Journal of Colloid and Interface Science 368 (2012) 540–546

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Adsorption and removal of tetracycline antibiotics from aqueous solution

by graphene oxide
Yuan Gao a, Yan Li a, Liang Zhang b, Hui Huang a, Junjie Hu a, Syed Mazhar Shah a, Xingguang Su a,⇑
a
Department of Analytical Chemistry, College of Chemistry, Jilin University, Changchun 130012, China
b
State Key Lab. of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China

a r t i c l e i n f o a b s t r a c t

Article history: Significant concerns have been raised over pollution of antibiotics including tetracyclines in aquatic envi-
Received 21 September 2011 ronments in recent years. Graphene oxide (GO) is a potential effective absorbent for tetracycline antibi-
Accepted 8 November 2011 otics and can be used to remove them from aqueous solution. Tetracycline strongly deposited on the GO
Available online 15 November 2011
surface via p–p interaction and cation–p bonding. The adsorption isotherm fits Langmuir and Temkin
models well, and the theoretical maximum of adsorption capacity calculated by Langmuir model is
Keywords: 313 mg g1, which is approximately in a close agreement with the measured data. The kinetics of adsorp-
Graphene oxide
tion fits pseudo-second-order model perfectly, and it has a better rate constant of sorption (k),
Tetracycline
Antibiotics
0.065 g mg1 h1, than other adsorbents. The adsorption capacities of tetracycline on GO decreased with
Adsorption the increase in pH or Na+ concentration. The adsorption isotherms of oxytetracycline and doxycycline on
GO were discussed and compared.
Crown Copyright Ó 2011 Published by Elsevier Inc. All rights reserved.

1. Introduction coal humic acid [7], activated carbon [17], single-walled carbon
nanotubes, and multiwalled carbon nanotubes [3]. However, there
Pharmaceutical antibiotics, which are used extensively world- is still an increasing demand for the development of efficient and
wide in human therapy and the farming industry, have attracted cost-effective treatment technologies for the removal of such
increasing concern in recent years, because they have been proved pollutants.
to be a class of potent pollutants [1,2]. Since most antibiotics Graphene, a novel two-dimensional carbon nanomaterial as
including tetracyclines are poorly metabolized and absorbed by well as being a fundamental building block for buckyballs, carbon
the treated humans and animals, large fractions are excreted nanotubes, and graphite [18], has attracted a great deal of scientific
through urine and feces as unmodified parent compound [3–6]. interest in recent years. It is a two-dimensional structure com-
Residues of these antibiotics discharged from agricultural runoff posed of a single layer of sp2 network of carbon atoms [19]. Graph-
and municipal wastewater treatment plants are frequently ene oxide (GO), as a precursor for graphene preparation, is always
detected in soil, surface water, groundwater, and even drinking obtained through the strong oxidation of graphite by modified
water [3,7]. The widespread use of antibiotics has become a serious Hummer method. Large quantities of oxygen atoms are present
problem as it has a variety of potential adverse effects, including on the surface of the resulting GO in the forms of epoxy, hydroxyl,
acute and chronic toxicity, impact on aquatic photosynthetic and carboxyl groups. The presence of all these functional groups on
organisms, disruption of indigenous microbial populations, and the GO makes it extremely hydrophilic [20] and provides the capa-
dissemination into antibiotic-resistant genes among microorgan- bility to apply GO in the aquatic and biological environment. In the
isms [6–8]. Specifically, the tetracycline antibiotics, a group of past years, GO was applied for biosensors, catalysts, and drug
commonly used antibiotics, have been shown to disrupt microbial delivery. Due to its specific surface structure, it can also be used
soil respiration [9], Fe(III) reduction [10], nitrification [11], and as an adsorbent. The focus on the removal of toxic elements and
phosphatase activities [9]. The removal of pharmaceutical antibiot- compounds from contaminated water/environment by GO is
ics by conventional water and wastewater treatment technologies emerging. Seredych and Bandosz [21] investigated the removal of
is generally incomplete [4]. Scientists investigated the adsorption ammonia in gas by GO via its intercalation and reactive adsorption.
and removal of tetracycline antibiotics by several materials, Matsuo et al. [22] also reported the removal of formaldehyde from
including smectite clay [12], montmorillonite [5], rectorite [13], the gas phase at low concentration by silylated GO. The polypyr-
palygorskite [14], chitosan particles [15], aluminum oxide [16], role-reduced graphene oxide composite showed a highly selective
Hg2+ removal capacity [23]. Yang and coworkers demonstrated
⇑ Corresponding author. that GO has excellent Cu2+ absorption capacity and it is one of
E-mail address: [email protected] (X. Su). the most effective absorbents for Cu2+ removal [24]. Wang’s group

