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The effects of the surface oxidation of activated carbon, thesolution pH and the temperature on adsorption of ibuprofen
Hanen Guedidi a,b, Laurence Reinert a, Jean-Marc Leveque a, Yasushi Soneda c,Nizar Bellakhal b, Laurent Duclaux a,*
a Laboratoire de Chimie Moleculaire et Environnement, Universite de Savoie, Le Bourget du Lac 73376, Franceb Laboratoire de Chimie Analytique et Electrochimie, Universite de Tunis, 2092 Manar II, Tunisiac National Institute of Advanced Industrial Science and Technology, Energy Technology Research Institute, 16-1 Onogawa,
Tsukuba, Ibaraki 305-8569, Japan
A R T I C L E I N F O
Article history:
Received 3 August 2012
Accepted 28 November 2012
Available online 7 December 2012
A B S T R A C T
A commercial microporous–mesoporous granular activated carbon was modified by oxida-
tion with either H2O2 in the presence or absence of ultrasonic irradiation, or NaOCl or by a
thermal treatment under nitrogen flow. Raw and modified materials were characterized by
N2 adsorption–desorption measurements at 77 K, Boehm titrations, pH measurements and
X-ray photoelectron spectroscopy. Ibuprofen adsorption kinetic and isotherm studies were
carried out at pH 3 and 7 on raw and modified materials. The thermodynamic parameters
of adsorption were calculated from the isotherms obtained at 298, 313 and 328 K. The pore
size distribution of carbon loaded with ibuprofen brought out that adsorption occurred
preferentially into the ultramicropores. The adsorption of ibuprofen on pristine activated
carbon was found endothermic, spontaneous (DG� = �1.1 kJ mol�1), and promoted at acidic
pH through dispersive interactions. All explored oxidative treatments led mainly to the for-
mation of carbonyl groups and in a less extent to lactonic and carboxylic groups. This then
helped to enhance the adsorption uptake while decreasing adsorption Gibbs energy (nota-
bly �7.3 kJ mol�1 after sonication in H2O2). The decrease of the adsorption capacity after
bleaching was attributed to the presence of phenolic groups.
� 2012 Elsevier Ltd. All rights reserved.
1. Introduction
Pharmaceutically active compounds (PhACs) are frequently
detected in treated wastewater arising from sewage treat-
ment plants, from which they are not completely removed
[1,2]. Moreover, recent studies have reported the presence of
traces or ultra traces (ng L�1) of PhACs in drinking water [3].
Many of these compounds are also suspected to have adverse
impact on humans and wild life [4].
According to literature, ibuprofen (IBP), a non steroidal
anti-inflammatory, is one of the most common drugs found
in water [5]. Indeed, the latter has been detected in the
effluents from several sewage-treatment plants at concentra-
tions up to 24.6 lg L�1 [6], possibly presenting a potential
hazard for human health [7].
The removal of IBP was already reported using different
techniques such as ultrasonic irradiation [8], combined ad-
vanced oxidation processes (AOPs) such as sonophotocatalyt-
ic degradation in the presence of Fe3+ and TiO2 [9],
electrochemical degradation [10], recognizing extraction
using molecularly imprinted polymers (MIPs) [11,12], adsorp-
tion on mesoporous silica [13] or activated carbons [14,15].
Activated carbon has several applications depending on
its porous structure and adsorption capacity [16]. In the
0008-6223/$ - see front matter � 2012 Elsevier Ltd. All rights reserved.http://dx.doi.org/10.1016/j.carbon.2012.11.059
* Corresponding author: Fax: +33 479758805.E-mail address: [email protected] (L. Duclaux).
C A R B O N 5 4 ( 2 0 1 3 ) 4 3 2 – 4 4 3
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journal homepage: www.elsev ier .com/ locate /carbon
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literature, numerous studies have shown that adsorption by
activated carbon is effective for the removal of various pollu-
tants in water and waste water such as heavy metals [17–19],
dyes [20–25], pesticide [26,27], fluoride [28] and PhACs [29].
Mestre et al. [15] previously reported that IBP adsorption
on activated carbons was enhanced by the presence of supe-
rmicropores and acidic pH values but was not by the variation
of temperature in the range of 298–313 K. In addition, they
emphasized the favorable effect of basic carbon surface [14]
on the IBP adsorption process and hypothesized that the pres-
ence of mesopores was crucial to ensure the accessibility to
the inner microporosity which had to be large enough
(0.7 nm) to accommodate IBP moieties. More recently, the
adsorption of IBP on a mesoporous activated carbon prepared
from Artemisia Vulgaris leaves [30] was reported to be endo-
thermic and the maximum uptake was observed at pH 2 sug-
gesting a physisorption mechanism involving the carboxylic
function of the adsorbate molecule.
The modification of the surface chemistry of activated car-
bons by treatments in liquid media with oxidative agents
such as HNO3, (NH4)2S2O8, and H2O2 is known to generate
an increase in the number of acidic surface sites. However,
this also leads to a drastic decrease in the total specific sur-
face area and micropore volume, explained by the presence
of oxygen groups at the entrance and the walls of the pores
[31]. For all cited treatments, except the one with H2O2, a
destruction of the basic sites was observed [31].
Functional oxygen groups play an important role in the
adsorption of aromatic molecules. Haydar et al. [32] reported
that oxidation by HNO3 greatly increased the number of car-
boxylic groups, withdrawing electrons from the graphene lay-
ers and thus reducing the p-nitrophenol uptake. Mattson
et al. [33] suggested that an interaction between carbonyl sur-
face groups (as electron donors) and aromatic rings of phenol
(acceptors) lead to the formation of donor–acceptor com-
plexes. Other authors explained the adsorption of phenol
through the formation of hydrogen bonds (of the OH function
of phenol) with carboxylic groups [34].
This present work aims at investigating the IBP adsorption
profile on chemically modified surfaces-bearing activated car-
bons. Thus, a commercial microporous–mesoporous acti-
vated carbon was treated in several different ways in order
to obtain adsorbents with different surface properties. The
adsorption properties of the modified and pristine activated
carbons were studied as a function of concentration, pH,
and temperature to investigate the impact of the surface
chemistry on the IBP adsorption.
