Chemical Engineering Journal 281 (2015) 379–388

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Adsorption and coadsorption of organic pollutants and a heavy metal by

graphene oxide and reduced graphene materials
Jun Wang, Baoliang Chen ⇑
Department of Environmental Science, Zhejiang University, Hangzhou, Zhejiang 310058, China
Zhejiang Provincial Key Laboratory of Organic Pollutant Process and Control, Zhejiang University, Hangzhou, Zhejiang 310058, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Adsorption of graphene nanosheets

Hydrophobic effect
depend on their oxygen contents and π-π interaction
conformation. Sieving effect

 Adsorption of 1-naphthol onto

Electrostatic
graphene is much stronger than that attraction
HOOC- -COOH
of naphthalene. Cation-π
Cd2+ -OH Cd2+
 n–p EDA interaction contributes to HOOC-
interaction
-COOH
OH
the adsorption of 1-naphthol onto Surface
complexation
graphene nanosheets.
2+
 Cd and organic pollutants are π-π interaction OH
H-bonding
coadsorbed by graphene via n-π EDA interaction
Lewis acid-base interaction
surface-bridging mechanisms.
 Multiple adsorption sites on graphene
nanosheets favor the adsorption and
coadsorption.

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

Article history: The adsorption and coadsorption of naphthalene, 1-naphthol and Cd2+ onto graphene oxide (GO), chem-
Received 8 May 2015 ically reduced graphene (CRG) and annealing reduced graphene (ARG) were compared to determine the
Received in revised form 23 June 2015 unique adsorption properties of graphene nanosheets. The adsorption capability of organic pollutants fol-
Accepted 24 June 2015
lowed the order CRG > ARG > GO, and all three adsorbents showed stronger adsorption to 1-naphthol
Available online 27 June 2015
than to naphthalene. In addition to a p–p interaction, the strong adsorption of 1-naphthol onto graphene
nanosheets was mainly attributed to the n–p electron-donor–acceptor (EDA) interactions between the –
Keywords:
OH groups of 1-naphthol and the electron-depleted sites on graphene nanosheets. The adsorption of
Graphene oxide
Reduced graphene oxide
1-naphthol on reduced graphene materials increased with increasing pH and reached a maximum around
Adsorption its pKa, supporting the n–p EDA interaction mechanism. GO with more functional groups on the
Organic pollutant nanosheets over CRG and ARG exhibited a strong affinity with Cd2+. The adsorption of Cd2+ onto GO
Heavy metal and CRG facilitated the coadsorption of naphthalene and 1-naphthol via surface-bridging mechanisms,
Mechanisms such as cation–p interactions. Notably, though ARG showed no significant Cd2+ adsorption, the sup-
pressed coadsorption of naphthalene onto ARG may be attributed to the sieving effect by hydrated
Cd2+ binding to the micropore edges on ARG.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction

Graphene, a one-atom-thick 2D layer of sp2-bonded carbon [1],

is the most intensively studied material in the world and possesses
⇑ Corresponding author. Tel./fax: +86 571 8898 2587. fantastic electrical, mechanical, optical and chemical properties,
E-mail addresses: jwanges@163.com (J. Wang), blchen@zju.edu.cn (B. Chen).

http://dx.doi.org/10.1016/j.cej.2015.06.102
1385-8947/Ó 2015 Elsevier B.V. All rights reserved.
380 J. Wang, B. Chen / Chemical Engineering Journal 281 (2015) 379–388

