Journal of Industrial and Engineering Chemistry 26 (2015) 354363

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Journal of Industrial and Engineering Chemistry

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A facile hydrothermal synthesis, adsorption kinetics and isotherms to

Congo Red azo-dye from aqueous solution of NiO/graphene
nanosheets adsorbent
Xinshan Rong a, Fengxian Qiu b,*, Jiao Qin b, Hao Zhao b, Jie Yan b, Dongya Yang b
a
b

School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013, China
School of Chemistry and Chemical Engineering, Jiangsu University, 212013 Zhenjiang, China

A R T I C L E I N F O

Article history:
Received 8 February 2014
Received in revised form 22 September 2014
Accepted 9 December 2014
Available online 18 December 2014
Keywords:
NiO/graphene
Congo Red
Adsorption
Kinetic
Isotherm

A B S T R A C T

A series of NiO/graphene nanosheets adsorbents (NGNS) were synthesized by a facile hydrothermal

method, and characterized by UVvis, XRD, TG, TEM, HRTEM, Raman, SAED and XPS methods. The NGNS
was applied to deal with wastewater solution containing Congo Red (CR); and adsorption efciency
attained 99.56% at optimum condition. The adsorption kinetic and isotherm of adsorbent toward CR
were investigated. The results indicated that pseudo second-order kinetic model and the equilibrium
data were well tted by RedlichPeterson model. The adsorbent can be separated from system
effectively and easily. The prepared adsorbent has potential application for the wastewater treatment
containing CR azo-dye.
2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction
Among the different pollutants released to the environment
from industries, dyes can be considered as one of the most
dangerous contaminants and about 15% of the annual output
enters into the environment through industrial annually, resulting
in large amounts of wastewater [1,2]. According to statistics, the
total dye consumption of the textile industry worldwide are in
excess of 107 kg/year [3] and over 4.4  106 m3 of aqueous waste
and dye efuents with persistent color and high BOD (biochemical
oxygen demand) loading is being discharged every day in
Mainland China [4]. The major methods used in dye removing
include degradation, coagulation, chemical oxidation, biological
treatment, ion exchange and adsorption [59]. Particularly,
adsorption process has become one of the most effective and
comparable low-cost methods for the removal of dyes from
aqueous solutions.
Congo Red (CR) [1-naphthalene sulfonic acid, 3,30-(4,40biphenylenebis(azo))bis(4-amino-) disodium salt, seen as Fig. 1]
is a typical and the rst synthetic dye of anionic azo dyes, which is
synthesized by coupling tetrazotised benzidine with two mole-

* Corresponding author. Tel.: +86 51188791800; fax: +86 51188791800.

E-mail address: fxqiuchem@163.com (F. Qiu).

cules of napthionic acid [10,11]. CR is used in the cellulose

industries such as cotton textile, wood pulp and paper [12]. And
these dyes belong to the class of aromatic and heterocyclic
compounds with the azo bond (N5
5N) which are recalcitrant and
even possess carcinogenic property [13]. Structural stability of CR
is the major challenge for its removal from wastewater treatment
[14], for which it is a benzidine-based azo dye with a complex
chemical structure and is highly soluble in aqueous solution.
Adsorption is an ideal way for its high removal efciency and
easy operation. Many kinds of adsorbents have been reported, such
as activated carbon [15], kaolin [16], and montmorillonite clay
[17], which can provide a large surface area to remove efciently
color from water. Nickel oxide (NiO), as a p-type wide band gap
semiconductor, is a very important functional oxide; and it has
been widely used in various elds, including catalysis, battery
anode, lithium ion batteries, fuel cells and electrochemical
capacitors [1821]. Wan et al. [22] reported process of NiO
nanoparticles in the degradation of methylene blue and the effect
of different alkali reactants on the photocatalytic activity in the
synthesis process. Li et al. [23] reported a facile one-step and
effective electrochemical strategy to synthesize graphene/NiO
nanocomposites as efcient electrocatalyst for glucose and
methanol. Hwang et al. [24] reported that a graphene/NiO
composite was prepared by simple chemical precipitation as
anode material for lithium ion batteries. Jiang et al. [25] reported

http://dx.doi.org/10.1016/j.jiec.2014.12.009
1226-086X/ 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

X. Rong et al. / Journal of Industrial and Engineering Chemistry 26 (2015) 354363

355

Fig. 1. Chemical structure of Congo Red.

