volumes of small (1) and large (2) micropores calculated by the Dubinin method
(cm3/g)
Greek symbols
maximum absorption wavelength (nm)
lmax

[14] followed a different approach. Starting from the

same material, a set of activated carbons differing in
their chemical surface properties was prepared. In the
mentioned work, a screening test was carried out in
order to evaluate the performance of the treated ACs in
the removal of a series of dyes. It was concluded that
basic carbons were the most efcient for the removal of
both cationic and anionic dyes.
In this work, a NORIT GAC 1240 PLUS activated
carbon is modied by selected oxidation and heat
treatments and characterised by different techniques.
The adsorbents prepared are subsequently tested in the
removal of three dyes and the equilibrium adsorption
data modelled with the Langmuir and Freundlich
equations. The results obtained are discussed in relation
to both textural and chemical properties of the
adsorbents and to the pH vs. pHpzc of the AC samples.
Our main goal is to account for the interactions between
the different classes of dyes and the surface groups of a
modied commercial activated carbon in order to
develop optimised adsorbent materials for the decolourisation of wastewaters.

2. Experimental
2.1. Preparation of modified activated carbons
A Norit GAC 1240 PLUS activated carbon was used
as supplied as the starting material for this study
(Sample AC1). This carbon was selected because it is
an acid washed granular activated carbon, which
offers good adsorption properties for water applications
and a high purity level. According to the supplier

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P.C.C. Faria et al. / Water Research 38 (2004) 20432052

specications, it has a neutral pH. The treatments

outlined below were carried out in order to obtain
materials with different surface chemistries, while
maintaining the original textural properties as far as
possible. All treatments were performed on the unground materials (0.42odo2 mm).
2.1.1. Oxidation treatments
Oxidation with HNO3 was performed using a 100 cm3
Soxhlet extraction apparatus. Initially 200 cm3 of 6 M
HNO3 were introduced into a 250 cm3 Pyrex roundbottom ask and heated to boiling temperature with a
heating mantle. The Soxhlet with 9 g of activated carbon
was connected to the boiling ask and to the condenser.
The reux was stopped after 3 h. The activated carbon
was washed with distilled water to neutral pH, dried in
an air convection oven at 110
C for 24 h and stored in a
desiccator for later use (Sample AC2). This sample was
used as the starting material for the thermal treatments
described below.
Sample AC3 was prepared by mixing 1 g of the
original material with 25 cm3 of 10 M H2O2 at room
temperature until complete degradation of the H2O2
(when there was no further gas evolution). The sample
was washed with distilled water to neutral pH, dried for
24 h in the oven at 110
C and stored in the desiccator
until used.

2045

et al. [17]. The adsorption data were also analysed with

the Dubinin equation. In all cases, a type IV deviation
was noted [18]. Two micropore structures were taken
into account, and the corresponding volumes, W01 and
W02, were calculated [18]. The Stoeckli equation [19] was
used to estimate the average micropore width of the
smaller pores (L1), using a value of 0.34 for the afnity
coefcient of nitrogen.

2.1.2. Thermal treatments

All the thermal treatments were performed on sample
AC2 since it is important that the starting material
presents a large amount of surface groups in order to
produce activated carbons with a high basic character
[15]. About 3 g of sample AC2 were placed in a fused
silica tubular reactor, heated to 700
C at 10
C/min
under a ow of H2 (50 cm3/min) and kept at this
temperature for 1 h. After cooling to room temperature
under the same atmosphere, a ow of air was introduced
into the reactor and these conditions were maintained
for 1 h. Finally the sample was collected and stored in a
desiccator (Sample AC4). The same treatment was
repeated under a ow of N2 at 700
C (sample AC5).
Thermal treatments under a ow of H2 are expected to
generate higher amounts of basic sites on the surface of
the carbon than thermal treatments under a ow of N2
[16].