0021-9797/$ - see front matter Crown Copyright Ó 2011 Published by Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2011.11.015
 Y. Gao et al. / Journal of Colloid and Interface Science 368 (2012) 540–546 541

also used GO for the removal of methyl blue as a model of dye used. The FT-IR spectrum was recorded on a Nicolet 400 Fourier
pollutant [25]. Zhang et al. developed composites based on graph- transform infrared spectrometer. Atomic force microscopy (AFM)
ene oxide (GO) cross-linked with ferric hydroxide for the effective images were recorded using Multimode-V microscope (Veeco
removal of arsenate from contaminated drinking water [26]. The Metrology. Inc.) in contact mode. AFM samples were prepared by
emergence of graphene and its derivates provides an opportunity drop casting the GO suspension in water onto freshly cleaved mica
for the application of these novel materials in water treatment. surfaces and dried under room temperature. Raman spectra were
From earlier reported literatures, it is known that the aromatic obtained using a Renishaw 1000 model confocal microscope.
compound can easily adsorbed on GO and graphene by p–p stack- X-ray powder diffraction (XRD) patterns were recorded using a
ing. Tetracycline consists of four aromatic rings with various func- D/MAX-2550 diffractometer (Rigaku,
0
Japan), equipped with a Cu
tional groups on each ring, including phenol, alcohol, ketone, and Ka radiation source (k = 1.5418 Å
A).
amino. The preliminary study of tetracycline removal by Fe3O4–
rGO composites has been reported [27]. In the present work, GO 2.3. Synthesis of graphene oxide
suspension was used as the adsorbent to treat three representative
tetracycline antibiotics, including tetracycline, oxytetracycline, and GO was synthesized from graphite powder according to the
doxycycline, whose structures are shown in Fig. 1. The mecha- modified Hummer’s method [28,29]. Briefly, graphite powder
nisms for strong adsorption of these tetracycline antibiotics on (2 g) was added to a solution consisting of concentrated H2SO4
GO were deduced from fitting adsorption isotherms and by study- (12 mL), K2S2O8 (2.5 g), and P2O5 (2.5 g) at 80 °C and reacted for
ing the effect of pH and salt concentration. 4.5 h. The mixture was then diluted with 0.5 L water. Then, the
mixture was filtered and washed with water using a 0.2-lm Nylon
2. Experimental Millipore filter to remove the residual acid. The product was dried
under ambient conditions overnight. This pre-oxidized graphite
2.1. Materials was added to cold concentrated H2SO4 (120 mL) followed by the
gradual addition of KMnO4 (15 g) under stirring, and the tempera-
All chemicals used were of analytical reagent grade and used ture was kept below 20 °C by cooling. This mixture was stirred at
without further purification. Oxytetracycline, doxycycline hydro- 35 °C for 30 min and 90 °C for 90 min. Afterward, the mixture
chloride, and tetracycline hydrochloride were obtained from Gen- was diluted with water (250 mL) and kept at 105 °C for 25 min.
view Chemical Co. Graphite powder was purchased from After the resulting mixture was stirred for 2 h, 0.7 L of water and
Sinopharm Chemical Reagent Co. Ltd. (China). The water used in 20 mL of 30% H2O2 were added to end the reaction. For purification,
all experiments had a resistivity higher than 18 MX cm. the mixture was filtered and washed with 1:10 HCl aqueous solu-
tion and water many times. Finally, the product was further puri-
2.2. Instrumentation fied by dialysis for 1 week to remove the remaining metal
species. Exfoliation was carried out by sonicating graphite oxide
UV–vis absorption spectra were obtained using a Varian GBC under ambient condition for 20 min. The obtained dispersion was
Cintra10e UV–vis spectrometer. A 1-cm path-length quartz cuvette centrifuged at 3000 rpm to remove any unexfoliated GO and then
was used. Allegra 64R centrifuge from Beckman coulter Inc. was centrifuged at 16,000 rpm for 10 min to collect the residue for
absorption experiment. The residue was re-dispersed in water to
obtain 0.544 mg mL1 GO stock solution.