such as high electrical conductivity, high strength, high trans- health. The effects of pH on adsorption were also examined.
parency and facile modification [2,3]. Due to its planar structure Graphene oxide (GO), chemically reduced graphene (CRG) and
and outstanding properties, graphene has a number of potential annealing reduced graphene (ARG) were selected as adsorbents
applications, especially in electronics and energy storage [4–6]. to better understand the adsorption characteristics of graphene
Recently, dozens of methods have been developed and used to pre- materials with different oxygen contents and microstructures.
pare graphene structures of different shapes, dimensions and qual-
ity [7–12]. Graphene has sparked tremendous scientific interest in
2. Materials and methods
environmental applications [13,14], especially in the adsorption of
pollutants, and the performance and mechanisms of these applica-
2.1. Preparation of graphene materials
tions of graphene have been explored [15–30]. Graphene materials
have already been investigated as efficient adsorbents for organic
GO was synthesized from natural graphite flakes (325 mesh,
and inorganic pollutants, such as polycyclic aromatic hydrocarbons
99.8%, Alfa Aesar) via a modified Hummers Method [33]. Then,
(PAHs) [15–18], phenolics [19,20], nitroaromatics [21], dyes [22–
the graphene oxide was exfoliated by sonication and dialyzed to
25], heavy metal ions [25–29] and anions [30]. Most adsorption
remove acids and other impurities. CRG was obtained by the
characteristics of graphene materials have been conducted in
reduction of exfoliated GO with hydrazine hydrate [7]. ARG was
single-solute systems, while few studies have considered
achieved by a 500 °C expansion under N2 using GO as the precursor
bi-solute adsorptions of various adsorbates to graphene.
[8]. GO, CRG and ARG of different oxygen contents were used as
However, a complex mix of organic pollutants and heavy metal
graphene-based adsorbents. Briefly, graphite powder (24 g) was
ions often coexist in the environments [31]; their sorption would
mixed with an 80 °C solution of concentrated H2SO4 (96 mL),
affect the fate and transport of contaminants [32]. Moreover, inter-
which contained K2S2O8 (20 g) and P2O5 (20 g), and was kept at
actions with the coexisting heavy metal ions may affect the
80 °C for 4.5 h. Pre-oxidized graphite was obtained after careful
adsorption of organic pollutants to graphene. This adsorption
washing and drying. The pre-oxidized graphite powder (20 g)
behavior may provide further insight into the structure and mech-
and NaNO3 (10 g) were added to cold (0 °C), concentrated H2SO4
anisms of the adsorptive sites of graphene materials. Therefore, the
(460 mL) in an ice bath. Then, KMnO4 (60 g) was slowly added
elucidation of the coadsorption behavior of organic pollutants and
under continuous agitation. The reaction was kept at 35 °C for
heavy metal ions is significant for evaluating the environmental
2 h. Then, deionized (DI) water (920 mL) was gradually added, pro-
impact of graphene materials and for developing novel functional
ducing much heat. Afterward, the mixture was kept at 98 °C for
materials for pollution management.
15 min, and 50 mL 30% H2O2 solution was slowly added to reduce
Due to its hydrophobic properties and strong p–p interactions
the residual KMnO4. The resultant brilliant yellow mixture was
of its aromatic 2D structure, graphene nanosheets exhibit superior
rinsed with 10% HCl solution (7.2 L) to remove residual SO24 and
adsorption capacities for persistent aromatic pollutants [15–18].
metal ions, followed by centrifugation at 8000 rpm. Then, the solid
However, oxygen-containing functional groups, such as ACOOH,
product was dissolved in DI water using vigorous agitation and
AOH and AC@O, are formed on the surface of graphene nanosheets
ultrasonication for 30 min at 250 W. The centrifugation and ultra-
as a result of the incomplete reduction of graphene oxide (GO) [7].
sonication steps were repeated several times. Then, the solution
These functional groups could significantly alter the adsorption of
was dialyzed to remove residual acids and other impurities. After
organic and inorganic pollutants. The adsorption of phenolics gen-
vacuum drying at 60 °C for 24 h, the GO sample was obtained
erally increased with an increasingly reduced GO [20], whereas the
and stored as a suspension in water. Chemically reduced graphene
reduction of GO decreased the adsorption of heavy metal ions [29].
(CRG) was produced via the hydrazine reduction of GO. A certain
The reduction of GO eliminated the oxygen-containing functional
amount of GO dispersion (1 mg/mL) was ultrasonicated (250 W)
groups and restored a sp2-hybridized structure [7], which resulted
and pelleted at 3000 rpm for 5 min. The supernatant was decanted
in strengthened p–p interactions between the organic pollutants
and loaded in a round-bottom flask; the pH was adjusted to 10
and graphene nanosheets, reduced water molecule competition
using ammonia hydroxide. Then, 10 mL hydrazine hydrate (98%,
with organic pollutants at the oxidized sites [15,19,20], and weak-
Aladdin Co., Ltd.) was added and the solution was heated in a
ened surface complexations between heavy metal ions and the oxi-
98 °C water bath under a water-cooled condenser for 24 h. The
dized sites [26–29]. Therefore, by regulating the varieties of
resultant black solid was isolated by filtration through a 0.22-lm
oxygen-containing functional groups on graphene nanosheets, gra-
membrane filter, and washed with deionized water and methanol
phene materials have great potential for applications in pollution
to remove excess hydrazine. After freeze drying, the CRG was
control, especially for complex mixes of organic and inorganic pol-
obtained as a black powder. Annealing reduced graphene (ARG)
lutants. In addition, the conformation of graphene nanosheets has
was produced via a 500 °C expansion under N2 gas using GO as
been demonstrated to have significant impact on the adsorptive
the precursor. A certain amount of GO powder was placed in a tube
sites for PAHs [15]. Because the conformations of graphene mate-
furnace under N2 gas. The tube temperature was increased to
rials with different oxygen contents are not the same [15,20], it
500 °C at a rate of 5 °C/min and kept at this temperature for 2 h.
is worthwhile to explore the effect of graphene conformation on
Annealing reduction carried out at 500 °C was to remove as many
the interfacial behavior of organic molecules.
surface oxygen groups as possible, while ensure the adequate exfo-
The main objective of this study was to recognize the unique
liation of GO. Afterward, the tube was cooled down and the ARG
adsorptive and coadsorptive properties of graphene nanosheets.
was obtained.
Specific experiments were designed to investigate: (i) the interfa-
cial behaviors of organic and inorganic pollutants adsorbed on gra-
phene as affected by the oxygen content and conformation of 2.2. Characterization of graphene materials
graphene materials; and (ii) the effect of the presence of coexisting
heavy metal ions on organic adsorption to graphene materials. The structure and surface morphologies of graphene materials
Naphthalene and 1-naphthol with different polarities were were characterized by elemental (C, H, and N) analyses, BET-N2
selected to determine their adsorption capacity on graphene mate- specific surface areas, Raman spectra, and scanning electron micro-
rials with and without the presence of Cd2+, while Cd2+ was scopy (SEM). The surface functional groups were analyzed by
selected as a typical toxic metal ion because it is commonly found Fourier transform infrared spectroscopy (FTIR), and the surface