2.2.2. Surface chemistry characterisation

Temperature-programmed desorption (TPD) proles
were obtained with a custom built set up, consisting of a
U-shaped tubular micro-reactor, placed inside an
electrical furnace. The mass ow rate of the helium
carrier gas (69 mg/s) and the temperature programme
from room temperature to 1100
C at a heating rate of
5
C/min were controlled with appropriate equipment.
The amounts of CO and CO2 desorbed from the
activated carbon (100 mg) were monitored with a
Spectramass Dataquad quadrupole mass spectrometer.
The masses monitored for all samples were 2 (H2), 16
(O), 18 (H2O), 28 (CO) and 44 (CO2).
The basicity of the carbon materials was estimated
mixing ca. 0.2 g of each sample with 25 cm3 of 0.025 M
HCl solution in a closed ask, and maintaining the
contact under agitation for 48 h at room temperature.
Then the suspension was decanted and the remaining
HCl in solution was determined by titration with a
0.025 M NaOH solution. The total acidity of each
sample was obtained by a similar procedure where a
0.025 M NaOH solution was put in contact with the
activated carbon and the titration solution was 0.025 M
HCl.
The determination of the pHpzc of the samples was
carried out as follows [20]: 50 cm3 of 0.01 M NaCl
solution was placed in a closed Erlenmeyer ask. The
pH was adjusted to a value between 2 and 12 by adding
HCl 0.1 M or NaOH 0.1 M solutions. Then, 0.15 g of
each AC sample was added and the nal pH measured
after 48 h under agitation at room temperature. The
pHpzc is the point were the curve pHnal vs. pHinital
crosses the line pHinitial=pHnal.
The materials used were also characterised by
elemental and proximate analyses, with a CARLO
ERBA EA 1108 Elemental Analyser and a Mettler TA
4000 thermal analyser, respectively.

2.2. Characterisation of the activated carbon samples

2.3. Adsorption experiments

2.2.1. Textural characterisation

The textural characterisation of the materials was
based on the N2 adsorption isotherms, determined at
77 K with a Coulter Omnisorp 100 CX apparatus. The
micropore volumes (Wmicro ) and mesopore surface areas
(Smeso ) were calculated by the t-method using the
standard isotherm proposed by Rodr!guez-Reinoso

Three dyes from different classes, with known

molecular structure, were used to evaluate the adsorption capacity of the prepared materials. The selected
dyes and their characteristics are shown in Table 1. In
order to reduce mass transfer resistances and, consequently, the time necessary to reach equilibrium, the
activated carbon was nely ground and only the fraction

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2046

with a particle diameter smaller than 50 mm was used.

Preliminary kinetic tests were carried out in order to
determine the equilibrium time, which was found to
depend on the specic dye (3 days for the basic dye, 4 for
the reactive and 5 days for the acid dye). It was assumed
that equilibrium was attained when no further changes
in dye uptake were observed after 24 h. Longer times are
necessary when larger particles are used, usually between
2 and 3 weeks [9,13].
The acid and basic dye solutions were prepared simply
by dissolving the desired amount of dye in distilled
water. Taking in consideration that in textile efuents
reactive dyes are in the hydrolysed state, an hydrolysis
procedure was carried out as described elsewhere [14].
The initial pH of all solutions was adjusted to 67. For
each dye solution the UV-Vis spectrum was previously
determined and the maximum absorption wavelength
identied (Table 1).
Adsorption isotherms were obtained by mixing 50 cm3
of dye solution of different concentrations (501000 mg/
dm3) with 50 mg of activated carbon nely ground
(do50 mm) in closed Erlenmeyer asks. The suspensions
were shaken at room temperature, until equilibrium was
reached. After that, they were centrifuged and the
remaining concentration of dye in solution was determined in a JASCO V-560 UV-Vis spectrophotometer.

3. Results and discussion

3.1. Characterisation of the activated carbon samples
The main goal of the present work is to study the
relationship between the surface chemical characteristics
of activated carbons and their performance on the

removal of dyes. For that purpose, a set of modied

activated carbons with different levels of acidity/basicity
but with no major differences in their textural parameters was prepared. Both liquid phase oxidations and
thermal treatments have been reported not to signicantly change these properties [11]. Oxidations with
HNO3 and H2O2 are known to generate acidic materials
[21]. Treatments with HNO3 originate materials with
large amounts of surface acidic groups, mainly carboxylic acids and, in less extent, lactones, anhydrides
and phenol groups [11], whereas treatments with H2O2
produce less acidic materials [14]. On the other hand,
heat treatments under inert or H2 atmosphere at high
temperatures are used to selectively remove some of the
surface oxygen groups, thus originating basic materials
[16].