2.4. Adsorption and removal of tetracyclines by graphene oxide

suspension

Four hundred microliters of GO stock solution (pH 3.6) was sub-

jected to a given concentration of tetracycline solution (8.33–
333.33 mg L1) and then mixed thoroughly by a vortex mixer.
The suspension was incubated at 25 °C overnight and wrapped in
aluminum foil to avoid possible photodegradation of tetracycline.
After incubation, the suspension was centrifuged at 20,000 rpm
for 15 min. The supernatant was collected for determination by
UV–vis absorbance at 357.2 nm, using a calibration curve built
with tetracycline solutions of different concentrations. Unless
noted specifically, the following absorption experiments were per-
formed under the same condition. To investigate the kinetics of the
absorption, 4 mL GO (pH 3.6) was mixed with 8 mL of different ini-
tial concentration of tetracycline (8.33, 33.33, and 166.67 mg L1).
One thousand and two hundred microliter mixture was taken for
centrifugation with 15-min interval after vigorous mixing by vor-
tex mixture. The concentrations of tetracycline in supernatant
were determined successively. The influence of temperature on
the sorption of tetracycline by GO was evaluated by incubating
the samples under different temperature conditions (4 °C, 25 °C,
35 °C, and 45 °C) overnight. The temperature was kept through
the process of experiment including under centrifugation. To study
the effect of pH on adsorption, the initial pH of GO was adjusted
from 3 to 11 using NaOH or HCl aqueous solution, and then GO
Fig. 1. The structures and pKa value of tetracycline, oxytetracycline, and solution was incubated with tetracycline overnight. To study the
doxycycline. effect of salt concentration on adsorption, different amounts of
542 Y. Gao et al. / Journal of Colloid and Interface Science 368 (2012) 540–546