in surface and underground waters which poses a threat to human electrical properties were measured from duplicate samples using
 J. Wang, B. Chen / Chemical Engineering Journal 281 (2015) 379–388
a Nano-ZS90 Zetasizer (Malvern Instruments, Ltd.). Elemental (C,
H, and N) analyses were conducted using an EA1112 CHN elemen-
tal analyzer (Thermo Finnigan). The Brunauer–Emmett–Teller
(BET) nitrogen specific surface areas of graphene materials were
estimated by nitrogen adsorption–desorption at 196 °C with a
NOVA-2000E surface area analyzer. Raman spectra were obtained
with a LabRamHRUV Raman spectrometer (JDbin-yvon, FR); the
laser excitation was provided by an Ar+ laser at a wavelength of
514 nm. The surface morphologies of graphene materials were
characterized using an S-4800 Field Emission Scanning Electron
Microscope (FE-SEM; Hitachi, Tokyo). The FTIR spectra were
recorded in the 4000–400 cm 1 region with a resolution of
4 cm 1 using a Bruker Vector 22 FTIR spectrometer. The surface
charge properties of graphene materials were measured with a
Zetasizer (Malvern ZEN3690). The pH of the graphene suspensions
was adjusted to pH 2–12 using 1 mol/L HNO3 or 1 mol/L NaOH.
2.3. Batch adsorption and coadsorption experiments
Naphthalene (greater than 98% purity, Acros Organics),
1-naphthol (99%, Aladdin Company) and Cd(NO3)2
4H2O (99%,
Shanghai Jinshan Chemistry Company) were selected as model
adsorbates. The single-solute adsorptions of naphthalene,
1-naphthol, and Cd2+ to GO, CRG, and ARG were carried out in
PTFE screw cap vials at 25 ± 1 °C. Isotherm experiments were per-
formed with different solid-to-water ratios for various adsorbates
in a background solution containing 0.01 M NaNO3 in deionized
water with 200 mg/L NaN3 as a bio-inhibitor at a 5.0 ± 0.1 pH.
Each measurement (blank and calibration control) was conducted
in duplicate. The initial concentrations of naphthalene (0.2–
20 mg/L), 1-naphthol (1–50 mg/L) and Cd2+ (0.2–10 mg/L for CRG
and ARG, 5–200 mg/L for GO) solutions were controlled to achieve
the desired equilibrium concentrations of the different compo-
nents. The vials were agitated continuously in the dark at
120 rpm for 24 h to reach adsorption equilibrium. Preliminary
experiments indicated that an apparent equilibrium was reached
in less than 24 h. After centrifugation at 3,000 rpm for 15 min,
the naphthalene concentrations in the supernatants were deter-
mined by an Agilent 1200 HPLC equipped with a fluorescence
detector. The mobile phases were acetonitrile:water (90:10, v:v)
at flow rates of 1 mL/min. Naphthalene detection was performed
using an excitation wavelength of 225 nm and an emission wave-
length of 335 nm. The 1-naphthol concentrations in the super-
natants were analyzed by a UV-2550 spectrophotometer at a
wavelength of 332 nm. The solutions of Cd2+ were filtered through
a 0.22-lm Millipore filter. After dilution with 0.2% HNO3, the fil-
trate was analyzed using atomic absorption spectroscopy (Perkin
Elmer Analyst 700) to determine the cadmium residues. The coad-
sorptions of naphthalene and 1-naphthol to graphene materials in
the presence of Cd2+ were carried out by batch technique. Other
than the addition of 10 mg/L Cd2+ ions in the organic solutions,
all conditions were identical to the single-solute adsorption exper-
iments mentioned above.
2.4. The effects of solution pH on the adsorption of graphene materials
The effects of pH on the adsorption of naphthalene, 1-naphthol
and Cd2+ onto GO, CRG and ARG were investigated. The initial con-
centrations were as follows: 2 and 20 mg/L for naphthalene, 5 and
50 mg/L for 1-naphthol, and 4 mg/L for Cd2+. For CRG and ARG, the
initial pH values of naphthalene and 1-naphthol were adjusted to
2–12 using 0.1 mol/L HNO3 or NaOH, while the initial pH values
of Cd2+ were adjusted to 2–8 because Cd(OH)2 precipitates above
pH 8 [27]. For GO, the initial pH values of the tested adsorbates
were adjusted to 2–7, because under alkaline conditions, the sepa-
ration of solid GO from liquid phase was too difficult [34]. After
381
equilibration conditions were reached, the adsorbate concentra-
tions in the supernatants were analyzed and the equilibrium pH
values were measured. The amounts of pollutants adsorbed by
the graphene materials were calculated from the differences
between the initial and equilibrium concentrations.
2.5. Data analysis
Using Origin 8.5, Freundlich and Langmuir models were applied
to analyze the adsorption isotherms. The Freundlich equation is
described as follows: qe = Kf CeN, where qe (mg/g) is the
equilibrium-sorbed concentration, Kf [(mg/g)/(mg/L)N] is the
Freundlich affinity coefficient, and N is the exponential coefficient.
The Langmuir equation is described as follows: qe = qm Ce/(KL + Ce),
where KL (L/g) is the Langmuir constant, and qm (mg/g) represents
the maximum adsorption capacity of the adsorbent.
3. Results and discussion
3.1. Characterization of graphene materials
The results of SEM, Raman, and FTIR characterizations of GO,
CRG, and ARG are presented in Fig. 1. The SEM images (Fig. 1a–c)
showed that all three samples displayed typical rippled and crum-
pled surfaces indicative of graphene [15]. The size of the GO
nanosheets was large and the surfaces were relatively flat
(Fig. 1c) compared with those of CRG and ARG. However, after
reduction, especially annealing reduction, the large GO nanosheets
were divided into a few small fragments (Fig. 1b). The inset of
Fig. 1a shows a magnified SEM image of CRG with wrinkles loosely
distributed on the basal plane. The micro-morphology of ARG
(inset of Fig. 1b) was distinctively different from that of CRG. The
ARG nanosheets were slightly aggregated, and a few micro-pores
were created by the packed layers. The BET-N2 specific surface
areas (SA) of GO, CRG, and ARG were 39, 376, and 286 m2/g, respec-
tively. The observed SA expansions after the reductions of GO to
CRG and ARG confirmed the exfoliation of graphene during the
reduction process and were comparable with the values observed
in other studies [7,8]. The discrepancy between the obtained and
theoretical (2630 m2/g) SA values of the graphene materials can
be attributed to an incomplete exfoliation and the aggregation of
graphene layers during synthesis.
The Raman spectra of graphene materials are shown in Fig. 1d.
The D band at approximately 1355 cm 1 originated from the vibra-
tion of defected and disordered sp3 carbon atoms, and the G band
at approximately 1594 cm 1 originated from the vibration of sp2
carbon atoms associated with the first order scattering of the E2g
phonon. The three samples showed similar spectra patterns, but
the intensity of D band of CRG was significantly higher than those
of GO or ARG. By calculating the intensity ratio of the D band to the
G band (Table 1), the ID/IG of CRG (1.27) was much higher than
those of GO (0.93) and ARG (0.92), indicating that CRG had more
graphitic structure defects [7].
The zeta potential is a physical parameter indicative of the sur-
face electric potential of solid particles and the stability of liquid
dispersions. As shown in Fig. 1f, the zeta potentials of the graphene
materials decreased with increasing pH. The isoelectric point of
CRG was achieved at pH 3.6, and the isoelectric point of ARG was
achieved at pH 3.2. The zeta potentials of GO were always negative
and below 30 mV for pH > 3, indicating the excellent stability of
GO dispersions over a wide pH range due to a strong electrostatic
repulsion between the GO sheets [20].
The FTIR spectra of graphene materials are presented in Fig. 1e.
For GO, the strong and broad band at 3390 cm 1 was attributed to
the vibration of O-H bonds. The peaks at 1721, 1401, 1218, and
382 J. Wang, B. Chen / Chemical Engineering Journal 281 (2015) 379–388