2. Experimental
2.1. Ibuprofen
2-[4-(2-Methylpropyl) phenyl] propanoic acid (Fig. 1), also
named ibuprofen, was purchased from the national
laboratory of the control of drugs (LNCM, Tunisia) and used
as received (99.1% purity). This molecule is very slightly
soluble in water (21 mg L�1) [35] but soluble in a majority of
organic solvents [36,37]. The dimensions were estimated
using ‘‘Chemsketch 3D Viewer’’ assuming a parallelepiped
shape: 1.13 · 0.50 · 0.31 nm3.
2.2. Raw and modified activated carbons
A commercial granulated activated carbon (Sigma–Aldrich,
Ref. 292591, 4–14 mesh) was milled and washed with a hydro-
chloric acid solution (0.1 mol L�1) for 24 h under stirring to re-
move metal salt impurities. The resulting suspension was
then filtered off and the recovered carbon was rinsed with
distilled water (�200 mL/g) until reaching a constant pH of
the filtrate [38]. After drying at 383 K for 24 h, this sample, re-
ferred to AC, was further chemically modified by four differ-
ent treatments as described here below:
(1) For the bleaching treatment, AC (1 g) was dispersed in
200 mL of a 0.13 mol L�1 NaOCl solution and stirred at
room temperature during 24 h.
(2) AC samples (2.5 g) were also oxidized by impregnation
at room temperature for 5 h with 50 mL of 35% H2O2,
or (3) by ultrasound irradiation for 5 h in H2O2 (35%,
50 mL). The sonication treatment was performed using
an ultrasonic probe (20 kHz, 43 lm amplitude, 19 mm
diameter, 350 W electrical power, Sonics and Materials
Ultrasonic Processor - VC505) dipped into the carbon
suspension, maintained at 298 K in a cylindrical dou-
bled-jacket cooled reactor.
All the oxidized samples were then recovered by
filtration at 0.45 lm on membrane filters (Durapore�-
Millipore), rinsed with distilled water until reaching a
neutral pH (1 L per g) and further dried at 353 K for 24 h.
The bleached AC was named AC[NaOCl]. The samples
oxidized with H2O2, and sonicated in H2O2 were
referred to AC[H2O2] and AC[H2O2]US, respectively.
(3) Sample named AC700N2 was prepared by heating at
973 K (10 K min�1, 1 h at 973 K), under a nitrogen flow
and kept under this inert atmosphere until cooling to
room temperature.
2.3. N2 adsorption–desorption at 77 K and CO2 adsorptionat 273 K
N2 adsorption–desorption isotherms of the activated carbons
were measured using an automatic sorptometer (ASAP 2020,
Micromeritics) at 77 K. The CO2 adsorption isotherms were
measured at 273 K on two samples (AC and AC loaded with
56.7 mg g�1 IBP at pH 7). Prior to measurements, samples (ex-
cept IBP loaded AC) were degassed for 12 h at 523 K under vac-
uum. IBP loaded AC was outgassed for 4 days at 323 K, below
ibuprofen melting point (348–350 K) [39].
The specific surface areas of the activated carbons were
calculated using the Brunauer–Emmett–Teller (BET) equation,
assuming the area of the nitrogen molecule to be 0.162 nm2.
As negative unrealistic C factors were obtained by applying
the BET model in the relative pressure range from 0.05 to
0.3, the BET specific surface areas were then preferentiallyFig. 1 – Molecular structure of Ibuprofen.
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computed in the relative pressure range from 0.01 to 0.05, as
for microporous materials.
The total pore volume was estimated as the liquid vol-
ume of N2 adsorbed at a relative pressure of 0.995. In addi-
tion, the micropore volume was determined by using the
Dubinin-Radushkevich equation for N2 adsorption (P/P0
from 0.01 to 0.05) and for CO2 adsorption [40]. The meso-
pore volume was calculated by difference of the total pore
volume and the micropore volume. The pore size distribu-
tions (PSD) of the pristine AC and IBP loaded AC (pH = 7
and 56.7 mg g�1 of IBP) were determined by using NLDFT
(non local density functional theory) models applied on
both the adsorption isotherms of N2 at 77 K and CO2 at
273 K. For that, infinite slit pores were assumed for CO2
adsorption (pores diameter from 0.35 to 1.1 nm), while finite
slit pores having a diameter-to-width aspect ratio of 12
were used for N2 adsorption simulations (pores diameter
from 3.5 to 250 A) [41]. N2 adsorption data at P/P0 < 0.01
were obtained using incremental fixed doses of �10 cm3 g�1
(STP), setting the equilibration interval at 300 s [42]. CO2
adsorption data were obtained at P/P0 ranging from
4 · 10�4 and 3.5 · 10�2, using 45 s equilibration interval.
2.4. pHs of carbons suspended in water
The pH of each activated carbon sample (0.5 g) was measured
in a distilled water suspension (12.5 mL) after heating at 90 �Cand then cooling to room temperature [43].
The pHPZC (pH value at which the surface has a zero net
charge) was determined by the so-called pH drift method
[34]. The pH of deoxygenized NaCl aqueous solutions (50 mL
at 0.01 mol L�1) were adjusted to successive initial values be-
tween 2 and 12 by adding either 0.1 mol L�1 HCl or NaOH. Sus-
pensions were prepared by adding activated carbon (0.15 g) to
each solution. After stirring for 48 h under N2, the final pH
was measured and plotted versus the initial pH. The pHPZC
was determined at the value for which pHfinal = pHinitial.