NaCl were dissolved in the mixture to get the Na+ concentration in adsorption isotherms decrease gradually. When initial concentra-
the range of 0–100 mmol L1. The adsorption isotherms of oxytet- tion is lower than 33.33 mg L1, the final equilibrium concentra-
racycline and doxycycline were plotted following the same opera- tion is lower than 9.54 mg L1 and the removal efficiencies are
tion as described above. higher than 71.4%. In the present work, the Langmuir, Freundlich,
and Temkin models, three classic adsorption models, were used
3. Results and discussion to describe the adsorption equilibrium. The mathematical repre-
sentations of the Langmuir, Freundlich, and Temkin models are
3.1. Characterization of graphene oxide given below
1 1 1
GO was prepared using modified Hummer’s method. AFM, TEM, ¼ þ ð1Þ
qe qm K L qm C e
FT-IR spectrum, and UV–vis spectrum were employed to character-
ize the prepared GO. GO was mostly single-layered with a topo- 1
graphic height of 1.198 nm after sonication for 30 min in water, ln qe ¼ ln K F þ ln C e ð2Þ
n
according to the atomic force microscopy (AFM) characterization
(Fig. S1.a). The TEM imaging was further used to characterize the qe ¼ K T ln C e þ K T ln f ð3Þ
graphene oxide, as shown in Fig. S1.b, and the prepared GO has
flake-like shapes. Fourier transform infrared (FTIR) spectrum where qm is the theoretical maximum adsorption capacity per unit
(Fig. S1.c) revealed the existence of OAH (3400 cm1), C@O weight of the adsorbent (mg g1), KL, KF, KT are adsorption constants
(1729 cm1), CAOH (1224 cm1), and CAO (1047 cm1) functional of Langmuir, Freundlich, and Temkin models, respectively, and n is
groups, suggesting that oxygen-containing groups are introduced the Freundlich linearity index. Langmuir model is an ideal model,
into the graphene. As shown in Fig. S1.d, the GO dispersion displays which possesses perfect adsorbent surface and monolayer molecule
a maximum absorption at 231 nm, which is due to the p–p tran- adsorption. As an empirical model, Freundlich model is used widely
sition of aromatic C@C bonds. Fig. S1.e is the XRD pattern of the in the field of chemistry. Temkin model is a proper model for the
prepared GO, which has a peak centered at 2h = 11.08°, corre- chemical adsorption based on strong electrostatic interaction
sponding to the (0 0 2) inter-planar spacing of 8.0 Å. In Fig. S1.f, between positive and negative charges [30].
the Raman spectrum showed a strong peak assigned to the vibra- The results of fitting these models are shown in Fig. 3b–d, and
tion of sp2-bonded carbon atoms at 1580 cm1 (G band) and other the fitting parameters for tetracycline are listed in Table 1. In the
strong peak assigned to the vibration of disordered sp3 carbon at range of tested concentration, the Langmuir (r2 = 0.992) and
1350 cm1 (D band). Temkin models (r2 = 0.986) fit the adsorption data well, while the
Freundlich model (r2 = 0.949) fits reasonably. Although the
Langmuir model globally fits well, it does not give apparently a
3.2. Adsorption isotherms of tetracycline on graphene oxide
nice fit at high concentration levels, showing the limitation of
the hypothesis about a monolayer adsorption. Considering the
The absorption spectra of GO, tetracycline, and GO with
Temkin model gives the best fitting at all tested concentration lev-
adsorbed tetracycline are shown in Fig. 2. It can be seen that the
els, we suspected that there was electrostatic interaction in the
spectrum of GO only has a strong adsorption at 231 nm, while it
process of adsorption. From Langmuir model, the ideal maximum
displays other adsorption peaks at 275 and 357 nm after the
adsorption capacity (qm) as a model fitting parameter was deter-
adsorption of tetracycline. The results illustrated that tetracycline
mined to be 313 mg g1. It was approximately in a close agreement
successfully adsorbed on GO surface. Adsorption isotherms for tet-
with the measured data (qm is 370 mg g1 at the Ce of 266 mg L1).
racycline with GO as adsorbent are presented in Fig. 3a. Ce (mg L1)
Using the Freundlich model, the obtained Freundlich constants (KF
denotes the equilibrium concentrations in aqueous phase after the
is 41.604 L mg1 and n is 2.346) were higher than those reported
adsorption of tetracycline on GO. The equilibrium adsorption
by Zhang (KF is 2.071 L mg1 and n is 0.993) [27], in which
capacity (qe, mg g1) of GO is the variation between initial (C0)
Fe3O4–rGO composites were used as adsorbent for tetracycline. It
and equilibrium concentration (Ce) caused by per unit weight of
is probably due to the difference in pH condition and the ratio of
the adsorbent, GO. In short, qe is calculated by (C0–Ce)/CGO. As
effective graphene surface in the per unit weight of adsorbent.
shown in Fig. 3a, adsorption capacities increase with the increase
The mechanism for strong adsorption of tetracyclines on graph-
in equilibrium concentration of adsorbates and the slopes of
ene oxide is not clear yet. p–p stacking interaction as a dominant
driving force has always been used to explain the mechanism of
aromatic adsorbate to graphene surface. As is well known, ssDNA
can be adsorbed by graphene oxide due to the p–p stacking inter-
action between the ring structure in the nucleobases and the hex-
agonal cells of the graphene oxide [31,32]. p–p interaction was
also found to be the dominating force for the deposition of porphy-
rin on the graphene oxide [33,34]. Considering here that four aro-
matic rings in the molecular structure of tetracyclines are present,
we suggested p–p interactions probably dominate the adsorption
of tetracyclines on graphene oxide. And the cation–p bonding
could also be responsible for adsorption. The cation–p bonding is
dominated by the cation-induced polarization and electrostatic
force between the cation and the permanent quadrupole of the
p-electron-rich aromatic structure [35]. Such bonding interactions
always take place between metal ions/protonated amino groups
and p-electron-rich structures. In previous studies, the cation–p
interactions are likely the reason for the enhanced uptake of PAHs
Fig. 2. The UV–vis absorption spectra of GO, tetracycline, and GO with adsorbed on the surfaces of bacteria, biopolymer (phospholipids), and clay,
tetracycline. respectively [3]. Tetracycline is almost in a cation form at low pH
 Y. Gao et al. / Journal of Colloid and Interface Science 368 (2012) 540–546 543

