ARTICLE IN PRESS

Water Research 38 (2004) 2043–2052

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!ımica, 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 influence 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 flow (basic materials). The specific 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 fit 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 flow 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 Despite the existence of a wide range of wastewaters

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 unfixed dyes and may
be highly coloured. The persisting colour and the non-
biodegradable nature of the spent dyebaths represent
serious problems to the environment. However, the
primary concern about effluent colour is its undesirable
aesthetic impact in receiving waters [1].
*Corresponding author. Tel.: +351-22-508-1468; fax: +351-
22-508-1449.
E-mail address: fpereira@fe.up.pt (M.F.R. Pereira).
treatment techniques, there is no single process capable
of adequate treatment for these effluents [2]. Thus, the
best solution for textile wastewater treatment appears as
a combination of different techniques. The conventional
association of biological and physical–chemical pro-
cesses results in the removal of most of the organic
content of the textile wastewaters. However, the result-
ing effluent is still fairly coloured. Ideally, a final refining
treatment is needed to remove the colour [3]. This final
step in the treatment of textile effluents 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
 ARTICLE IN PRESS
2044 P.C.C. Faria et al. / Water Research 38 (2004) 2043–2052
Nomenclature
AC activated carbon
a.u. arbitrary units
Ce adsorbate equilibrium liquid phase concen-
tration (mg/dm3)
CI Colour Index
d particle diameter
KF parameter in the Freundlich equation
ðmg=gAC ðdm3 =mgÞ1=n Þ
KL parameter in the Langmuir equation (dm3/
gAC)
L1 average width of the small micropores (nm)
n parameter in the Freundlich equation
N number of points
pHpzc point of zero charge
qe adsorbate equilibrium solid phase concentra-
tion (mg=gAC )
successful efficient alternatives for the removal of dyes in
wastewater. Studies involving the application of a wide
range of adsorbents in the decolourisation of waste-
waters are reported in literature [5,6], adsorption on
activated carbon (AC) being one of the most studied
techniques [7–9].
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 capa-
city 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 char-
acteristics for specific applications [10]. Yet, little
attention has been given to the role of the AC surface
chemistry in the adsorption process. Karanfil et al. [12]
evaluated the uptake of two organic contaminants on a
set of commercial and treated ACs in order to study the
influence 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 effluents
[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 t-
method (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) micro-
pores calculated by the Dubinin method
(cm3/g)
Greek symbols
lmax maximum absorption wavelength (nm)
[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 efficient for the removal of
both cationic and anionic dyes.
In this work, a NORIT GAC 1240 PLUS activated
carbon is modified 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
modified commercial activated carbon in order to
develop optimised adsorbent materials for the decolour-
isation 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
 ARTICLE IN PRESS
P.C.C. Faria et al. / Water Research 38 (2004) 2043–2052
specifications, 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 un-
ground 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 round-
bottom flask and heated to boiling temperature with a
heating mantle. The Soxhlet with 9 g of activated carbon
was connected to the boiling flask and to the condenser.
The reflux 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.
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 flow of H2 (50 cm3/min) and kept at this
temperature for 1 h. After cooling to room temperature
under the same atmosphere, a flow 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 flow of N2 at 700
C (sample AC5).
Thermal treatments under a flow of H2 are expected to
generate higher amounts of basic sites on the surface of
the carbon than thermal treatments under a flow of N2
[16].
2.2. Characterisation of the activated carbon samples
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!ıguez-Reinoso
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 affinity
coefficient of nitrogen.
2.2.2. Surface chemistry characterisation
Temperature-programmed desorption (TPD) profiles
were obtained with a custom built set up, consisting of a
U-shaped tubular micro-reactor, placed inside an
electrical furnace. The mass flow 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 flask, 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 flask. 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 final pH measured
after 48 h under agitation at room temperature. The
pHpzc is the point were the curve pHfinal vs. pHinital
crosses the line pHinitial=pHfinal.
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.
2.3. Adsorption experiments
Three dyes from different classes, with known
molecular structure, were used to evaluate the adsorp-
tion capacity of the prepared materials. The selected
dyes and their characteristics are shown in Table 1. In
order to reduce mass transfer resistances and, conse-
quently, the time necessary to reach equilibrium, the
activated carbon was finely ground and only the fraction
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2046 P.C.C. Faria et al. / Water Research 38 (2004) 2043–2052

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 specific 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 effluents
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 6–7. For
each dye solution the UV-Vis spectrum was previously
determined and the maximum absorption wavelength
identified (Table 1).
Adsorption isotherms were obtained by mixing 50 cm3
of dye solution of different concentrations (50–1000 mg/
dm3) with 50 mg of activated carbon finely ground
(do50 mm) in closed Erlenmeyer flasks. 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 deter-
mined 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 modified
activated carbons with different levels of acidity/basicity
but with no major differences in their textural para-
meters was prepared. Both liquid phase oxidations and
thermal treatments have been reported not to signifi-
cantly 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 car-
boxylic 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 men-
tioned 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 Astrazon Brilliant Red 4G CI basic red 14 Cyanine 514