2.5. Boehm titrations
Boehm titrations quantify the basic and oxygenated acid sur-
face groups on activated carbons [44]. Surface functional
groups such as carboxyl (R–COOH), lactone (R–OCO), phenol
(Ar–OH), carbonyl or quinone (RR 0C@O) and basic groups were
determined using different reactants, assuming that: NaOC2-
H5 reacted with all groups; NaOH did not react with RR 0C@O
groups; Na2CO3 did not react with RR 0C@O nor R–OH groups
and that NaHCO3 only reacted with R–COOH groups. The pro-
cedure was as follows: about 0.15 g of each carbon sample
was mixed in a closed erlenmeyer with 50 mL of a 0.1 mol L�1
aqueous reactant solution (NaOH, Na2CO3 or NaHCO3). In the
case of NaOC2H5, only 0.1 g of carbon sample was added to
50 mL of 0.01 mol L�1 solutions. The mixtures were stirred
for 24 h at constant speed (650 rpm) and room temperature
and then filtered off. Back-titrations of the filtrate (10 mL)
were then achieved with standard HCl (0.01 mol L�1) to deter-
mine the oxygenated groups contents. Basic groups contents
were also determined by back titration of the filtrate with
NaOH (0.01 mol L�1) after stirring of the activated carbon
(0.15 g) in HCl (50 mL, 0.01 mol L�1) for 24 h.
2.6. X-ray photoelectron spectroscopy
X-ray photoelectron spectroscopy (XPS) measurements were
performed using an ESCALAB 250 spectrometer (Thermo Fish-
er Scientific) at monochromated Al-Ka anode X-ray radiation,
on a 150 · 800 lm2 analysis region, under 2 · 10�9 mbar vac-
uum. The high-resolution scans (0.1 eV) were obtained over
the 280.1–299.9 eV (C1s) and 523.1–539.9 eV (O1s) energy
ranges with a pass energy of 20 eV. After baseline subtraction,
the curve fitting was performed assuming a mixed Gaussian–
Lorentzian peak shape (the ratio of Gaussian to Lorentzian
form was equal to 0.3). The carbon 1s electron binding energy
corresponding to graphitic carbon was referenced at 284.6 eV
for the calibration [45].
2.7. Adsorption experiments: kinetics and isotherms
The IBP solutions were prepared from UHQ water (Ultra High
Quality, 18.2 MX purity) containing 10 vol.% of methanol
(99.9%, Sigma–Aldrich) in order to increase the solubility.
The kinetics were studied at room temperature at pH 3 and
7. Suspensions of 10 mg of the differently treated ACs in
30 mL of 100 ppm IBP solution were put to stirring at
650 rpm and then filtered at different intervals between
15 min and 7 days. The IBP concentrations were subsequently
determined by UV–visible spectrometry (Varian, Cary50). The
maximum absorbance was observed at 220 nm at pH = 3, and
222 nm at pH = 7.
The isotherms of adsorption of IBP on the various acti-
vated carbons were studied at three constant temperatures:
298, 313 and 328 K, at pH 3 and 7. Activated carbons (10 mg)
were introduced in IBP solutions (30 mL) of varying concentra-
tions (5–100 mg L�1) and stirred for 5 days.
The equilibrium IBP uptake Qads (mg g�1) was calculated
from equation:
Qads ¼ðCe � CiÞ � V
m
where V is the solution volume (mL), Ci is the initial IBP con-
centration (mg L�1), Ce is the equilibrium IBP concentration
(mg L�1) and m is the weight of the dry activated carbon (mg).
3. Results and discussion
3.1. Characterization of activated carbons
3.1.1. Surface chemistryThe Boehm titrations of AC revealed the overall presence of
more basic than acidic functional groups (Table 1), confirmed
by the pH value (9.05). When AC was oxidized respectively by
NaOCl or by H2O2 with and without ultrasonic irradiation, the
pH values decreased due to the increase of the oxygenated
surface groups concentrations from 0.37 to �2.1, 3.9 and
3.5 meq g�1. The value of pHPZC slightly decreased for the
bleached activated carbon (from 7.76 to 7.60) but increased
for both AC[H2O2] and AC[H2O2]US (Table 1). This slight in-
crease in pHPZC could be attributed to the higher amount of
carbonyl groups (2.10 and 2.25 meq g�1 for AC[H2O2] and
AC[H2O2]US, respectively) and lactonic groups (0.77 and
1.32 meq g�1 for AC[H2O2] and AC[H2O2]US, respectively)
434 C A R B O N 5 4 ( 2 0 1 3 ) 4 3 2 – 4 4 3
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which possess high pKa values (pKa-carbonyl �16–20, pKa-
lactonic �8.2).
The oxidation by ultrasonic irradiation in H2O2 (AC[H2O2]-
US sample) compared to the silent analog (AC[H2O2] sample)
yielded to a slight decrease of the carbonyl groups. By con-
trast, additional phenolic groups (0.27 meq g�1) were found
under ultrasound irradiation, whose origin can be attributed
to the reaction between atoms of carbon and free OH� radicals
generated by the sonolytic degradation of H2O2 [46]. Ultra-
sonic and silent treatments with hydrogen peroxide gener-
ated the highest contents in carbonyl and lactonic groups
(Table 1) while the bleaching treatment yielded to the highest
amount of phenolic groups (0.5 meq g�1). The carbonyl and
lactonic contents were lower in bleached samples
(�1 meq g�1) than in samples treated with H2O2 (>2 meq g�1).
The ultrasonic treatment also induced a significant particle
size reduction due to the cavitation phenomenon [47]. Laser
granulometry characterization (not shown) confirmed that
AC[H2O2]US was mainly formed of submicrometric particles
(median size d50 = 1 lm) while oxidation in H2O2 without
ultrasound preserved the micrometric particles
(d50 = 100 lm), such as for the raw AC (d50 = 700 lm).
Boehm titrations (Table 1) revealed quite different surface
groups contents for a ‘‘fresh’’ sample characterized just after
annealing under N2 atmosphere, in comparison to a one-year
air atmosphere aged sample. The ‘‘fresh’’ AC700N2 sample
was found to be the most basic sample, which is in agreement
with its measured pH and pHPZC values. Although the anneal-
ing under N2 atmosphere removed many oxygen surface
groups, the sample underwent again oxidation with time
when exposed to air atmosphere (Table 1), leading to a similar
carbonyl content (�1 meq g�1) than the bleached sample. In
fact, a N2 thermal treatment is known to be only temporarily
efficient for removing the oxygen containing surface groups,
as it also generates very reactive surface sites that further re-
act with oxygen from air, enabling the formation of new oxy-
genated surface groups [48].