(a) (b) (c)

20
G
(d) D
(e) 3390 10
(f)
1585 1218 0
1095

Zeta Potentials (mV)

Intensity(a.u.)

1721 1401 -10

Absorbance

S3 CRG
2D
Graphene Oxide -20
ARG
1113 GO

GO -30
3435 1560
Annealing Reduced Graphene
1385 1108
ARG 1735 -40

Chemical Reduced Graphene 1391 -50

CRG
-60
1000 1500 2000 2500 3000 4000 3500 1500 1000 2 4 6 8 10 12
-1 -1 pH
Raman Shift(cm ) Wavenumbers (cm )

Fig. 1. The SEM images of CRG (a), ARG (b) and GO (c). Inset of images show characteristic micro-structures of CRG, ARG and GO. Raman spectra (d), FTIR spectra (e), and zeta
potentials (f) of CRG, ARG and GO.

90.7% for ARG, indicating an increasing reduction by the annealing

Table 1
Elemental composition and atomic ratios, BET-N2 surface area (SA) and ID/IG of Raman
treatments. The H/C, O/C and [(O + N)/C] atomic ratios on the sur-
spectra of graphene oxide (GO), chemically reduced graphene (CRG), and annealing faces of the graphene materials were calculated. The lower H/C
reduced graphene (ARG).a ratio indicated that ARG was more aromatic than CRG and GO,
Sample CRG GO ARG
while the decreased O/C ratio from GO to CRG and ARG suggested
a less hydrophilic surface. The tiny polarity index [(O + N)/C] of
C/(wt)% 81.0 53.9 90.7
H/(wt)% 0.759 2.15 0.20
ARG reflected the presence of very few polar groups. The distinct
O/(wt)% 13.7 44.0 8.31 microstructures and surface properties of GO, CRG and ARG may
N/(wt)% 4.53 0 0.790 play a critical role on their adsorption and coadsorption behaviors
H/C 0.112 0.479 0.0265 for different sorbents.
O/C 0.127 0.612 0.0687
(O + N)/C 0.175 0.612 0.0762
SA/m2 g 1 376 39 286 3.2. Single-solute adsorption of graphene materials
ID/IG 1.27 0.93 0.92
a
H/C: atomic ratio of hydrogen to carbon. O/C: atomic ratio of oxygen to carbon. The adsorption isotherms of naphthalene, 1-naphthol, and Cd2+
(O + N)/C: atomic ratio of sum of nitrogen and oxygen to carbon. ID/IG was the onto GO, CRG, and ARG are shown in Fig. 2. Freundlich and
intensity ratio of the D band to the G band of Raman spectra of CRG, ARG and GO.
Langmuir models were used to fit the isotherms. In general, all
adsorption isotherms were nonlinear, and the regression parame-
1095 cm 1 corresponded to the stretching vibration of the C@O, ters of the isotherms by the Freundlich and Langmuir models are
OAC@O (carboxyl), CAOAC (epoxy) and CAO (alkoxy) bonds, listed in Table 2.
respectively [15,19]. The band at 1585 cm 1 was indicative of For naphthalene, the adsorption affinities to the three adsor-
C@C (CAC) skeletal vibrations, indicating the presence of bents followed the order of GO < ARG < CRG. The trend correlated
graphene-like domain on the GO nanosheets. The abundant num- with that of the specific surface areas (SA) of the graphene materi-
bers of functional groups on GO resulted in higher hydrophilicity, als (Table 1). However, the adsorption affinities was not the only
better water dispersibility. For CRG and ARG, the peaks at factor governing the adsorption processes because the SA of CRG
1560 cm 1 were assigned to the C@C stretching vibration. It is evi- (378 m2/g) was approximately 1.5 times that of ARG (276 m2/g),
dent that the intensity of the OAH bond at 3435 cm 1 was weaker while the adsorption capacity of CRG (Qmax = 145 mg/g) was
compared with that of GO, and the peaks at 1735 cm 1 (C@O), approximately 3 times that of ARG (Qmax = 52.4 mg/g). As previ-
approximately 1390 cm 1 (O@CAO), 1218 cm 1 (CAOAC) and ously reported [15], graphene materials with diverse surface prop-
approximately 1110 cm 1 (alkoxy C-O) were weaker or absent. erties possessed different adsorption sites for PAHs. Even the
These indicated that many oxygen-containing functional groups surface of CRG was less hydrophobic than that of ARG, and the
were removed via chemical or annealing reductions, and the sur- adsorption affinity of CRG for the hydrophobic naphthalene was
faces of CRG and ARG were highly hydrophobic. Notably, the prominent. The adsorption of 1-naphthol onto CRG was slightly
C@O bond at 1735 cm 1 on CRG was absent when compared with stronger than that onto ARG, and both were considerably stronger
the spectra of GO and ARG, indicating that functional groups con- than the adsorption onto GO. Surprisingly, 1-naphthol was less
taining a C@O bond could be altered or eliminated by hydrazine hydrophobic than naphthalene, but the adsorptions of
reduction. The elemental compositions of the graphene materials 1-naphthol onto the tested graphene materials were significantly
are presented in Table 1 and agree with the FTIR results. The car- higher than the adsorptions of naphthalene. This unique adsorp-
bon contents increased from 53.9% for GO to 81.0% for CRG and tion was likely correlated with the specific electronic properties
 J. Wang, B. Chen / Chemical Engineering Journal 281 (2015) 379–388 383