3.1.1. Textural characterisation

The results obtained from the N2 equilibrium
adsorption isotherms at 77 K are presented in Table 2.
As expected, no major differences in the textural
properties of the materials were observed, particularly
in the case of the micropores volume. The mesopores
area, as well as the volume of micropores, slightly
decreased for the sample oxidised with HNO3. This may
be due to the abundant presence of oxygen-containing
groups on the surface of the activated carbon, which
makes part of the carbon surface inaccessible. The
increase in micropores volume and mesopores area in
samples AC4 and AC5, relatively to sample AC2, can be
explained by the thermal decomposition of the mentioned oxygen groups. As previously discussed [14], no
drastic changes in the textural properties of the prepared
samples were observed, suggesting that the differences in

Table 1
Characteristics of the dyes selected for this study
Class

Commercial name

Generic name

Chemical class

lmax (nm)

Basic
Reactive
Acid

Astrazon Brilliant Red 4G

Rifax Red 3BN
Erionyl Navy R

CI basic red 14
CI reactive red 241
CI acid blue 113

Cyanine
Monoazo
Diazo

514
540
566

Table 2
Textural characterisation of the AC samples
Sample

Wmicro (cm3/g)

Smeso (m2/g)

W01 (cm3/g)

W02 (cm3/g)

L1 (nm)

SBET (m2/g)

AC1
AC2
AC3
AC4
AC5

0.367
0.353
0.365
0.375
0.356

125
91
110
103
114

0.312
0.303
0.311
0.318
0.301

0.058
0.048
0.054
0.058
0.050

1.1
1.1
1.2
1.2
1.2

972
909
949
972
946

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the adsorption capacities of the samples will be mainly

due to their chemical surface properties.
3.1.2. Surface chemistry characterisation
Fig. 1 shows the TPD spectra of the commercial
activated carbon as received and after the different
treatments. Surface oxygen groups on carbon materials
decompose upon heating releasing CO and CO2 at
different temperatures. According to this it is possible to
identify and estimate the amount of oxygenated groups
on a given carbon by TPD experiments. It has been
reported [11] that CO2 peaks result from the decomposition of carboxylic acids at low temperatures or
lactones at high temperatures, and anhydrides originate
both CO and CO2. Groups such as phenols, carbonyls,
ethers and quinones originate CO peaks. Analysing the
results, it is clear that sample AC2, which was oxidised
with HNO3, has the highest amount of surface oxygencontaining groups. Comparing to sample AC1, the H2O2
treated sample contains a higher amount of oxygenated
surface groups, mainly carboxylic ones, which means
that sample AC3 is more acidic than the starting
material. Thermal treatments originate materials with
quite low content of oxygen-containing groups. As can
be seen in the TPD spectra of samples AC4 and AC5,
the CO2 releasing groups have almost completely been
2.5
AC2

CO (a.u.)

2.0
1.5
AC3

1.0
AC5

0.5
AC1
AC4

(a)

0.0
0

200

400

600

800

1000

T (C)
0.6
AC2

CO2 (a.u.)

0.5
0.4
0.3

removed, but some groups releasing CO at high

temperatures still remain on the carbon surface. These
ones are presumed to be part of the carbonyl groups that
have not been decomposed by the treatment at 700
C,
and pyrone type groups, which have basic nature and
decompose at high temperatures. Thermally treated
samples have a basic character which is due to this kind
of oxygen-containing groups and mainly to the electron
rich oxygen-free sites located on the carbon basal planes
[22]. According to Men!endez et al. [16], heat treatments
under inert atmosphere at high temperatures are
effective in removing oxygen but the resulting activated
carbon has a surface with reactive sites capable of
readsorbing oxygen leading to the formation of some of
the previously removed groups. Treatments with H2 also
remove oxygen groups but leave stable basic surfaces by
forming CH bonds, thus preventing further adsorption
of oxygen. This is in agreement with the results
obtained, since the TPD spectrum of sample AC5 shows
a higher amount of CO2 releasing groups than sample
AC4.
The acidity and basicity of the samples and the values
of the pHpzc are shown in Table 3. These two kinds of
results are complementary. As expected, the total
surface acidity increased for the oxidised samples,
whereas the total surface basicity decreased. These
treatments yielded ACs with the lowest pHpzc. The
greatest total surface acidity was obtained for sample
AC2 due to the introduction of several oxygen-containing functional groups, namely carboxylic acids. Sample
AC3 has a more acidic character than the starting
material. However, the oxidation with H2O2 originates a
smaller amount of acid groups on the surface than
oxidation with HNO3, which is also conrmed by TPD
results. On the other hand, sample AC4 has the highest
basic character. Comparing the results obtained for
samples AC4 and AC5, one can say that the treatment
under H2 atmosphere leads to more basic materials than
the treatment under inert atmosphere, which is in
agreement with previous studies reported in the literature [16].
Table 4 shows the results of proximate and elemental
analyses, which are consistent with the data from the
previous characterisation techniques. It can be seen that
oxidation with HNO3 leads to a substantial increase in
Table 3
Acidity/basicity of the AC samples