Surface chemical groups of the different activated carbons
were also characterized by XPS. Fig. 2 presents the O1s spec-
trum of the raw and treated activated carbons. Deconvolution
of the C1s and O1s spectra gave respectively five and four
peaks (Table 2).
XPS analysis of the aged AC700N2 sample confirmed a
slight oxidation compared to raw AC, through C1s spectrum
deconvolution and brought out the highest content in ad-
sorbed O detected by XPS (Table 2).
Whatever the oxidized activated carbons, their contents in
graphitic carbon (at 284.6 eV) were lower than in pristine AC,
and the percentages of oxygen bonded to carbon increased
after oxidation (Table 2), in agreement with the Boehm
titrations.
The C1s spectra (Table 2) displayed higher carbonyl (or qui-
none) and carboxylic (or ester or lactone) groups contents in
AC[H2O2] (8.05% of C@O group; 5.82% of O–C@O groups) and
AC[H2O2]US (9.82% of C@O group; 7.69% of O–C@O groups)
compared to the bleached AC[NaOCl] sample (4.45% of O–
C@O, and 7.02% of C@O), for which the levels were quite sim-
ilar to the AC sample. By contrast, Cagnon et al. [49] reported
an increase in carboxylic and carbonyl groups XPS contents
after bleaching treatment of an activated carbon but without
mentioning the used concentration of NaOCl. Perrad et al. [50]
also showed by XPS an increase in the formation of carboxylic
groups after oxidation of an activated carbon cloth by NaOCl
(0.53 M) for 90 min.
XPS O1s (Fig. 2) analyses confirmed that oxidation was
more efficient under ultrasonic irradiation in hydrogen
Table 1 – Surface groups (in meq g�1) obtained from ‘‘Boehm’’ titrations, pH and pHPZC values of raw and modified activatedcarbons.
Sample AC AC[NaOCl] AC[H2O2] AC[H2O2]US AC700N2a AC700N2
b
Carboxylic groups 0 0.15 0.32 0.37 0 0Lactonic groups 0.03 0.35 1.32 0.77 0 0.23Phenolic groups 0.10 0.50 0 0.27 0 0.03Carbonyl groups 0.24 1.08 2.25 2.10 0.10 1.02Total oxygenated groups 0.37 2.08 3.89 3.51 0.10 1.28Total basic groups 0.99 0.99 0.65 0.62 1.14 0.77pH 9.05 7.18 8.38 8.03 10.14 8.74pHPZC 7.76 7.60 7.80 8.03 9.08 8.44a Fresh AC700N2.b Aged AC700N2.
Fig. 2 – O1s XPS spectra of raw and modified activated
carbons.
C A R B O N 5 4 ( 2 0 1 3 ) 4 3 2 – 4 4 3 435
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peroxide (14.37 at.0% in sample AC[H2O2]US) compared to the
silent analog reaction (11.97 at.0% in sample AC[H2O2]).
XPS analyses (Table 1), indicated higher carbonyl and lac-
tonic groups amount in AC[H2O2]US compared to AC[H2O2],
disagreeing with the contents determined by Boehm titra-
tions that are known to be only semi-quantitative.
After NaOCl treatment, the increase of the number of C-O
bonds from phenols and lactones (16.77% of C–O for AC[NaO-
Cl] compared to 10.22% for AC) was consistent with the evolu-
tion observed by Boehm titrations.
Whatever the activated carbon, the O1s analyses (Table 2)
showed O–C at.% lower than the C–O content obtained from
the C1s spectra, which could be the signature of the presence
of ether bridges in all of the activated carbons.
The O1s analyses after deconvolution (Table 2) indicated
also O@C at.% lower than the C@O content obtained from
the C1s spectra, particularly for raw AC and samples treated
with H2O2 as already reported for other oxidized activated car-
bons [51,52]. This revealed the difficulties for XPS analysis to
take into account all the surface oxygen groups species in
particular ethers and anhydrides, etc.
The peak at the lowest energies (530.42–531.01 eV) related
to the presence of metal oxides, increased after oxidation by
H2O2. Indeed, the X-ray micro-analysis showed the presence
of metals, such as Al and Fe on the surface of AC which might
have formed metal oxides after their oxidation by hydrogen
peroxide.
3.1.2. Porosity characterizationThe nitrogen adsorption–desorption isotherms for the raw
(Fig. 3) and modified carbons are quite similar (not shown),
except for AC[NaOCl] sample (Fig. 3). They were typical of
microporous–mesoporous adsorbents (type I and IV in the IU-
PAC classification) with a hysteresis loop (H4 types) in the
desorption branch at relative pressures above 0.5. The adsorp-
tion–desorption hysteresis on AC isotherm showed clearly
that liquid nitrogen was condensed in slit-shaped mesopores.
The N2 isotherms at 77 K showed a slight decrease of the
BET surface area (Table 3, SBET = 709 m2 g�1 for AC[NaOCl],
781 m2 g�1 for AC[H2O2] and 762 m2 g�1 for AC[H2O2]US) of
the oxidized carbons compared to the pristine AC (SBET = 800 -
m2 g�1). The decrease in the specific surface areas after oxida-
tion was related only to the decrease in the micropore
volumes observed either by N2 or CO2 adsorption (Table 3).
This reduction after oxidation treatment was the highest for
the AC[NaOCl] sample. A blockage of the micropores due to
the formation of surface functional groups might be the cause
of this slight reduction in the surface area as already stated
before [53]. By contrast, the very small increase in the BET
specific area (SBET = 809 m2 g�1) and in the micropore volume
(0.32 cm3 g�1) for AC700N2 compared to raw AC, might be
attributed to the removal of the functional groups from the
inner pores through the thermal treatment (Table 1).
The ultramicropore volumes obtained from the DFT PSD
analysis of CO2 isotherms (Table 3) were found quite similar
(about 0.14 cm3 g�1) for all the modified activated carbons
and slightly lower than to the one of AC (0.18 cm3 g�1).