Table 2
Regression parameters of adsorption isotherms of naphthalene, 1-naphthol and Cd2+
(a) Naphthalene
Adsorbed Concentration, (mg/g)

100 onto CRG, ARG and GO fitted by Freundlich and Langmuir models.

Adsorbent Compound Freundlich model

Kf N R2
10
CRG Naphthalene 45.4 ± 3.04 0.430 ± 0.030 0.962
1-Naphthol 59.3 ± 8.65 0.399 ± 0.046 0.875
Cd2+ 3.28 ± 0.106 0.309 ± 0.020 0.963
1 ARG Naphthalene 14.2 ± 0.649 0.485 ± 0.222 0.986
CRG 1-Naphthol 35.8 ± 3.15 0.503 ± 0.027 0.975
ARG Cd2+ 0.105 ± 0.005 0.543 ± 0.022 0.988
GO
0.1 Freundlich GO Naphthalene 4.88 ± 0.065 0.625 ± 0.001 0.998
Langmuir 1-Naphthol 13.1 ± 2.34 0.406 ± 0.063 0.828
Cd2+ 3.16 ± 0.127 0.334 ± 0.024 0.958
Adsorbent Compound Langmuir model
0.01
0.01 0.1 1 10 Qmax KL R2

Equilibrium Concentration, (mg/L) CRG Naphthalene 145 ± 12.3 2.00 ± 0.609 0.898
1-Naphthol 269 ± 12.9 4.86 ± 0.772 0.950
Cd2+ 6.32 ± 0.159 0.748 ± 0.080 0.976
ARG Naphthalene 52.4 ± 4.36 3.03 ± 0.737 0.957
(b) 1-Naphthol
Adsorbed Concentration, (mg/g)

1-Naphthol 282 ± 15.8 11.8 ± 1.78 0.972

Cd2+ 0.499 ± 0.020 4.04 ± 0.388 0.991
GO Naphthalene 21.4 ± 1.59 3.35 ± 0.484 0.990
100 1-Naphthol 57.7 ± 4.02 4.99 ± 1.02 0.942
Cd2+ 35.7 ± 2.34 0.563 ± 0.260 0.787

Notably, as calculated from the Langmuir equation, it can be

seen that the Qmax of CRG for naphthalene at pH 5 was 145 mg/g,
while the Qmax of ARG for 1-naphthol was 282 mg/g, and the
Qmax of GO for Cd2+ was 35.7 mg/g. By comparison with other com-
mon adsorbents, such as C60 (Qmax = 101.2 mg/g for naphthalene)
10
[36], orange peel biochar pyrolyzed at 700 °C (Qmax = 80 mg/g for
1-naphthol) [37], multi-walled carbon nanotubes
(Qmax = 54.3 mg/g for 1-naphthol) [38] and activated carbon
1 10 100
(Qmax = 19.6 mg/g for Cd2+) [39], graphene materials with different
Equilibrium Concentration, (mg/L) oxygen contents were efficient adsorbents for polar and nonpolar
100 organic contaminants and heavy metal ions. This suggests that
the graphene materials show great potential in pollution control
Adsorbed Concentration, (mg/g)

(c) Cd2+ applications.

10
3.3. Coadsorption of organic pollutants and heavy metals to graphene
materials
1
The effects of heavy metal ions on the adsorption of polar
(1-naphthol) and nonpolar (naphthalene) aromatic organic com-
0.1
pounds are presented in Fig. 3. When Cd2+ (10 mg/L) was present
in solution, the affinity of naphthalene onto GO was enhanced by
30% (Fig. 3e) and by 10% onto CRG (Fig. 3a). However, the uptake
0.01
of naphthalene onto ARG was suppressed by 25% (Fig. 3c), indicat-
ing that the observed coadsorption was gradually promoted as the
concentration of polar functional groups increased on the graphene
1E-3
0.01 0.1 1 10 100 nanosheets. Interestingly, the presence of Cd2+ (10 mg/L) enhanced
the adsorption of 1-naphthol onto GO by 120% (Fig. 3f), but showed
Equilibrium Concentration, (mg/L) negligible effects on the adsorption by CRG and ARG. Therefore, the
coexisting Cd2+ had different effects on the adsorption of polar and
Fig. 2. Adsorption isotherms of naphthalene (a), 1-naphthol (b), Cd2+ (c) onto CRG,
ARG and GO. Solid lines represent isotherms fitted by Freundlich model, and dashed nonpolar aromatics onto graphene materials of different structures
lines represent isotherms fitted by Langmuir model. and surface properties. The detailed mechanisms are discussed in
the following section. Here, we are the first to report on the
of 1-naphthol originating from the hydroxyl functional groups enhanced adsorption of organic pollutants to graphene materials
[35]. The adsorptions of Cd2+ to CRG and ARG were much less than in the presence of heavy metals.
that on GO, which followed with the oxygen content of graphene
materials. ARG, at a higher reduction degree than CRG, showed 3.4. Effects of pH on adsorption of graphene materials
an extremely low adsorption for Cd2+, indicating that
oxygen-containing functional groups on graphene materials played Fig. 4a–c show the pH effects on the adsorptions of naphthalene
critical roles in the adsorption of heavy metals in aqueous (C0 = 20 mg/L), 1-naphthol (C0 = 50 mg/L), and Cd2+ (C0 = 4 mg/L)
solutions. onto graphene materials, respectively. For naphthalene, the effects
384 J. Wang, B. Chen / Chemical Engineering Journal 281 (2015) 379–388