0.2

AC3

0.1

AC1

AC5

200

400

600

Sample

Acidity
(meq/gAC)

Basicity
(meq/gAC)

pHpzc

AC1
AC2
AC3
AC4
AC5

149
716
358
89
179

302
34
153
437
365

9.7
2.7
5.4
10.8
9.9

AC4

0.0

(b)

2047

800

1000

T (C)

Fig. 1. TPD spectra for AC samples: (a) CO evolution and (b)

CO2 evolution.

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2048

Table 4
Proximate and elemental analyses of the AC samples
Elemental analysis

Moisture (wt%)

Volatiles (wt%)

Cxed (wt%)

Ash (wt%)

C (wt%)

H (wt%)

N (wt%)

S (wt%)

O (wt%)

3.3
4.2
3.7
1.4
2.3

5.3
13.7
9.5
5.2
7.0

85.9
78.7
81.5
88.4
86.0

5.5
3.4
5.3
5.0
4.7

94.9
78.5
90.8
98.1
93.9

0.3
0.8
0.4
0.3
0.2

0.2
0.3
0.3
0.4
0.2

1.0
0.7
0.9
0.5
0.8

3.6
19.7
7.6
0.7
4.9

volatiles content, which is also corroborated by the

increase in oxygen content obtained by elemental
analysis. Some of the ash content in sample AC2 may
have been removed during the oxidation in liquid phase.
As mentioned before, the treatment with H2O2 originates less acidic samples. This is conrmed by the results
of Table 4. There is a smaller increase both in volatile
matter and oxygen content in sample AC3 than in
sample AC2 comparatively to the commercial carbon.
Comparing samples AC4 and AC5 with the associated
starting material (AC2), a decrease in both volatile
matter and oxygen content is evident, which is in
agreement with the previous results. Both thermal
treatments result in the removal of the oxygen groups
from the surface of the carbon. Even though sample
AC5 has a higher amount of oxygen than the
commercial carbon (AC1), it is noticeable that after
the thermal treatments the activated carbon does not
recover the oxygen groups initially present. Elemental
analysis of sample AC4 revealed that this material is
almost free of oxygen.
Summarising the results obtained from the different
techniques, it is clear that sample AC2 has a strong acid
character while samples AC4 and AC5 have basic
characteristics.

400

300

qe (mg/gAC)

AC1
AC2
AC3
AC4
AC5

Proximate analysis

200

100

(a)

0
0

200

400

600

800

1000

800

1000

Ce (mg/L)
300

qe (mg/gAC)

Sample

200

100

(b)

200

400

600

Ce (mg/L)

3.2. Equilibrium adsorption isotherms

800

qe qm

KL Ce
1 KL Ce

600

qe (mg/gAC)

The adsorption isotherms at room temperature of the

three selected dyes on the activated carbon samples are
presented in Fig. 2. The results were analysed using
Langmuir and Freundlich isotherms:

400

200

and
qe KF Ce1=n ;

respectively, where Ce and qe are the adsorbate

equilibrium concentrations in the liquid and solid
phases, qm is the maximum adsorption capacity according to the Langmuir model, KL ; KF and n are constants.

(c)

0
0

100

200

300

400

500

600

Ce (mg/L)
Fig. 2. Adsorption isotherms at room temperature of (a) acid,
(b) reactive and (c) basic dyes on commercial and treated ACs:
AC1 (&), AC2 (J), AC3 (n), AC4 (,) and AC5 (B).

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The model equations can be linearized, leading to

Ce
1
1

Ce
3
qm KL qm
qe
and
1
ln qe ln KF ln Ce
n

and tted to experimental data. The corresponding

parameters are shown in Tables 5 and 6, as well as the
standard deviations associated to the linear ts. The
Langmuir adsorption isotherm provides the best t for
the systems ACs/basic dye. In general, for acid and
reactive dyes, both Langmuir and Freundlich models
similarly represent the experimental data. However, the
Langmuir model was preferred due to the physical
meaning attributed to its constants, particularly qm ;
which is used for the discussion of the results on the
basis of the chemical properties of the samples. The
curves associated to the Langmuir model are also
represented in Fig. 2.
3.3. Discussion of adsorption results on the basis of the
chemical properties of the AC samples
Since no drastic changes were made in the textural
properties of the adsorbents, the disparity in dye uptakes
for the different activated carbons may be explained