Reactive Rifafix Red 3BN CI reactive red 241 Monoazo 540
Acid Erionyl Navy R CI acid blue 113 Diazo 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 0.367 125 0.312 0.058 1.1 972

AC2 0.353 91 0.303 0.048 1.1 909
AC3 0.365 110 0.311 0.054 1.2 949
AC4 0.375 103 0.318 0.058 1.2 972
AC5 0.356 114 0.301 0.050 1.2 946
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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 decom-
position 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 oxygen-
containing 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
2.0
CO (a.u.)
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 C–H 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-contain-
ing functional groups, namely carboxylic acids. Sample
AC3 has a more acidic character than the starting
material. However, the oxidation with H2O2 originates a

1.5
smaller amount of acid groups on the surface than
AC3 oxidation with HNO3, which is also confirmed by TPD
1.0 results. On the other hand, sample AC4 has the highest
AC5
basic character. Comparing the results obtained for
0.5 samples AC4 and AC5, one can say that the treatment
AC1
AC4 under H2 atmosphere leads to more basic materials than
0.0 the treatment under inert atmosphere, which is in
(a) 0 200 400 600 800 1000
agreement with previous studies reported in the litera-
T (ºC)
ture [16].
0.6
AC2 Table 4 shows the results of proximate and elemental
0.5
analyses, which are consistent with the data from the
previous characterisation techniques. It can be seen that
0.4 oxidation with HNO3 leads to a substantial increase in
CO2 (a.u.)

0.3 Table 3
Acidity/basicity of the AC samples
0.2 AC3
Sample Acidity Basicity pHpzc
0.1 (meq/gAC) (meq/gAC)
AC1
AC5 AC4
0.0 AC1 149 302 9.7
(b) 0 200 400 600 800 1000 AC2 716 34 2.7
T (ºC) AC3 358 153 5.4
AC4 89 437 10.8
Fig. 1. TPD spectra for AC samples: (a) CO evolution and (b) AC5 179 365 9.9
CO2 evolution.
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2048 P.C.C. Faria et al. / Water Research 38 (2004) 2043–2052

Table 4
Proximate and elemental analyses of the AC samples

Sample Proximate analysis Elemental analysis

Moisture (wt%) Volatiles (wt%) Cfixed (wt%) Ash (wt%) C (wt%) H (wt%) N (wt%) S (wt%) O (wt%)

AC1 3.3 5.3 85.9 5.5 94.9 0.3 0.2 1.0 3.6
AC2 4.2 13.7 78.7 3.4 78.5 0.8 0.3 0.7 19.7
AC3 3.7 9.5 81.5 5.3 90.8 0.4 0.3 0.9 7.6
AC4 1.4 5.2 88.4 5.0 98.1 0.3 0.4 0.5 0.7
AC5 2.3 7.0 86.0 4.7 93.9 0.2 0.2 0.8 4.9

volatiles content, which is also corroborated by the

increase in oxygen content obtained by elemental 400
analysis. Some of the ash content in sample AC2 may
have been removed during the oxidation in liquid phase.
300
As mentioned before, the treatment with H2O2 origi-

qe (mg/gAC)
nates less acidic samples. This is confirmed by the results
of Table 4. There is a smaller increase both in volatile 200
matter and oxygen content in sample AC3 than in
sample AC2 comparatively to the commercial carbon.
100
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 0
agreement with the previous results. Both thermal (a) 0 200 400 600 800 1000
treatments result in the removal of the oxygen groups Ce (mg/L)
from the surface of the carbon. Even though sample 300
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
200
qe (mg/gAC)

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 100
techniques, it is clear that sample AC2 has a strong acid
character while samples AC4 and AC5 have basic
characteristics.
0
(b) 0 200 400 600 800 1000

3.2. Equilibrium adsorption isotherms Ce (mg/L)

800
The adsorption isotherms at room temperature of the
three selected dyes on the activated carbon samples are
600
presented in Fig. 2. The results were analysed using
qe (mg/gAC)

Langmuir and Freundlich isotherms:

400
KL Ce
qe ¼ qm ð1Þ
1 þ KL Ce
200
and

qe ¼ KF Ce1=n ; ð2Þ 0
(c) 0 100 200 300 400 500 600
Ce (mg/L)
respectively, where Ce and qe are the adsorbate
equilibrium concentrations in the liquid and solid Fig. 2. Adsorption isotherms at room temperature of (a) acid,
phases, qm is the maximum adsorption capacity accord- (b) reactive and (c) basic dyes on commercial and treated ACs:
ing to the Langmuir model, KL ; KF and n are constants. AC1 (&), AC2 (J), AC3 (n), AC4 (,) and AC5 (B).
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P.C.C. Faria et al. / Water Research 38 (2004) 2043–2052 2049