300
180

160
(a) CRG 250
(b) CRG
Adsorbed Concentration, (mg/g)

140
200
120

100 150
80
100
60

40 Naphthalene with 10 ppm Cd2+ 50 1-Naphthol with 10 ppm Cd2+

Naphthalene 1-Naphthol
20
0
0

-2 0 2 4 6 8 10 12 14 16 0 10 20 30 40
Equilibrium Concentration, (mg/L) Equilibrium Concentration, (mg/L)
50 300

(c) ARG 250

(d) ARG
40
Adsorbed Concentration, (mg/g)

200
30

150
20
100

10
Naphthalene with 10 ppm Cd2+ 50 1-Naphthol with 10 ppm Cd2+
Naphthalene 1-Naphthol
0 0

-2 0 2 4 6 8 10 12 14 16 0 10 20 30 40 50
Equilibrium Concentration, (mg/L) Equilibrium Concentration, (mg/L)
120
18

16 (e) GO 100
(f) GO
Adsorbed Concentration, (mg/g)

14
80
12

10
60
8

6 40

4 2+ 2+
Naphthalene with 10 ppm Cd 20 1-Naphthol with 10 ppm Cd
2 Naphthalene 1-Naphthol
0 0
-2
0 1 2 3 4 5 0 5 10 15 20 25 30 35
Equilibrium Concentration, (mg/L) Equilibrium Concentration, (mg/L)

Fig. 3. Adsorption isotherms of naphthalene (a, c, and e) and 1-naphthol (b, d, and f) on CRG (a and b), ARG (c and d) and GO (e and f) in the presence (solid) and absence
(hollow) of 10 mg/L Cd2+.

of pH on the adsorptions to GO, CRG, and ARG were not obvious. affected by the solution pH, suggesting that graphene materials as
However, the surface properties of the graphene materials, such adsorbents could be efficient in the removal of PAHs over a wide
as surface charge, and the protonation-deprotonation transition pH range.
of functional groups were significantly affected as the pH varied As shown in Fig. 4b, the adsorptions of 1-naphthol on CRG and
over from 2 to 12 (and from 2 to 7 for GO), as indicated by the zeta ARG increased with the pH and presented peaks at the point where
potentials presented in Fig. 1f. The effective adsorption sites of GO, the pH value was the same as the pKa value (9.34) of 1-naphthol.
CRG and ARG for nonpolar organic pollutants were not significantly Interestingly, this trend was more significantly pronounced for
 J. Wang, B. Chen / Chemical Engineering Journal 281 (2015) 379–388 385

200 was weaker at pH 12 than at pH 9, but was considerably stronger

CRG than those at lower pH values (pH 2–8). However, the adsorption
(a) ARG of 1-naphthol onto GO decreased over the pH range of 2–7, sug-
160 GO gesting that the dominant mechanisms of the adsorption processes
Adsorbed Concentration, (mg/g)

of 1-naphthol onto graphene materials with different surface func-

tional groups were diverse. Interestingly, ARG exhibited remark-
120
ably high adsorption capacities (exceeding 400 mg/g) toward
1-naphthol for pH values around the pKa (9.34) of 1-naphthol.
80 This value was even higher than the adsorption of 1-naphthol onto
sulfonated graphene (Qmax = 345 mg/g) [16]. The excellent adsorp-
tion capacity of 1-naphthol onto ARG indicated that ARG would be
40 a promising candidate for the management of polar organic pollu-
tants. The pH effect experiments of naphthalene (2 mg/L) and
1-naphthol (5 mg/L) at low concentrations are presented in
0 Fig. 5; similar trends as those at high concentrations were
2 4 6 8 10 12 observed. The unique effects of pH on the adsorption of organic
pollutants onto graphene materials were regulated by the
pH
oxygen-containing contents of the adsorbents and the polarities
of the organic sorbates.
400 (b) The pH dependence of Cd2+ uptake onto graphene materials are
also shown in Fig. 4c. It is clear that for all three graphene-based
adsorbents, the uptake of Cd2+ increased with increasing solution
Adsorbed Concentration, (mg/g)

300 pH, which is consistent with the observations of previous studies

[27]. Notably, the trend was more significantly pronounced for
the adsorptions onto GO than onto CRG and ARG, indicating that
200 the uptake of heavy metal ions onto graphene materials correlated
with the surface oxygen content.

100 3.5. Adsorption and coadsorption mechanisms of graphene materials

The p–p interaction, hydrophobic effect, H-bonding and elec-

0 trostatic interaction have commonly been applied to interpret
the adsorption mechanisms of aromatic organic pollutants onto
2 4 6 8 10 12 carbon-based materials such as carbon nanotubes, biochar and gra-
pH phene [15–23,37,38]. PAHs were demonstrated to adsorb onto gra-
phene nanosheets primarily through p–p interactions (Fig. 6a). The
30
elimination of oxygen-containing functional groups significantly
(c) enhanced the interaction between the p system of graphene and
25 the p units of aromatic molecules [15,19]. However, in the current
Adsorbed Concentration, (mg/g)

study, ARG showed a lower adsorption capacity (Qmax = 52.4 mg/g)

20
15
10
5 dent on the density of oxygen-containing functional groups on the
0 molecules onto graphene was primarily dependent on the p sys-
2 3 4 5
pH
Fig. 4. pH-Dependent adsorptions of naphthalene (a), 1-naphthol (b) and Cd2+ (c)
onto CRG, ARG and GO. The initial concentrations of naphthalene, 1-naphthol and
Cd2+ were 20, 50, and 4 mg/L, respectively. The solid lines represent the general
trend of adsorption capacities of adsorbates by graphene materials with the change
of pH.
the adsorption to ARG than to CRG. When the pH value exceeded
the pKa (9.34), the trends observed for CRG and ARG were distinctly
different. The adsorption of 1-naphthol onto CRG sharply fell, and
the uptake at pH 12 decreased by 50% compared with that under
extremely acidic conditions (pH = 2). The adsorption onto ARG
for naphthalene than that of CRG (Qmax = 145 mg/g), despite having
a higher reduction level than CRG. This cannot be fully explained
by the SA differences between CRG (376 m2/g) and ARG (278 m2/g).
The uptake of naphthalene onto GO was largely enhanced (30%)
in the presence of Cd2+, while that onto CRG (with fewer functional
groups) was only slightly enhanced (10%). It was reported that the
adsorption of heavy metal ions onto graphene was closely depen-
graphene nanosheets [26–29]. While, the adsorption of organic
tem [15–19]. Therefore, the adsorption of Cd2+ onto the
6 7 8 oxygen-containing functional groups might not compete on
adsorption sites with nonpolar organic molecules, but may instead
create new adsorption sites. Previous studies have reported that
the presence of heavy metal ions can bridge organic compounds
and functional groups on carbon nanomaterials [31,40,41]. We
speculated that the Cd2+ adsorbed onto the oxidized sites on gra-
phene nanosheets could bridge naphthalene and graphene via
cation–p interactions [31] because PAHs are p-electron rich donors
and show high affinities for cations adsorbed on carbon nanomate-
rials. However, if the adsorption mechanisms are different for GO
and CRG, the enhanced adsorptions of naphthalene normalized to
the adsorbed amounts of Cd2+ and SA should be significantly differ-
ent. The quantitative contributions of the adsorbed Cd2+ toward
the enhancement of naphthalene adsorptions onto GO and CRG
per unit SA were calculated. When the pH was 5 and the initial
386 J. Wang, B. Chen / Chemical Engineering Journal 281 (2015) 379–388

120
CRG
60
(a) ARG
(b)
GO
Adsorbed Concentration, (mg/g)

Adsorbed Concentration, (mg/g)

80

40

40

20

0
0
2 4 6 8 10 12 2 4 6 8 10 12
pH pH

Fig. 5. pH-dependent adsorptions of naphthalene (a) and 1-naphthol (b) onto CRG, ARG and GO. The initial concentrations of naphthalene and 1-naphthol were 2 and 5 mg/L,
respectively.