The N2 DFT pore size distribution of the pristine AC (not
shown) confirmed that the AC material was both of micropo-
rous and mesoporous nature. The micropore and mesopore
volumes computed from the N2 DFT model were 0.31 and
0.21 cm3 g�1, respectively.
The N2 adsorption–desorption isotherm of raw AC and IBP-
loaded AC (Fig. 4 left) had a very similar profile but the iso-
therm of the loaded sample was shifted towards lower
adsorption volumes. This difference is due to a decrease of
the microporous volume concomitant to IBP adsorption. The
volume occupied by IBP calculated from loading content:
0.05 cm3 g�1 was similar than to the volume calculated from
the difference of microporous volumes before after loading
(0.05 cm3 g�1 from N2 adsorption) (Table 3). An activated car-
bon (AC or treated AC) saturated by IBP at pH 3, where the up-
Table 2 – Atomic percentages of carbon (C1s) and oxygen (O1s) obtained by XPS analysis of raw and modified AC.
Signal attribution E(eV) AC AC[NaOCl] AC[H2O2] AC[H2O2]US AC700N2
C1s C–C (284.6) 62.04 53.02 51.77 46.74 54.74C–O (285.13–285.55) 10.22 16.77 12.07 18.84 11.57C@O (285.99–286.75) 6.50 7.02 8.05 9.82 7.21O–C@O (286.83–289.14) 4.44 4.45 5.82 7.69 4.98Carbonate, p–p transition (288.57–291.48) 9.92 6.49 10.38 2.53 10.51
O1s Metal oxide (530.42–531.01) 0.85 0.83 2.31 2.48 1.02O@C (531.8–532.29) 1.89 6.28 3.51 5.40 4.91O–C (532.96–533.77) 2.87 4.63 3.93 5.71 2.40Chemisorbed O (534.7–535.22) 1.27 0.51 2.16 0.78 2.67
Total atomic O% 6.88 12.25 11.91 14.37 11
0
50
100
150
200
250
300
350
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1P/P0
Vads
(cm
3 g-1
STP)
Fig. 3 – N2 adsorption–desorption isotherms at 77 K of the
pristine AC (h: adsorption, j: desorption) and AC[NaOCl] (4:
adsorption, m: desorption).
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take is maximum, contains 130–165 mg g�1 of adsorbate,
which means a volume of 0.11 cm3 g�1 for the uptake volume
of IBP (taking into account the volume of IBP : 0.23 nm3 men-
tioned in Section 2.1). As the IBP uptake volume is lower than
the microporous volumes of the studied activated carbons,
this molecule can be accommodated in the micropores (Vol-
ume of micropores �0.31 cm3 g�1 for AC). The ultramicropore
volume values, investigated by CO2 adsorption before and
after loading (Table 3), have confirmed that these smaller
micropores were occupied by IBP (IBP uptake volume deduced
from ultramicropore volumes: 0.06 cm3 g�1). The PSD plots of
pristine AC and IBP-loaded AC (Fig. 4 right) clearly displayed
that the adsorption occurred in the ultramicropores of diam-
eter lower than�0.6 nm. Similarly we have studied the micro-
porosity of a IBP-loaded AC700N2 by CO2 adsorption (Volume
of ultramicropores �0.09 cm3 g�1 for IBP-loaded AC700N2),
and we have confirmed that IBP was also adsorbed into ultra-
micropores. Mestre et al. [14] studied a series of activated car-
bons with various surface chemistry and showed that a large
fraction of ultramicropores were not appropriate to effectively
remove ibuprofen. In our activated carbon, IBP is preferen-
tially adsorbed in the slit shape ultramicropores which are
accessible to the molecule in terms of dimensions.
3.2. Adsorption kinetics of raw activated carbon
Fig. 5 shows the effect of contact time on the adsorption of IBP
onto AC. The equilibrium adsorption time was found at about
4000 min. The kinetics of adsorption of IBP by AC was
investigated by four models, namely, the Lagergren pseudo-
first-order model (1) [54], the pseudo-second-order model (2)
[55], the Elovich model (3) [56] and the intraparticle diffusion
model (4) [57].
The first-order equation is:
dqt
dt¼ k1ðqe � qtÞ ð1Þ
where k1 is the rate constant of pseudo-first-order adsorption
(min�1), qe and qt (mg g�1) are the amounts of adsorbed IBP at
equilibrium and at time t (min), respectively.
The second-order equation is:
dqt
dt¼ k2ðqe � qtÞ
2 ð2Þ
where k2 is the rate constant of pseudo-second-order adsorp-
tion (g mg�1 min�1), qe and qt (mg g�1) are the amounts of ad-
sorbed IBP at equilibrium and at time t (min), respectively.
Table 3 – Textural properties obtained by N2 adsorption/desorption and CO2 adsorption studies.
Sample AC AC[NaOCl] AC[H2O2] AC[H2O2]US AC700N2 IBP loaded AC
BET surface area SBET (m2 g�1) 800 709 781 762 809 655Micropore volumea (N2) (cm3 g�1) 0.31 0.28 0.31 0.30 0.32 0.26Mesoporous volume (cm3 g�1) 0.21 0.21 0.25 0.25 0.23 0.22Total pore volumeb (cm3 g�1) 0.52 0.49 0.56 0.55 0.55 0.48Micropore volumea (CO2) (cm3 g�1) 0.27 0.23 0.26 0.25 0.27 0.18Ultramicropore volumec (CO2) (cm3 g�1) 0.18 0.14 0.14 0.14 0.15 0.12a From Dubinin-Radushkevich.b Single point adsorption at P/P0 = 0.995.c From NLDFT slit pore model.
Isotherms
0
50
100
150
200
250
300
350
400
0.000001 0.00001 0.0001 0.001 0.01 0.1 1P/P0
Vads
(cm
3 g-1
STP)
PSD
0
0.01
0.02
0.03
0.04
0.05
0.06
3 5 7 9Pore width (Å)
Incr
emen
tal v
olum
e (c
m3 g-1
)
Fig. 4 – Adsorption isotherms of N2 at 77 K (s: AC, h: 56.7 mg g�1 IBP loaded AC at pH 7), and of CO2 at 273 K (4: AC, �: IBP
loaded AC), and NLDFT pore size distributions of AC (4) and IBP loaded AC (�), from CO2 isotherms.