2049

almost entirely by the differences in the chemical nature

of the prepared samples. For basic dyes, no signicant
correlation could be established between the textural
properties and the colour removal. For instance, with
samples AC1, AC2 and AC3, the dye removal increased
with the decrease in both Wmicro and Smeso ; as shown in
Fig. 3. Similar behaviour was observed for samples AC4
and AC5, in relation to Smeso : These observations
demonstrate that the textural properties of the studied
materials cannot explain the behaviour of these adsorbents towards basic dyes. Nevertheless, the inuence of
the adsorbent texture in the dye uptake should not be
completely discarded as for acid and reactive dyes weak
correlations between the adsorption capacity of the ACs
and their textural properties might be found. In
contrast, strong correlations between acidity/basicity
and maximum adsorption capacity for acid and reactive
dyes are clearly shown in Fig. 4 and will be discussed
below.
Activated carbons are materials with amphoteric
character; thus, depending on the pH of the solution,
their surfaces might be positively or negatively charged.
At pH>pHpzc the carbon surface becomes negatively
charged favouring the adsorption of cationic species. On
the other hand, adsorption of anionic species will be
favoured at pHopHpzc [23]. In the present work the
initial pH of the aqueous dyestuff solutions was set to

Table 5
Parameters of the Langmuir model
Sample

Acid dye
qm (mg/gAC)

Reactive dye
KL (dm3/mg)

SDa

qm (mg/gAC)

AC1
AC2
AC3
AC4
AC5

310
0.120
0.010
190
197
0.025
0.085
157
244
0.057
0.081
201
345
0.058
0.032
246
262
0.093
0.030
223
r


PN
a
calc 2 =N  1 ; y C =q :
SD
e
e
i1 y  y

Basic dye
KL (dm3/mg)

SDa

qm (mg/gAC)

KL (dm3/mg)

SDa

0.052
0.030
0.034
0.061
0.055

0.074
0.156
0.157
0.050
0.081

546
633
568
714
680

0.963
0.994
0.640
0.828
0.955

0.004
0.002
0.005
0.002
0.003

Table 6
Parameters of the Freundlich model
Sample

Acid dye
n

AC1
AC2
AC3
AC4
AC5

Reactive dye
3

1=n

KF mg=gAC dm =mg

SD

11
175
0.037
5.6
60
0.051
7.6 106
0.052
9.8 177
0.016
6.7 107
0.078

r

PN
a
calc 2 =N  1 ; y ln q :
SD
e
i1 y  y

Basic dye
3

KF mg=gAC dm =mg

4.9
5.7
5.8
4.9
5.1

53
49
65
71
66

1=n

SD

KF mg=gAC dm3 =mg1=n

SDa

0.131
0.049
0.058
0.117
0.166

23
17
19
13
16

431
469
424
490
495

0.049
0.081
0.041
0.090
0.088

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P.C.C. Faria et al. / Water Research 38 (2004) 20432052

2050

400

800
AC4

AC4

AC5

r = 0.888

AC2

300

AC3

AC5

AC1

AC3

qm (mg /gAC)

qm (mg/gAC )

600

AC1

400

AC4
AC2

200

AC5
AC3

AC2

AC1

r = 0.899

100

200
0
0

(a)

0
0.350

0.355 0.360 0.365 0.370

100

200

300

0.375 0.380

500

800

Wmicro (cm /g)

AC4
AC5
AC2

800

600

AC4

AC1

AC3

AC 5

600

AC3

AC1

qm (mg /gAC)

r = 0.992

AC 2

qm (mg/gAC )

400

Basicity (eq/gAC )

400

200

400

200

200

400

600

800

Acidity (eq /gAC )

(b)

0
90

95 100 105 110 115 120 125 130

2

Smeso (m /g)
Fig. 3. Maximum adsorption capacity for the basic dye versus
Wmicro (a) and Smeso (b) of the AC samples.