(a)
Hydrophobic effect
π-π interaction
Sieving effect

Electrostatic
attraction
HOOC- -COOH
Cation-π
(b) Cd2+ -OH Cd2+ (d)
interaction
HOOC- -COOH
Surface OH
complexation

π-π interaction OH
H-bonding
n-π EDA interaction
Lewis acid-base interaction

(c)

Fig. 6. Adsorption (a, b, c) and coadsorption (d) mechanisms of naphthalene (a), 1-naphthol (c) and Cd2+ (b) onto graphene materials.

concentration of Cd2+ was 10 mg/L, the uptakes of Cd2+ by GO and preventing naphthalene from reaching the adsorption sites
CRG in the single-solute system were approximately 16 and (Fig. 6a and d). Therefore, the observed naphthalene adsorption
6 mg/g, respectively, while the added amounts of naphthalene differences between ARG and CRG may be attributed to the sieving
(C0 = 20 mg/L) adsorbed onto GO and CRG in the presence of Cd2+ effect of micropores on ARG weakening the interaction between
were 3.9 and 14 mg/g, respectively. Therefore, by normalizing the rigid nonpolar organic molecules and porous ARG. Additionally,
SA, the enhanced adsorption of naphthalene onto GO normalized more defected sites were present on the surface of CRG than on
by the adsorbed amounts of Cd2+ and SSA was 0.0063 g/m2, which ARG, as indicated by the ID/IG ratios in Table 1. Defected sites are
approaches that calculated for CRG (0.0062 g/m2). These observa- generally regarded as high surface energy sites on graphene
tions strongly indicated that the cation–p interactions between nanosheets [43]; thus, the abundance of defected sites on CRG
Cd2+ and naphthalene facilitated naphthalene adsorption onto dif- could be another reason for its high adsorption capacity for
ferent graphene interfaces (Fig. 6d). However, the uptake of naph- naphthalene.
thalene onto ARG was unexpectedly suppressed. Because the The presence of oxygen-containing functional groups on gra-
amount of Cd2+ adsorbed onto ARG was very small phene nanosheets partly compromised the p-electron conjugated
(Qmax < 0.4 mg/g), such a trace amount would not significantly structure, reduced the hydrophobicity [7,44], and made the surface
affect the adsorption of naphthalene onto ARG. Unlike CRG, ARG charge more electronegative (i.e., more responsive to pH changes)
was fragmented into multiple small pieces leading to the forma- [20]. As shown in Fig. 1f, the zeta potentials of graphene materials
tion of micropores created by packed layers (Fig. 1a and b). significantly decreased with increasing pH values, but the adsorp-
While the oxygen content of ARG was lower than that of CRG, tion of naphthalene was nearly independent of pH, indicating that
the FTIR spectra (Fig. 1e) clearly showed that carboxyl groups were the protonation-deprotonation transition had little effect on the
absent on CRG whereas a few were present on ARG. Because car- interaction between graphene materials and nonpolar molecules.
boxyl groups are known to be distributed on the edge of graphene For 1-naphthol, the adsorption capacity (Qmax) of ARG was com-
nanosheets [42], the hydrated Cd2+ ions were more likely to bind to parable with that of CRG, but was much stronger than that of GO
the edge of the micropores on ARG and provide a steric hindrance (Fig. 2b). Meanwhile, the uptake of 1-naphthol on the three
 J. Wang, B. Chen / Chemical Engineering Journal 281 (2015) 379–388 387

adsorbents was much stronger than that of naphthalene. 1000000

Compared with naphthalene, 1-naphthol contains an AOH group (a) Naphthalene
CRG
and has a lower hydrophobicity [19]. Thus, a hydrophobic effect ARG
does not dominate the adsorption of 1-naphthol onto graphene GO
materials. Furthermore, the p–p interactions between 1-naphthol
100000
and graphene materials, as indicated by previous works [16,19],
cannot explain the powerful adsorption capacity of 1-naphthol

Kd, (L/kg)
over naphthalene.
Unlike naphthalene, the presence of Cd2+ had no significant
influence on the adsorptions of 1-naphthol onto CRG and ARG. 10000
The AOH of 1-naphthol could directly interact with functional
groups on graphene through hydrogen bonding (Fig. 6c) [19]. In
the presence of Cd2+, the oxygen-containing groups would be
preferably occupied by Cd2+ over 1-naphthol and the direct
H-bonding would be replaced by a comparatively strong cation– 1000
0.01 0.1 1 10 100
p interaction between Cd2+ and 1-naphthol (Fig. 6d). The adsorp-
tion of 1-naphthol onto ARG was significantly larger than that of Equilibrium Concentration, (mg/L)
naphthalene. This was not suppressed in the presence of Cd2+, indi-
cating that the adsorption of 1-naphthol was not dependent on the 100000 (b) 1-Naphthol
porous structure of ARG. Notably, the presence of Cd2+ significantly
enhanced the adsorption of 1-naphthol onto GO. The calculated
adsorption coefficient (Kd) values at different equilibrium concen-
10000
trations based on naphthalene, 1-naphthol and Cd2+ isotherms
onto graphene materials are shown in Fig. 7. The adsorption affin-
ity of Cd2+ onto GO was much higher than that of 1-naphthol, indi- Kd, (L/kg)
1000
cating that the presence of Cd2+ ions in solution would be more
prone to interact with functional groups on GO (Fig. 6b). It is
known that the presence of heavy metal ions could compress the
double layer, thereby neutralizing the negative charges on the sur- 100
face of carbon materials [31], which may relieve the electronic
repulsion between the negatively charged GO and ionized
1-naphthol. It has been demonstrated that hydration shell could 10
form around GO nanosheets due to the extremely hydrophilic sur- 1 10 100
face of GO, which would hinder the H bonding and p–p interaction Equilibrium Concentration, (mg/L)
between polar organics and GO [22]. Because Cd2+ with a small
1000000
hydrated radius (4.26 Å) [45] showed strong affinity to GO, the 2+
(c) Cd
adsorption of Cd2+ might decrease the effective size of hydration
shells of dense water around GO [31], and mitigate the competitive 100000
adsorption of water molecules, thus facilitating the
surface-bridging, H-bonding and p–p interaction between
1-naphthol and GO. This would enhance the adsorption of 10000
Kd, (L/kg)

1-naphthol onto the hydrophilic surfaces of GO.