00.10.20.30.40.50.60.70.80.9
1
0 1000 2000 3000 4000 5000 6000Time (min)
C/C0
Fig. 5 – Kinetic result of Ibuprofen adsorption onto AC at
25 �C and pH 3 ([IBP] = 100 mg L�1, madsorbent = 10 mg,
VIBP = 30 mL, stirring speed = 650 rpm).
C A R B O N 5 4 ( 2 0 1 3 ) 4 3 2 – 4 4 3 437
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The Elovich equation is:
qt ¼ 1b
lnða� bÞ þ 1b
lnðtþ t0Þ ð3Þ
where a is the adsorption initial rate (mg g�1 min�1, t0 = 1/
(a · b)) and b is a constant (g mg�1) related to the external sur-
face area and activation energy of adsorption
(chemisorption).
The intraparticle diffusion model is formulated by:
qt � kpt0:5 ð4Þ
where kp (mg g�1 min�1/2) is the intraparticle diffusion rate
constant.
The fitted parameters of adsorption kinetics at pH 7 and 3
(Table 4) were calculated from the non linear regressions of
the integrated Eqs. (1)–(3). The profiles of each fitted curve dis-
played in Fig. 6, in comparison with the experimental kinetics
at pH 3, were very similar to the ones of fitted kinetic plots at
pH 7 (not shown). Whatever the pH value, the intraparticle
diffusion model (Fig. 6) was not in good agreement with the
experimental kinetics. The best fit of adsorption kinetics at
pH 3 (R2 = 0.985) was obtained for the pseudo-second-order
model. The IBP uptake decreased while the pH increased from
3 to 7. The pseudo-second-order constant k2 obtained at
pH = 7 was higher than at pH = 3 meaning that the IBP adsorp-
tion at pH = 7 required higher amount of AC than at pH = 3. As
a consequence, activated carbon AC has more affinity for IBP
at acidic pH. On the other hand, the Elovich model showed a
satisfactory correlation coefficient (R2 = 0.982 at pH = 3). Thus,
both pseudo-second-order and Elovich models are applicable
to reproduce the adsorption kinetics of IBP on AC at pH = 3.
Besides, the Elovich model was found to be the best model
at pH = 7 (R2 = 0.997). The adsorption initial rate of ibuprofen
(a) decreased as the pH of the ibuprofen solution became ba-
sic. The value of 1/b, indicative of the number of sites avail-
able for adsorption, was higher at pH = 3 (1/b � 11) than at
pH = 7 (1/b � 5).
3.3. Adsorption isotherms
3.3.1. Effect of pHpH remains one of the most important factors controlling the
adsorption capacity of activated carbons, by influencing both
the chemistry of the surface groups and the IBP charge (pKa of
IBP equals to 4.91 [58]). Its impact was subsequently studied at
pH � pKa-2 and pH � pKa+2 (i.e. pH = 3 and 7). For pH values
higher than pKa(IBP), the molecule was present under its an-
ionic form. The pHPZC of AC was equal to 7.76 (Table 1). At
pH < pHPZC, the activated carbon was positively charged.
Thus, at pH = 7, the negatively charged IBP species were at-
tracted by the positive AC surface (electrostatic interactions),
which was not the case at pH = 3. At such a value, the surface
of AC remained positively charged (pH < pHPZC) whereas IBP
moieties existed under their neutral form disabling the favor-
able electrostatic interactions between both. However, the
dominant dispersive interactions explained the higher
adsorption capacity at this low pH. Indeed, the uptake of
IBP by AC was found higher at pH = 3 (Fig. 7, qmax = 130 -
mg g�1) than at pH = 7 (Fig. 7, qmax = 75 mg g�1).
Whatever the explored pH, adsorption capacities of the
raw and the modified carbons were different. As the studied
carbons probed by N2 adsorption at 77 K and CO2 adsorption
at 273 K were very similar in term of microporous and ultra-
microporous accessible volumes (Section 3.1.2, Table 3), nota-
bly lower than the uptake volume of IBP (0.11 cm3 g�1,
Section 3.1.2); the difference in uptakes of the various carbons
can only be attributed to the variety of their surface
chemistry.
While the bleaching treatment led to a decrease of the
adsorption uptake at pH = 7, the latter increased with the oxi-
dative treatment by H2O2 with or without ultrasound (Fig. 7).
In addition, IBP adsorption is claimed to operate mainly
through interactions with the p-electron system of the
Table 4 – Results of the best IBP kinetic fittings (R-square correlation coefficient > 0.91) for AC sample (pseudo-first order,pseudo-second order and Elovich models).
Kinetic model Parameters pH = 3 pH = 7
Pseudo-first-order qe (mg g�1) 132.90 67.14k1 (min�1) 0.087 0.121R2 0.949 0.912
Pseudo-second-order qe (mg g�1) 138.10 69.75k2 (mg g�1 min�1) 0.000436 0.001147R2 0.985 0.952
Elovich a (mg g�1 min�1) 2148 1492b (g mg�1) 0.092 0.183R2 0.982 0.997
0
20
40
60
80
100
120
140
160
180
0 1000 2000 3000 4000 5000 6000
Time (min)
Ibup
rofe
n up
take
(mg
g-1
)
AC at pH=3
pseudo 1storderpseudo 2ndorderIntraparticlediffusionElovich
Fig. 6 – Fitted profiles of ibuprofen adsorption kinetics of AC
sample at pH 3 (�) by pseudo-first-order, pseudo-second
order, Elovich and intraparticle diffusion models.
438 C A R B O N 5 4 ( 2 0 1 3 ) 4 3 2 – 4 4 3
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graphitic rings. One thus would expect that additional acidic
surface oxygen groups might have withdrawn the electrons
from the p-system. However, this explanation is not fully sat-
isfactory here as the oxidation by H2O2 treatment led to an in-
crease in the adsorption uptake.