The model equations can be linearized, leading to
Ce 1 1
¼ þ Ce ð3Þ
qe qm KL qm
and
1
ln qe ¼ ln KF þ ln Ce
n Fig. 3. Similar behaviour was observed for samples AC4
and fitted to experimental data. The corresponding
parameters are shown in Tables 5 and 6, as well as the
standard deviations associated to the linear fits. The
Langmuir adsorption isotherm provides the best fit 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
almost entirely by the differences in the chemical nature
of the prepared samples. For basic dyes, no significant
correlation could be established between the textural
properties and the colour removal. For instance, with
samples AC1, AC2 and AC3, the dye removal increased
ð4Þ with the decrease in both Wmicro and Smeso ; as shown in
and AC5, in relation to Smeso : These observations
demonstrate that the textural properties of the studied
materials cannot explain the behaviour of these adsor-
bents towards basic dyes. Nevertheless, the influence 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 Reactive dye Basic dye

qm (mg/gAC) KL (dm3/mg) SDa qm (mg/gAC) KL (dm3/mg) SDa qm (mg/gAC) KL (dm3/mg) SDa

AC1 310 0.120 0.010 190 0.052 0.074 546 0.963 0.004
AC2 197 0.025 0.085 157 0.030 0.156 633 0.994 0.002
AC3 244 0.057 0.081 201 0.034 0.157 568 0.640 0.005
AC4 345 0.058 0.032 246 0.061 0.050 714 0.828 0.002
AC5 262 0.093 0.030 223 0.055 0.081 680 0.955 0.003
r
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

a PN calc Þ2 =ðN  1Þ ; y ¼ ðC =q Þ:
SD ¼ i¼1 ðy  y e e

Table 6
Parameters of the Freundlich model

Sample Acid dye Reactive dye Basic dye

a a
n KF ðmg=gAC ðdm =mgÞ 3 1=n
Þ SD n 3
KF ðmg=gAC ðdm =mgÞ 1=n
Þ SD n KF ðmg=gAC ðdm3 =mgÞ1=n Þ SDa

AC1 11 175 0.037 4.9 53 0.131 23 431 0.049

AC2 5.6 60 0.051 5.7 49 0.049 17 469 0.081
AC3 7.6 106 0.052 5.8 65 0.058 19 424 0.041
AC4 9.8 177 0.016 4.9 71 0.117 13 490 0.090
AC5 6.7 107 0.078 5.1 66 0.166 16 495 0.088
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

a PN calc Þ2 =ðN  1Þ ; y ¼ ln q :
SD ¼ i¼1 ðy  y e
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2050 P.C.C. Faria et al. / Water Research 38 (2004) 2043–2052

800 400
AC4 AC4
AC5
AC2 r = 0.888 AC1
300
600 AC3
AC1 AC5
AC3

qm (mg /gAC)
qm (mg/gAC )

AC4
AC2 AC5
200 AC3
AC1
400
AC2
r = 0.899
100

200
0
0 100 200 300 400 500
0 Basicity (µeq/gAC )
(a) 0.350 0.355 0.360 0.365 0.370 0.375 0.380
3
800
Wmicro (cm /g) AC4
AC5
AC2
800
AC4 600 AC1
AC3
AC 5 r = 0.992
AC 2

qm (mg /gAC)
600 AC3
AC1 400
qm (mg/gAC )

400 200

0
200 0 200 400 600 800
Acidity (µeq /gAC )

0 Fig. 4. Correlation between samples acidity/basicity and

(b) 90 95 100 105 110 115 120 125 130 maximum adsorption capacity for acid (&), reactive (J),
2 and basic (,) dyes.
Smeso (m /g)