The uptake of 1-naphthol on graphene materials was dependent
on the pH. For CRG and ARG, the adsorption of 1-naphthol
increased with increasing pH and reached a prominent adsorption
maximum as the pH approached the pKa (9.34) of 1-naphthol.
Other studies have also observed analogous phenomena for polar
organic compounds adsorbed on graphite and carbon nanotubes
[40,46]. This could be attributed to the n–p electron
donor-accepter (EDA) interaction between electron-depleted sites
on carbon nanomaterials and organic compounds (Fig. 6c), which
contain oxygen or nitrogen with lone electron pairs [32,47]. The
AOH group on 1-naphthol dissociates to AO under high pH con-
ditions. As a result, the electron-donating strength improves,
resulting in the proposed n–p EDA interaction. Because the aro-
maticity of ARG was higher than that of CRG, both p–p and n–p
EDA interactions between ARG and 1-naphthol were stronger than
that of CRG, as indicated by the significantly increased uptake of
1-naphthol by ARG within the pH range of 2–10 compared with
that observed with CRG. Additionally, the zeta potentials of CRG
and ARG were negative at pH 12 (Fig. 1f). The strong electronic
repulsion between the negatively charged CRG and dissociated
1-naphthol at pH 12 largely suppressed the uptake of
1-naphthol, but was slightly lower for ARG, suggesting that the
strong interactions between ARG and 1-naphthol could more effec-
tively offset the electrostatic repulsion. Although the SAs and
1000
100
10
0.01 0.1 1 10 100
Equilibrium Concentration. (mg/L)
Fig. 7. The distribution coefficients (Kd) with equilibrium concentrations for
adsorption of naphthalene (a), 1-naphthol (b) and Cd2+ (c) onto CRG, ARG and GO.
geometries were quite different, CRG and ARG exhibited compara-
ble adsorption capacities toward 1-naphthol. In contrast, the
adsorption of 1-naphthol onto GO decreased with increasing pH
(2 to 7). The aromatic adsorption sites on GO were unavailable in
the aqueous solution for the p–p interaction and n–p EDA interac-
tion. At low pH values, the surface of GO was electron depleted and
could serve as a Lewis acid. Correspondingly, 1-naphthol could
serve as a Lewis base, and thus, the adsorption of 1-naphthol onto
GO was stronger at low pH values because of the more electron
depleted GO [16].
388 J. Wang, B. Chen / Chemical Engineering Journal 281 (2015) 379–388
4. Conclusions
The adsorption and coadsorption of polar and nonpolar organics
in aqueous solutions with or without the presence of heavy metal
ions onto graphene materials are highly dependent by the contents
of the oxygen-containing functional groups of graphene
nanosheets. Multiple interaction mechanisms, such as p–p,
cation–p and n–p EDA interactions, H-bonds, and hydrophobic
effects, are involved in the adsorption and coadsorption processes.
For a wide pH range, GO, CRG and ARG showed excellent adsorp-
tion capacities for Cd2+, naphthalene and 1-naphthol, respectively.
By regulating the oxygen-containing functional groups on gra-
phene nanosheets, graphene materials have great potential in pol-
lution control applications, even in complex solutions of organic
and inorganic pollutants.
Acknowledgments
This project was supported by the National Science Foundation
for Distinguished Young Scholars of China (Grant 2142500268), the
National Basic Research Program of China (Grant 2014CB441106),
the National Natural Science Foundation of China (Grant
21277120).
References
[1] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.V.
Grigorieva, A.A. Firsov, Electric field effect in atomically thin carbon films,
Science 306 (2004) 666–669.
[2] K.S. Novoselov, V.I. Fal’ko, L. Colombo, P.R. Gellert, M.G. Schwab, K. Kim, A
roadmap for graphene, Nature 490 (2012) 192–200.
[3] V. Georgakilas, M. Otyepka, A.B. Bourlinos, V. Chandra, N. Kim, K.C. Kemp, P.
Hobza, R. Zboril, K.S. Kim, Functionalization of graphene: covalent and non-
covalent approaches, derivatives and applications, Chem. Rev. 112 (2012)
6156–6214.
[4] Q. He, S. Wu, S. Gao, X. Cao, Z. Yin, H. Li, P. Chen, H. Zhang, Transparent, flexible,
all-reduced graphene oxide thin film transistors, ACS Nano 5 (2011) 5038–
5044.
[5] J. Yan, Z. Fan, W. Sun, G. Ning, T. Wei, Q. Zhang, R. Zhang, L. Zhi, F. Wei,
Advanced asymmetric supercapacitors based on Ni(OH)2/graphene and porous
graphene electrodes with high energy density, Adv. Funct. Mater. 22 (2012)
2632–2641.
[6] J.L. Xie, C.X. Guo, C.M. Li, Construction of one-dimensional nanostructures on
graphene for efficient energy conversion and storage, Energy Environ. Sci. 7
(2014) 2559–2579.
[7] S. Stankovich, D.A. Dikin, R.D. Piner, K.A. Kohlhaas, A. Kleinhammes, Y. Jia, Y.
Wu, S.T. Nguyen, R.S. Ruoff, Synthesis of graphene-based nanosheets via
chemical reduction of exfoliated graphite oxide, Carbon 45 (2007) 1558–1565.
[8] W. Lv, D. Tang, Y. He, C. You, Z. Shi, X. Chen, C. Chen, P. Hou, C. Liu, Q. Yang,
Low-temperature exfoliated graphenes: vacuum-promoted exfoliation and
electrochemical energy storage, ACS Nano 3 (2009) 3730–3736.
[9] R.S. Weatherup, B. Dlubak, S. Hofmann, Kinetic control of catalytic CVD for
high-quality graphene at low temperatures, ACS Nano 6 (2012) 9996–10003.
[10] M. Choucair, P. Thordarson, J.A. Stride, Gram-scale production of graphene
based on solvothermal synthesis and sonication, Nat. Nanotechnol. 4 (2008)
30–33.
[11] Y. Xu, Q. Wu, Y. Sun, H. Bai, G. Shi, Three-dimensional self-assembly of
graphene oxide and DNA into multifunctional hydrogels, ACS Nano 4 (2010)
7358–7362.
[12] Q. Fang, Y. Shen, B. Chen, Synthesis, decoration and properties of three-
dimensional graphene-based macrostructures: a review, Chem. Eng. J. 264
(2015) 753–771.
[13] K.C. Kemp, H. Seema, M. Saleh, N.H. Le, K. Mahesh, V. Chandra, K.S. Kim,
Environmental applications using graphene composites: water remediation
and gas adsorption, Nanoscale 5 (2013) 3149–3171.
[14] Y. Shen, Q. Fang, B. Chen, Environmental applications of three-dimensional
graphene-based macrostructures: adsorption, transformation, and detection,
Environ. Sci. Technol. 49 (2015) 67–84.
[15] J. Wang, Z. Chen, B. Chen, Adsorption of polycyclic aromatic hydrocarbons by
graphene and graphene oxide nanosheets, Environ. Sci. Technol. 48 (2014)
4817–4825.
[16] G. Zhao, L. Jiang, Y. He, J. Li, H. Dong, X. Wang, W. Hu, Sulfonated graphene for
persistent aromatic pollutant, Adv. Mater. 23 (2011) 3959–3963.
[17] J. Zhao, Z. Wang, Q. Zhao, B. Xing, Adsorption of phenanthrene on multilayer
graphene as affected by surfactant and exfoliation, Environ. Sci. Technol. 48
(2014) 331–339.
[18] K. Yang, J. Wang, B. Chen, Facile fabrication of stable monolayer and few-layer
graphene nanosheets as superior sorbents for persistent aromatic pollutant
management in water, J. Mater. Chem. A 2 (2014) 18219–18224.
[19] Z. Pei, L. Li, L. Sun, S. Zhang, X. Shao, S. Yang, B. Wen, Adsorption characteristics
of 1,2,4-trichlorobenzene, 2,4,6-trichlorophenol, 2-naphthol and naphthalene
on graphene and graphene oxide, Carbon 51 (2013) 156–163.
[20] X. Wang, S. Huang, L. Zhu, X. Tian, S. Li, H. Tang, Correlation between the
adsorption ability and reduction degree of graphene oxide and tuning of
adsorption of phenolic compounds, Carbon 69 (2014) 101–112.
[21] X. Chen, B. Chen, Macroscopic and spectroscopic investigations of the
adsorption of nitroaromatic compounds on graphene oxide, reduced
graphene oxide, and graphene nanosheets, Environ. Sci. Technol. 49 (2015)
6181–6189.
[22] J. Barkauskas, I. Stankevicien, J. Daksevic, A. Padarauskas, Interaction between
graphite oxide and Congo red in aqueous media, Carbon 49 (2011) 5373–5381.
[23] Q. Fang, B. Chen, Self-assembly of graphene oxide aerogels by layered double
hydroxides cross-linking and their application in water purification, J. Mater.
Chem. A 2 (2014) 8941–8951.
[24] Y. Jiang, W.N. Wang, P. Biswas, J.D. Fortner, Facile aerosol synthesis and
characterization of ternary crumpled graphene-TiO2-magnetite
nanocomposites for advanced water treatment, ACS Appl. Mater. Interfaces 6
(2014) 11766–11774.
[25] Y. Shen, B. Chen, Sulfonated graphene nanosheets as a superb adsorbent for
various environmental pollutants in water, Environ. Sci. Technol. 49 (2015)
7364–7372.
[26] S. Dong, X. Dou, D. Mohan, C.U. Pittman, J. Luo, Synthesis of graphene oxide/
schwertmannite nanocomposites and their application in Sb(V) adsorption
from water, Chem. Eng. J. 270 (2015) 205–214.
[27] G. Zhao, J. Li, X. Ren, C. Chen, X. Wang, Few-layered graphene oxide nanosheets
as superior sorbents for heavy metal ion pollution management, Environ. Sci.
Technol. 45 (2011) 10454–10462.
[28] Y. Sun, D. Shao, C. Chen, S. Yang, X. Wang, Highly efficient enrichment of
radionuclides on graphene oxide-supported polyaniline, Environ. Sci. Technol.
47 (2013) 9904–9910.
[29] W. Gao, M. Majumder, L.B. Alemany, T.N. Narayanan, M.A. Ibarra, B.K. Pradhan,
P.M. Ajayan, Engineered graphite oxide materials for application in water
purification, ACS. Appl. Mater. Interfaces 3 (2011) 1821–1826.
[30] Y. Chen, Q. Zhang, L. Chen, H. Bai, L. Li, Basic aluminum sulfate@graphene
hydrogel composites: preparation and application for removal of fluoride, J.
Mater. Chem. A 1 (2013) 13101–13110.
[31] J. Chen, D. Zhu, C. Sun, Effect of heavy metals on the sorption of hydrophobic
organic compounds to wood charcoal, Environ. Sci. Technol. 41 (2007) 2536–
2541.
[32] J. Zhao, Z. Wang, J.C. White, B. Xing, Graphene in the aquatic environment:
adsorption, dispersion, toxicity and transformation, Environ. Sci. Technol. 48
(2014) 9995–10009.
[33] W.S. Hummers, R.E. Offeman, Preparation of graphitic oxide, J. Am. Chem. Soc.
80 (1958) 1339.
[34] I. Chowdhury, M.C. Duch, N.D. Mansukhani, M.C. Hersam, D. Bouchard,
Colloidal properties and stability of graphene oxide nanomaterials in the
aquatic environment, Environ. Sci. Technol. 47 (2013) 6288–6296.
[35] F.A. Carey, Organic Chemistry, McGraw-Hill, New York, 2005.
[36] X. Cheng, A.T. Kan, M.B. Tomson, Naphthalene adsorption and desorption from
aqueous C60 fullerene, J. Chem. Eng. Data 49 (2004) 675–683.
[37] B. Chen, Z. Chen, Sorption of naphthalene and 1-naphthol by biochars of
orange peels with different pyrolytic temperatures, Chemosphere 76 (2009)
127–133.
[38] G.D. Sheng, D.D. Shao, X.M. Ren, X.Q. Wang, J.X. Li, Y.X. Chen, X.K. Wang,
Kinetics and thermodynamics of adsorption of ionizable aromatic compounds
from aqueous solutions by as-prepared and oxidized multiwalled carbon
nanotubes, J. Hazard. Mater. 178 (2010) 505–516.
[39] M.M. Rao, A. Ramesh, G.P.C. Rao, K. Seshaiah, Removal of copper and cadmium
from the aqueous solutions by activated carbon derived from Ceiba pentandra
hulls, J. Hazard. Mater. 129 (2006) 123–129.
[40] S. Yang, Z. Guo, G. Sheng, X. Wang, Investigation of the sequestration
mechanisms of Cd(II) and 1-naphthol on discharged multi-walled carbon
nanotubes in aqueous environment, Sci. Total Environ. 420 (2012) 214–221.
[41] F. Lian, Z. Song, Z. Liu, L. Zhu, B. Xing, Mechanistic understanding of
tetracycline sorption on waste tire powder and its chars as affected by Cu2+
and pH, Environ. Pollut. 178 (2013) 264–270.
[42] J. Kim, L.J. Cote, F. Kim, W. Yuan, K.R. Shull, J. Huang, Graphene oxide sheets at
interfaces, J. Am. Chem. Soc. 132 (2010) 8180–8186.
[43] P. Lazar, F. Karlicky, P. Jurečka, M. Kocman, E. Otyepkova, K. Šafářova, M.
Otyepka, Adsorption of small organic molecules on graphene, J. Am. Chem. Soc.
135 (2013) 6372–6377.
[44] W. Gao, L.B. Alemany, L. Ci, P.M. Ajayan, New insights into the structure and
reduction of graphite oxide, Nat. Chem. 1 (2009) 403–408.
[45] E.R. Nightingale, Phenomenological theory of ion solvation. Effective radii of
hydrated ions, J. Phys. Chem. 63 (1959) 1381–1387.
[46] F. Xiao, J.J. Pignatello, Effect of adsorption nonlinearity on the pH adsorption
profile of ionizable organic compounds, Langmuir 30 (2014) 1994–2001.
[47] W. Chen, L. Duan, L. Wang, D. Zhu, Adsorption of hydroxyl- and amino-
substituted aromatics to carbon nanotubes, Environ. Sci. Technol. 42 (2008)
6862–6869.