Indeed, the knee of the adsorption isotherm of AC[H2O2]US
was more pronounced compared to any other samples indi-
cating that strong interactions with this sample occurred
even at low concentration. As both XPS characterization and
Boehm titrations (Section 3.1.1) showed that the main differ-
ence in terms of resulting surface chemistry, between the
H2O2 and NaOCl oxidation treatments, laid in the amount of
carbonyl and lactonic groups; the higher IBP uptake could
be thus related to the higher amount of carbonyl (also from
quinones) and lactonic groups, created after H2O2 oxidation.
These carbonyl groups could have interacted with the aro-
matic ring of ibuprofen in a donor–acceptor bond as previ-
ously reported [40]. In fact, the oxygen lone pair electrons
are known to be responsible of the formation of donor–accep-
tor complexes via a dipole moment interaction; the carbonyl
groups acting as the electron donor and the aromatic ring act-
ing as the acceptor. As the carbonyl oxygen groups have more
intense dipole moments than carboxylic acid oxygen’s, they
have been reported as stronger donors [33]. In their molecular
form, the carboxylic acid could also interact in a different
manner by Van der Waals, hydrogen bonds with the carbox-
ylic groups of IBP, enabling the formations of dimers [34].
The functionalization of activated carbons by oxidation with
NaOCl yielded to specific oxygen surface groups (mainly phe-
nolic). Some of these groups might be inappropriate for ben-
eficial interaction with IPB, leading to a decrease of the
dispersive interactions, through decreasing the p-electron
density of the graphene layers [59]. Thus the uptake of
AC[NaOCl] remained rather similar to AC at pH 3 and lower
at pH 7.
A significant increase of the adsorption capacity compared
to AC was observed for AC700N2 ‘‘aged’’ sample: the uptake,
equal to 92 mg g�1 at pH = 7, reached a maximum of
160 mg g�1 at pH = 3, showing that the adsorption was also
promoted on slightly oxidized activated carbons. Moreover,
at pH 7, the electrostatic attraction contribution might in-
crease slightly in the AC700N2 sample due to the shift of
pHPZC towards basic values (pHPZC of AC700N2 equals to
9.08). At pH 3, the increase in adsorption uptake for
AC700N2, was attributed to beneficial interactions of IBP with
the oxygenated surface groups (mainly carbonyl groups).
3.3.2. Effect of temperatureThe effect of temperature was studied at pH 3 in order to
determine the thermodynamic parameters of adsorption of
IBP on three different activated carbons (Figs. 8–10: samples
AC, AC[H2O2]US and AC700N2, respectively) and to compare
the interactions energies.
As the temperature increased from 298 to 328 K, the
adsorption capacities increased from 130 to 180 mg g�1 for
AC (Fig. 8), from 140 to 160 mg g�1 for AC[H2O2]US (Fig. 9)
and from 163 to 230 mg g�1 for AC700N2 (Fig. 10).
To investigate the temperature dependency of the adsorp-
tion capacity, four equilibrium models were analyzed, including
Langmuir, Freundlich, Langmuir–Freundlich and Redlich–
Peterson. All the isotherms were simulated using an iterative
0
50
100
150
200
250
0 20 40 60 80 100Ce (mg L-1)
Qad
s(m
g g-1
)
Fig. 8 – Experimental adsorption isotherms of ibuprofen on
AC at pH 3, and at 298 K (�), 313 K (m) and 328 K (j) fitted by
the Langmuir–Freundlich model (lines).
pH=7
0
20
40
60
80
100
120
140
160
180
0 20 40 60 80Equilibrium solution concentration (mg/L)
Ibup
rofe
n up
take
(mg/
g)
pH=3
0
20
40
60
80
100
120
140
160
180
0 20 40 60 80Equilibrium solution concentration (mg/L)
Ibup
rofe
n up
take
(mg/
g)
Fig. 7 – Adsorption isotherms of ibuprofen at 25 �C onto raw and modified activated carbons (�: AC, d: AC[H2O2], j:
AC[H2O2]US, *: AC[NaOCl] and m: AC700N2) at pH 3 and 7 ([IBP] = 5–100 mg L�1, madsorbent = 10 mg, VIBP = 30 mL, contact
time = 5 days, stirring speed = 650 rpm).
C A R B O N 5 4 ( 2 0 1 3 ) 4 3 2 – 4 4 3 439
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procedure based on a non-linear least-squares algorithm. The
Langmuir adsorption isotherm equation, expressed as follows
requires for its applicability a mono-layered coverage on the
surface of adsorbent [60]:
qe ¼qmaxKLCe
ð1þ KLCeÞ
where qe, KL, qmax and Ce are the ibuprofen uptake at equilib-
rium (mg g�1), the Langmuir constant (L mg�1), the monolayer
adsorption capacity (mg g�1) and the solution concentration
at equilibrium (mg L�1), respectively.
The Freundlich equation is applicable for multi component
adsorption. The Freundlich isotherm is expressed by:
qe ¼ KF � C1=ne
where KF is the Freundlich constant (mg1-1/n L1/n g�1) and n is
the Freundlich exponent.
The Freundlich equation was successfully used to fit the
experimental data for many fluid–solid systems, but one of
the main drawbacks of this equation is that it doesn’t tend
to a limiting value while the equilibrium concentration in-
creases. The Langmuir–Freundlich equation is a way to over-
come this problem [61]. It is expressed as follows:
qe ¼qmaxKLCn
e
1þ KLCne
The Redlich–Peterson isotherm, proposed by considering
the limitations of Freundlich and Langmuir isotherms [62],
is given by:
qe ¼KRCe
1þ aRCbe
where KR (L g�1) and aR (L mg�1) are the Redlich–Peterson iso-
therm constants and b is the exponent, ranging between 0
and 1.
The experimental data of IBP adsorption on AC and modi-
fied carbons at pH 3 were well fitted by the Langmuir–Freund-
lich and Redlich–Peterson models. In terms of R2, the
Langmuir–Freundlich model provided better fitting
(R2 > 0.96). Figs. 8–10 present the fittings by the Langmuir–
Freundlich equation of isotherms at pH 3.
The estimated parameters for the Langmuir–Freundlich
model are reported in Table 5.