that a new porous graphene/NiO was prepared successfully by

hydrothermal method and its application in electrochemical
capacitors. In addition to the above applications, nickel materials
have attracted considerable research interest in the application of
adsorption in recent years. Cheng et al. [26] reported synthesis of
hierarchical Ni(OH)2 and NiO with porous structures and its
application of adsorption for Congo Red.
In this work, a novel NiO/graphene nanosheets adsorbent
(NGNS) was prepared by a facile hydrothermal method using
nickel acetate as precursors of NiO, urea as precipitating agent,
PEG-200 as template agent and graphene oxide (GO) as precursors
of graphene. The structure, surface morphology and chemical
composition of NGNS were investigated by UVvis, XRD, Raman,
TEM, HRTEM, SAED and XPS. The obtained nickel material could
shorten the equilibrium time by the addition of graphene, which
can adsorb the CR azo-dye molecules via pp conjugation due to
its huge surface area and the ring structure resembling of benzene
[27,28]. To the best our knowledge, this is the rst time that the
obtained NiO/graphene nanosheets adsorbent is reported.

Synthesis of NiO/graphene nanosheets adsorbent

Nickel acetate (Ni(CH3COO)24H2O, 99%), urea (H2NCONH2,

99%), polyethylene glycol (PEG-200) were purchased from Aladdin
Chemical Reagent Company. Graphite powder (99%), potassium
permanganate (KMnO4, 98%), sulfuric acid (H2SO4, 98%), hydrogen
peroxide (H2O2, 30%), sodium nitrate (NaNO3, 99%) and Congo Red
(CR, 99%, C.I. = 22,120) were purchased from Shanghai Chemical
Reagent Co. Ltd., China All reagents were used without further
purication.

The synthesis of the NiO/graphene nanosheets adsorbent

(NGNS) by a facile hydrothermal method contained three steps,
as described in Scheme 1. In the rst step, 5.0 g of nickel acetate
as precursors of NiO, 4.8 g of urea as precipitating agent, 2.0 g of
PEG-200 as template agent and 43 mL H2O were added into threenecked ask under followed by stirring for 2 h at room temperature to obtain solution B. Then, the solution A as precursors of
graphene was added into solution B with vigorous stirring for
30 min and the mixture was transferred to Teon-sealed autoclave
and maintained at 160 8C for 12 h. After reaction, the resulting
composite was separated by centrifugation, washed with deionized water and ethanol for several times until pH = 7.0, and nally
dried at 80 8C under vacuum to get precursor Ni(OH)2/graphene.
The third step, as-prepared Ni(OH)2/graphene were calcined at
300 8C for 4 h to get the nal product NiO/graphene nanosheets
adsorbent (NGNS). For comparison, pure NiO was prepared in the
absence of GO according to the above method; and graphene (GR)
was prepared in the absence of solution B by the hydrothermal
process.
In this work, a series of NiO/graphene nanosheets adsorbents
with adding different mass content of GO (m(GO)/m(Nickel acetate)*100%mass GO to mass of nickel acetate) of 0.2%, 0.4%, 0.6%, 0.8%,
1.0%, and 1.2% were expressed as NGNS-1, NGNS-2, NGNS-3,
NGNS-4, NGNS-5 and NGNS-6, respectively. For comparison, pure
NiO was prepared without the presence of GO according to
the above method, and graphene (GR) was prepared without the
presence of solution B by the hydrothermal process.
In this work, varying the proportion of GO, a series of NiO/
graphene nanosheets adsorbents were prepared with different GO
mass content of 01.2%, as shown in Table 1.

Preparation of graphene oxide solution

Characterizations

Graphene oxide (GO) was prepared from natural graphite

powder by a modied Hummers method. In a typical procedure,
23 mL of concentrated H2SO4 was added in the 250 mL ask which
was cooled to 0 8C in an ice bath, and then 1.0 g of graphite and
1.0 g of NaNO3 were added to the ask slowly, respectively. Under
vigorous stirring, 3.0 g of KMnO4 was added to the reaction
suspension and kept in an ice bath for 1 h. Later, the ice bath was
removed and the reaction mixture was heated to 35 8C for 3 h for
gas releasing under continuous stirring. Thereafter, 46 mL of
deionized water was added slowly and the reaction temperature
was raised to 98 8C for 2 h. Then, the resultant bright-yellow
suspension was terminated by addition of 140 mL deionized water,
followed by 10 mL of hydrogen peroxide solution (H2O2, 30%). For
purication, the solid product was separated by centrifugation and
washed with 5% hydrogen chloride solution, and deionized water
until pH = 7.0. Finally, the powder was vacuum-dried at 60 8C for
12 h. The graphene oxide (GO) was obtained.
A certain amount of GO was dissolved in a solution of H2O
(80 mL) and ethanol (40 mL) using ultrasonic treatment for 2 h to
obtain GO solution, expressed as solution A.