Fig. 3. Adsorption isotherms of tetracycline, oxytetracycline, and doxycycline on GO (a); Langmuir (b); Freundlich (c), and Temkin (d) model fitting for the adsorption of
tetracycline by GO. Experiment condition: pH 3.6; 25 °C; incubation for overnight; GO 0.181 mg mL1.

Table 1
Langmuir, Freundlich, and Temkin adsorption isotherms fitting parameters of tetracycline, oxytetracycline, and doxycycline on GO.

Langmuir Freundlich Temkin

qm (mg g1) KL (L mg1) r2 KF (L mg1) n r2 KT r2
Tetracycline 313.480 0.080 0.992 41.604 2.346 0.949 67.195 0.986
Oxytetracycline 212.314 0.349 0.864 46.498 2.385 0.995 68.904 0.865
Doxycycline 398.406 0.110 0.950 42.403 1.775 0.995 139.557 0.905

(pH < 4), in a zwitterion form in the pH range of 5–7, and in an an-
ionic form at high pH [36]. However, since all species of tetracy-
cline contain a positively charged group in their structure,
regardless of the zero net charge or negative net charge, it is likely
that the molecules arrange at the surface in such a way that the
positively charged group is located very close to the surface, lead-
ing to cation–p bonding [37]. In the present study, the cation–p
bonding may happen between the easily protonated amino group
which is on the ring C4 of the tetracycline molecule and the graph-
ene p-electrons. Ji also inferred that the adsorption of tetracycline
on carbon nanotubes and graphite was due to p–p electron donor–
accepter interaction and cation–p bonding [3].

3.3. Effect of incubation time and temperature on the adsorption of

tetracycline
Fig. 4. The adsorption kinetics (a) and the pseudo-second-order kinetics model for
adsorption (b) of tetracycline on GO suspension; Experiment condition: pH 3.6;
The effect of incubation time and temperature on the adsorp- 25 °C; GO 0.181 mg mL1; initial concentration of tetracycline is 8.33 mg L1 (h),
tion capacity of tetracycline by GO was studied in this paper. Three 33.33 mg L1 (s), and 166.67 mg L1 (4),respectively.
different initial concentrations of tetracycline, 8.33, 33.33, and
166.67 mg L1, were tested in this experiment. As shown in
Fig. 4a, the adsorption capacities (q) of tetracycline at medium equilibrium. In the present study, Ho’s pseudo-second-order kinet-
and low initial concentration achieved equilibrium in a short term, ics model was exploited to test the fitness of the experimental data
while the adsorption capacities of tetracycline at high initial con- and to assess the kinetics of the adsorption of tetracycline on the
centration increased with the increase in the adsorption time, GO. The pseudo-second-order kinetics model was based on the
and reached a plateau at adsorption time of 90 min. It demon- assumption that the rate-limiting step involves chemisorption
strated that the equilibrium time is related to the initial concentra- [38], which has been widely applied to the sorption of pollutants
tion of tetracycline. In the following experiment, we chose from aqueous solutions in recent years [12]. The linear form of
overnight incubation to ensure that all samples reach adsorption the pseudo-second-order equation is represented as follows:
544 Y. Gao et al. / Journal of Colloid and Interface Science 368 (2012) 540–546