The adsorption capacities, qmax increased as temperature
increased for each carbon indicating an endothermic adsorp-
tion. The Langmuir–Freundlich constants KL were the highest
for AC[H2O2]US suggesting that this activated carbon has a
higher adsorption affinity to IBP than AC and AC700N2. Com-
petitive adsorption of water molecules and IBP might have
also occurred as the carbon became more hydrophilic upon
oxidation by H2O2 with ultrasonic irradiation [34]. Moreover,
as n value is near to unity for AC[H2O2]US, the adsorption pro-
cess of IBP rather follows the Langmuir model. The n increase
for AC and AC700N2 together with temperature suggested
that adsorption affinity of IBP for the substrates increased
as heating.
3.4. Thermodynamic parameters
The isosteric Gibbs free energy DG� of adsorption of IBP onto
three activated carbons (AC, AC[H2O2]US and AC700N2) was
calculated using the results obtained from the simulations
(Table 5) and the following equation:
LnðKdÞ ¼ LnðCa=CeÞ ¼ �DG�=RT
where Kd is the equilibrium constant, Ca is the amount of IBP
adsorbed at equilibrium (mg L�1), Ce is the concentration of
IBP remaining in the solution at equilibrium (mg L�1), T is
the solution temperature (K) and R is the perfect gas constant.
The isosteric enthalpy DH� and entropy DS� of adsorption
were also calculated from the slope and the intercept of the
plot of Ln(Kd) versus 1/T, respectively, using the equation:
DG� = DH � TDS�. Thermodynamic parameters were calcu-
lated for the adsorption of IBP onto raw and modified acti-
vated carbons at constant adsorption uptake value equal to
100 mg g�1 and at pH = 3 (Table 6).
At pH = 3, the adsorption capacity of IBP onto all studied
activated carbons increased as the temperature increased
from 298 K to 328 K, that was consistent with the positive val-
ues obtained for DH�. This suggested that the adsorption of
IBP by the three activated carbons was an endothermic pro-
cess at this pH in agreement with the work of Dubey et al.
[30] for the adsorption of IBP at natural pH on an activated
carbon prepared from Artemisia vulgaris. At pH 3, the esti-
mated values for DG� were �1.1, �7.3 and �4.5 kJ moL�1,
respectively for AC, AC[H2O2]US and AC700N2, indicating a
0
50
100
150
200
250
0 10 20 30 40 50 60 70 80Ce (mg L-1)
Qad
s(m
g g-1
)
Fig. 9 – Experimental adsorption isotherms of ibuprofen on
AC[H2O2]US at pH 3, and at 298 K (�), 313 K (m) and 328 K (j)
fitted by the Langmuir–Freundlich model (lines).
0
50
100
150
200
250
0 10 20 30 40 50 60 70 80Ce (mg L-1)
Qad
s(m
g g-1
)
Fig. 10 – Experimental adsorption isotherms of ibuprofen on
AC700N2 at pH 3, and at 298 K (�), 313 K (m) and 328 K (j)
fitted by the Langmuir–Freundlich model (lines).
440 C A R B O N 5 4 ( 2 0 1 3 ) 4 3 2 – 4 4 3
Author's personal copy
spontaneous physisorption process [63]. The DH� values were
less endothermic as increasing the amount of oxygenated
groups, suggesting an exothermic interaction of some of
them with IBP.
The positive values of DS� showed an increase of the disor-
der at the solid-solution interface, probably due to the desorp-
tion of solvent molecules (water and methanol) prior to IBP
adsorption. The positive values of DS� could indicate the com-
petitive adsorption between IBP and solvent molecules.
The highest absolute value of Gibbs energy (�7.3 kJ mol�1)
for the AC[H2O2]US sample suggested the presence of high en-
ergy adsorption sites related to particular oxygenated groups
formed by sonication in hydrogen peroxide. The characteriza-
tion of the surface chemistry suggested that these sites might
be carbonyl (or lactonic) groups mainly formed through
hydrogen peroxide oxidation. The increase in the adsorption
energy compared to pristine AC (�4.5 kJ mol�1 compared to
�1.1 kJ mol�1) was also observed for ‘‘aged’’ AC700N2, maybe
through the interaction with quite similar beneficial oxygen-
ated groups, but in a lower amount.
4. Conclusion
We showed that the adsorption of ibuprofen occurred prefer-
entially into the ultramicropores of the raw and N2 heat trea-
ted activated carbons. The adsorption of IBP is strongly
dependent on pH and is promoted by dominant dispersive
interactions which are increasing when the molecule is pres-
ent on its neutral form. For this reason at pH 7, as the electro-
static interaction predominates, the adsorption uptake
subsequently decreases compared to pH 3 where the adsorp-
tion was found endothermic and entropically promoted as
the competition with solvent molecules occurs. We brought
out that some particular surface chemistry nature, such as
carbonyl or lactonic or quinone groups can influence posi-
tively the adsorption uptake of IBP.
As an example, oxidation treatment in hydrogen perox-
ide combined or not with ultrasonic irradiation enables
increasing slightly the adsorption capacity, and the Gibbs
energy of adsorption at acidic pH. This might be attributed
to a donor–acceptor mechanism between the created car-
bonyl groups (also in lactonic and carboxylic groups) and
the p aromatic ring of ibuprofen. Both appropriate oxidation
or reduction treatments can increase the adsorption uptake,
but the reduction of the surface functionality (by annealing
at 973 K under N2) also gives a higher adsorption capacity
whatever the pH value as the carbon becomes slightly oxi-
dized after aging, favoring dispersive interactions. However
treatment with NaOCl does not benefit to ibuprofen uptake
because it preferentially leads to the formation of phenolic
groups and a lack of carbonyl adsorption sites [32]. The
Langmuir–Freundlich model allows describing well the ibu-
profen adsorption at pH 3. DH� values indicate that the
adsorption of ibuprofen on the studied activated carbons
is an endothermic process, in relation with solvent
interaction.
Acknowledgments
Generous MIRA grant of the ‘‘Region Rhone-Alpes’’ (France) is
thankfully acknowledged.
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