67. If the electrostatic interactions were the main

adsorption mechanism, cationic (basic) dyes would be
expected to have greater afnity for samples AC2 and
AC3 (pHpzcopH) and anionic (reactive and acid) dyes
would preferably adsorb on samples AC1, AC4, and
AC5 (pHpzc>pH). Nonetheless, two parallel adsorption
mechanisms, one involving electrostatic interactions and
a second one involving dispersive interactions were
report to explain the adsorption of organics in activated
carbons [24]; thus, one cannot only account for the role
of electrostatic interactions.
For the acid and reactive dyes, a strong correlation
between the basicity of the AC samples and the dye
uptakes is shown in Fig. 4, which is in agreement with
the previous reasoning. Comparing both heat-treated
samples it is evident that sample AC4 has the best
adsorption capacity for both acid and reactive dyes.
According to Leon y Leon et al. [22], basic carbons are
characterised by a high content of electron rich sites on
their basal planes and a low concentration of electron

Fig. 4. Correlation between samples acidity/basicity and

maximum adsorption capacity for acid (&), reactive (J),
and basic (,) dyes.

withdrawing groups. The interaction of the molecules of

dyes and the activated carbon surface is expected to
occur between the delocalised p electrons of the oxygenfree Lewis basic sites and the free electrons of the dye
molecule present in the aromatic rings and multiple
bonds. The same authors have reported evidence for the
protonation of basal plane sites on basic carbon. They
state that oxygen-free carbon sites can adsorb protons
from the solution, conferring a positively charged
surface to the carbon. Thus, it is possible that negatively
charged ions of the dyes also interact with these sites.
The presence of oxygen-containing functional groups,
which are electron-withdrawing groups, has a negative
effect on the adsorption of anionic species, as can be
observed for sample AC2. These groups reduce the
electron density on the surface of the carbon [24], thus
decreasing the adsorption potential for the dye molecules. Simultaneously there is an increase in repulsive
electrostatic interactions between the anions of the dyes
and the negatively charged surface of sample AC2.
When dissolved in water, basic dyes are positively
charged; thus it was expected that these dyes would
preferably adsorb onto activated carbons with acid
characteristics. In fact, when comparing the behaviour

ARTICLE IN PRESS
P.C.C. Faria et al. / Water Research 38 (2004) 20432052

of anionic and cationic dyes, we observe that sample

AC2 has a better performance for the latter ones,
relatively to AC1. This was expected due to the
electrostatic interactions between the cations and the
negatively charged surface of acid samples. For basic
dyes there is a strong correlation between the dye uptake
and the increasing acidity of samples AC1, AC3 and
AC2 (Fig. 4). However, samples AC4 and AC5 provide
higher adsorption uptakes than the previous samples.
This observation leads to the conclusion that, even
though adsorption of cationic species on activated
carbons is enhanced by the presence of surface acid
groups, basic carbons still present better performances,
indicating that dispersive interactions between the
delocalised p electrons on the surface of the basic
activated carbons and the free electrons of the dye
molecule present in the aromatic rings and multiple
bonds play a dominant role in the adsorption mechanism.

4. Conclusions
The following conclusions can be drawn from the
present work:
1. The Langmuir adsorption isotherm provides the best
t for the systems ACs/basic dye. The adsorption
data for the remaining systems are well tted with
both Langmuir and Freundlich models.
2. It is possible to tailor the surface of activated carbons
in order to optimise their adsorption capacity
towards dye molecules. Among the several treatments performed, thermal treatment with H2 at
700
C proved to be the most efcient for the removal
of both anionic and cationic dyes.
3. The differences in the textural properties of the
activated carbons cannot explain the disparity in dyes
adsorption on the samples, leading to the conclusion
that surface chemistry plays a key role in the
adsorption process.
4. For reactive and acid dyes, a close relationship
between the surface basicity of the adsorbents and
dye adsorption was shown. The interaction between
the oxygen-free Lewis basic sites and the free
electrons of the dye molecule, as well as the
electrostatic interactions between the anions and the
protonated sites of the carbon are the main adsorption mechanisms.
5. For the basic dye, the acid oxygen-containing surface
groups have a positive effect on the adsorption, but
thermally treated samples still present better performances, showing the existence of two adsorption
mechanisms involving electrostatic and dispersive
interactions.

2051

Acknowledgements
The authors are indebted to NORIT N.V., Amersfoort, The Netherlands, and to Jos!e Morgado and
!
!
Antonio
Vieira from CITEVE (Centro Tecnologico
das
Industrias T#extil e do Vestua! rio de Portugal) for
providing samples. This work was carried out with the
support of Funda@*ao para a Ci#encia e a Tecnologia
(FCT) under programme POCTI/FEDER (POCTI/
1181) and Ag#encia de Inova@*ao (ADI) under programme POCTI/FEDER (project ANOXITRATA).

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