t 1 1
¼ þ t ð4Þ
qt kq2e qe

where k (g mg1 h1) is the rate constant of sorption, qe (mg g1) is

the amount of tetracycline adsorbed at equilibrium, qt (mg g1) is
the amount of tetracycline adsorbed on the surface of the sorbent
2
at any time, and kqe is the initial rate (mg g1 h1). The linear fitting
results are plotted in Fig. 4b with the coefficients of determinations
of 0.9934, 0.9985, and 0.9996, respectively. The calculated adsorp-
tion capacity (qe) values estimated by the pseudo-second-order
model are 35, 125, and 318 mg g1, respectively, which showed
good consistency with the detected values in experiment (38 ± 2,
126 ± 2, and 311 ± 2 mg g1, respectively). As discussed above, the
tetracycline adsorption on GO suspensions can be well described
by the pseudo-second-order kinetic model. Since the kinetic data
of tetracycline at high initial concentration fit pseudo-second-order
2
kinetics model best, the initial rate (kqe ) from this linear fitting was Fig. 6. Effect of pH on adsorption capacity of tetracycline. Experiment condition:
calculated to be 6614 mg g1 h1 and the rate constant of sorption incubation for overnight; 25 °C; GO 0.181 mg mL1; initial concentration of
tetracycline is 8.33 mg L1 (h), 33.33 mg L1 (s), 166.67 mg L1 (4), respectively.
(k) is 0.065 g mg1 h1. The rate constants and the initial rates were
2
much higher than those of tetracycline adsorption on rectorite (kqe
1 1 1 1
is 167 mg g h ; k is 0.017 g mg h ) [13] and smectite (kqe is
2 observed pH effect on the adsorption of tetracycline on graphene
1667 mg g1 h1; k is 0.045 g mg1 h1) [12]. oxide is related to the molecular structure of tetracycline and the
The temperature effect on the adsorption capacities of tetracy- functional groups present on the surface of GO, which also can sup-
cline is shown in Fig. 5. It can be seen that the effect of temperature port the proposed mechanisms of p–p interactions and cation–p
on the adsorption capacities of tetracycline at medium and low ini- bonding. GO possess negative charges due to the abundance of
tial concentration is not obvious. However, when the initial con- oxygen-containing functional group on its surface. Tetracycline
centration of tetracycline is high, the adsorption of tetracycline has several polar/ionizable groups, including amino, carboxyl, phe-
slightly increases at 45 °C, which may be attributed to the increase nol, alcohol, and ketone. It has three acid dissociation constants
either in the number of active surface sites available for adsorption (pKa = 3.3, 7.7, and 9.7) and exists as a cationic, zwitterionic, and
on the adsorbent or in the diffusion rate of tetracycline [23]. anionic species under acidic, moderately acidic to neutral, and
alkaline conditions [36]. Specially, the amino group on the ring
C4 has pKa of 9.7 and is easily protonated under favorable condi-
3.4. Effect of pH and ionic strength on the adsorption of tetracycline
tions. The charges on GO and tetracycline are both dependent on
pH value. Increasing pH facilitates the deprotonation of the groups,
The effect of pH on the adsorption of tetracycline on GO suspen-
including charged amino and enol groups on the tetracycline mol-
sion is presented in Fig. 6. It can be seen that the adsorption of tet-
ecule and carboxyl group on GO. The electron-acceptor ability of
racycline on GO exhibited a strong pH dependence between pH 3
these moieties was weakened by increasing the pH, suppressing
and 11. The adsorption capacities of tetracycline at three different
the cation–p bonding and p–p stacking with graphene oxide.
initial concentrations decrease with the increase in pH. For high
In this study, different amounts of NaCl were added to the mix-
initial concentration of tetracycline, the adsorption capacities
ture of tetracycline and GO suspensions to investigate the effect of
decrease from 386.85 mg g1 to 133.62 mg g1, approximately by
ionic strength on the adsorption capacities. The results are shown
three times, over the tested pH range of 3–11. For medium and
in Fig. 7. It can be seen that the adsorption capacities decrease with
low initial concentrations of tetracycline, the adsorption capacities
the addition of NaCl. When the initial concentration of tetracycline
were 8- and 14-fold decrease over the tested pH range, respec-
was 166.67 mg L1, the adsorption capacities decreased by more
tively. The change extent of adsorption capacities amplified with
than 50% after the addition of 100 mmol L1 NaCl. When the tetra-
the decrease in the initial concentration of tetracycline. The
cycline concentration was 8.33 or 33.33 mg L1, the variation in
the adsorption capacities in the NaCl concentration range of
20–100 mmol L1 is not significant. The same inhibition trends
were also observed by Ji et al. [4], which used carbon tubes as
adsorbents. As previously reported, the added NaCl can influence
adsorption capacities of tetracycline on carbon material by the
electrostatics screening effect. We supposed that the increase in
ionic strength would resist the electrostatic interactions between
the charged amino group of tetracycline and the deprotonated car-
boxyl groups of graphene oxide, and the cation–p bonding was
weakened owing to electronic screening of the surface charge sites
by the added Na+. In previous studies, competition between tetra-
cycline species and Na+ ions for adsorbents surface via a similar
mechanism has also been suggested for the interaction of tetracy-
cline with humic substances [36].