Fig. 3. Maximum adsorption capacity for the basic dye versus

Wmicro (a) and Smeso (b) of the AC samples.
6–7. If the electrostatic interactions were the main
adsorption mechanism, cationic (basic) dyes would be
expected to have greater affinity 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
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 oxygen-
free 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 mole-
cules. 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) 2043–2052
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 mechan-
ism.
4. Conclusions
The following conclusions can be drawn from the
present work:
1. The Langmuir adsorption isotherm provides the best
fit for the systems ACs/basic dye. The adsorption
data for the remaining systems are well fitted 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 treat-
ments performed, thermal treatment with H2 at
700
C proved to be the most efficient 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 adsorp-
tion 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 perfor-
mances, showing the existence of two adsorption
mechanisms involving electrostatic and dispersive
interactions.
2051
Acknowledgements
The authors are indebted to NORIT N.V., Amers-
foort, 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 pro-
gramme POCTI/FEDER (project ANOXITRATA).
References
[1] USEPA, 1996. Best management practices for pollution
prevention in the textile industry. EPA/625/R-96/004.
Cincinnati, OH: US Environmental Protection Agency.
[2] Cooper P. Removing colour from dyehouse wastewaters—
a critical review of technology available. J Soc Dyers
Colour 1993;109:97–100.
[3] Marmagne O, Coste C. Color removal from textile plant
effluents. Am Dyestuff Reporter 1996;85:15–21.
[4] Rott U, Minke R. Overview of wastewater treatment and
recycling in the textile processing industry. Water Sci
Technol 1999;40:137–44.
[5] Bhavani KD, Dutta PK. Physico-chemical adsorption
properties on chitosan for dyehouse effluent. Am Dyestuff
Reporter 1999;88:53–8.
[6] Bousher A, Shen X, Edyvean RGJ. Removal of coloured
organic matter by adsorption onto low-cost waste materi-
als. Water Res 1997;31:2087–92.
[7] Choy KKH, McKay G, Porter JF. Sorption of acid dyes
from effluents using activated carbon. Resour Conservat
Recycling 1999;27:57–71.
[8] Walker GM, Weatherley LR. Adsorption of acid dyes
onto granular activated carbon in fixed beds. Water Res
1997;31:2093–101.
[9] Walker GM, Weatherley LR. CDO removal from textile
industry effluent: pilot plant studies. Chem Eng J 2001;
84:125–31.
[10] Bansal RC, Donnet JB, Stoeckli F. Active carbon. New
York: Marcel Decker; 1988.
[11] Figueiredo JL, Pereira MFR, Freitas MMA, Orf* ! ao JJM.
Modification of the surface chemistry of activated carbons.
Carbon 1999;37:1379–89.
[12] Karanfil T, Kilduff JE. Role of granular activated carbon
surface chemistry on the adsorption of organic com-
pounds. 1. Priority pollutants. Environ Sci Technol
1999;3217–24.
[13] Al-Degs Y, Khraisheh MAM, Allen SJ, Ahmad MN.
Effect of carbon surface chemistry on the removal of
reactive dyes from textile effluent. Water Res 2000;34:
927–35.
[14] Pereira MFR, Soares SF, Orf* ! ao JJM, Figueiredo JL.
Adsorption of dyes on activated carbons: influence of
surface chemical groups. Carbon 2003;41:811–21.
[15] Papirer E, Li S, Donnet JB. Contribution to the study of
basic surface groups on carbon. Carbon 1987;25:243–7.
 ARTICLE IN PRESS
2052 P.C.C. Faria et al. / Water Research 38 (2004) 2043–2052
[16] Men!endez JA, Phillips J, Xia B, Radovic LR. On the
modification and characterization of chemical surface
properties of activated carbon: in the search of carbons
with stable basic properties; Langmuir 1996;4404–10.
[17] Rodr!ıguez-Reinoso F, Martin-Martinez JM, Prado-Bur-
guete C, McEnaney B. A standard adsorption isotherm for
the charaterization of activated carbons. J Phys Chem
1987;91:515–6.
[18] Linares-Solano A.Textural characterization of porous
carbons by physical adsorption of gases. In: Carbon and
coal gasification, Nato ASI Series, E105. Figueiredo JL,
Moulijn JA, editors. Dordrecht: Martinus Nijhoff Publish-
ers, 1986.
[19] Stoeckli HF, Ballerini L, De Bernardini S. On the
evolution of micropore widths and areas in the course of
activation. Carbon 1989;27:501–2.
[20] Rivera-Utrilla J, Bautista-Toledo I, Ferro-Garc!ıa MA,
Moreno-Castilla C. Activated carbon surface modifica-
tions by adsorption of bacteria and their effect on aqueous
lead adsorption. J Chem Technol Biotechnol 2001;76:
1209–15.
[21] !
Moreno-Castilla C, Lopez-Ram! on MV, Carrasco-Mar!ın
F. Changes in surface chemistry of activated carbons by
wet oxidation. Carbon 2000;38:1995–2001.
[22] Leon y Leon CA, Solar JM, Calemma V, Radovic LR.
Evidence for the protonation of basal plane sites on
carbon. Carbon 1992;30:797–811.
[23] Rodr!ıguez-Reinoso F. The role of carbon materials in
heterogeneous catalysis. Carbon 1998;36:159–75.
[24] Radovic LR, Silva IF, Ume JI, Men!endez JA, Leon y Leon
CA, Scaroni AW. An experimental and theoretical study
of the adsorption of aromatics possessing electron-with-
drawing and electron-donating functional groups by
chemically modified activated carbons. Carbon 1997;
35:1339–48.