3.5. Adsorption isotherms of oxytetracycline and doxycycline on

graphene oxide
Fig. 5. Effect of temperature on the adsorption capacity of tetracycline. Experiment
condition: pH 3.6; incubation for overnight; GO 0.181 mg mL1; initial concentra-
tion of tetracycline is 8.33 mg L1 (h), 33.33 mg L1 (s), and 166.67 mg L1 (4), Tetracycline is just the typical one of tetracycline antibiotics,
respectively. which has basic structure of four aromatic rings. Oxytetracycline
 Y. Gao et al. / Journal of Colloid and Interface Science 368 (2012) 540–546 545

4. Conclusion

In the present work, graphene oxide was used as an adsorbent

for tetracycline antibiotics’ removal from the aqueous solution ow-
ing to its excellent hydrophilicity, special structure, and high sur-
face area. The mechanism for the adsorption of tetracycline on
graphene oxide was deduced to be via p–p interaction and cat-
ion–p bonding. The ring structure in tetracycline molecule and
the hexagonal cells of the graphene oxide facilitate p–p interaction
between them, and cation–p bonding was likely to take place
between the amino group on the ring C4 of tetracycline and graph-
ene p-electron-rich structures. The kinetic of adsorption fits pseu-
do-second-order model perfectly. The effects of pH and ionic
strength on the adsorption capacities have been investigated in
detail.

Fig. 7. Effect of ionic strength (NaCl) on adsorption capacity of tetracycline. Acknowledgments

Experiment condition: pH 3.6; incubation for overnight; 25 °C; GO 0.181 mg mL1;
initial concentration of tetracycline is 8.33 mg L1 (h), 33.33 mg L1 (s), and
166.67 mg L1 (4), respectively.
This work was financially supported by the National Natural
Science Foundation of China (Nos. 20875036,21075050), the Devel-
opment Program of the Ministry of Science and Technology of Jilin
Table 2 Province, China (No. 20080544), and the Scientific Research
Maximum adsorption capacity (qm) of various adsorbents for tetracycline and Foundation for the Returned Overseas Chinese Scholars, State
oxytetracycline. Education Ministry.
Adsorbent qm (mg g1) Refs.
For Tetracycline Appendix A. Supplementary material
SWNTa 340b [3]
MWNTa 100b [3] Supplementary data associated with this article can be found, in
Montmorillonite 84b [5]
Smectite 462 [12]
the online version, at doi:10.1016/j.jcis.2011.11.015.
Palygorskite 99 [14]
Fe3O4–rGO composites 95 [27] References
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