The phase of the powers was identied by an X-ray

diffractometer (XRD, Shimadzu LabX-6000) with a Cu Ka radiation
at 40 kV and 30 mA over the 2u range of 15858 at a scanning speed
of 48/min with a sampling angle interval of 0.048. Thermogravimetric analysis (TGA) of the adsorbents were performed on a
Netzsch instrument (STA 449C, Netzsch, Seligenstadt, Germany) at
a heating rate of 10 8C/min. Raman test was carried out using
Thermo Scientic DXR Smart Raman spectrometer equipped with a
532 nm excitation. UVvis spectra were formed at room temperature on an UVvis spectrophotometer (UV-3010). Transmission
electron microscopy (TEM, PHI-Tecnai 12) was used to characterize the size and shape of the adsorbent. High resolution
transmission electron microscopy (HRTEM) and selected area
electron diffraction (SAED) were performed on a Philips CM200
eld-emission gun transmission electron microscope (FEI-TecnaiG2F30S-Twin) operating at 197 kV. The X-ray photoelectron
spectroscopy (XPS) of sample was performed using an XPS
spectrometer (XPS, ESCALAB250) with an Al Ka monochromatized
source. The nitrogen adsorption and desorption isotherms were
measured at 196 8C using a NDVA2000e analytical system made

Materials and methods

Materials

X. Rong et al. / Journal of Industrial and Engineering Chemistry 26 (2015) 354363

356

by Quntachrome Corporation (USA). The specic surface area was

calculated by BrunauerEmmettTeller (BET) method.
Adsorption experiment
In the adsorption experiment, a typical process was as follows:
different mass of adsorbent was added into 100 mL of CR solution
with initial concentration of 20 mg/L (pH = 7). The resulting
mixture was continuously stirred (rotation speed of 1000 rpm)
in a home-made lucifugal apparatus at pre-settled temperature
until equilibrium was reached. The solution was analyzed by UV
vis absorption at the wavelength of 498 nm. The adsorption
efciency (D) of solution was calculated according to the following
Eq. (1):
D%

Co  Ct
 100
Co

(1)

where Co and Ct are the concentration of the CR azo-dye solution in

the absence and in the presence of NGNS adsorbent, respectively.
The amount of CR adsorbed onto the samples was determined
according to the change of concentration before and after
adsorption. The adsorption amount of CR onto the NGNS was
calculated according to the following Eq. (2):
qt

VC o  C t
m

(2)

where qt is the amount of adsorbed CR dye by NGNS (mg/g); Co and

Ct are the initial and temporary concentrations of CR respectively
(mg/L); V is the volume of the CR dye solution (L); and m is the mass
of the NGNS adsorbent (g). The amount of CR at equilibrium qe (mg/
g) on the adsorbent samples was calculated from the following
Eq. (3):
qe

VC o  C e
m

(3)

where qe is the adsorbed CR amount at equilibrium and Ce is the

equilibrium CR concentration.
Results and discussion
Material characterization
The crystal phase and structure information of the products
were analyzed by XRD; and the XRD patterns of graphene (a),
pure NiO (b) and NGNS-5 (c) are shown in Fig. 2. As can be seen
from Fig. 2(a), it shows a typical 2u peak for graphene at about
24.68 (0 0 2), corresponding to d-spacing of about 0.37 nm.
Although the d-spacing is higher than that of natural graphite
(about 0.33 nm), the values are similar for pristine graphene and
the composites, suggesting that the NiO nanocrystallites have not
greatly affected the orientation of the graphene layers [2931]. For
XRD pattern of NiO (b), regular diffraction peaks appearing at 2u
values of 37.0, 43.0, 62.8, 75.4 and 79.48 correspond to the crystal
planes of NiO of (1 1 1), (2 0 0), (2 2 0), (2 2 2) and (3 1 1),
respectively [32,33]. Compared with the pure NiO, an additional
small and light broad diffraction peak appears at about 24.68 for
XRD pattern of NGNS-5 (c), corresponding to the (0 0 2) diffraction
peak of the disorderedly stacked graphene sheets, which is clearly

Scheme 1. The synthetic route of NGNS adsorbent.

Table 1
Effect of proportion of GO on the adsorption efciency.
Adsorbents

NiO

NGNS-1

NGNS-2

NGNS-3

NGNS-4

NGNS-5

NGNS-6

Proportion of GOa (%)

D (%)

0.0
46.18

0.2
91.56

0.4
93.87

0.6
95.91

0.8
98.14

1.0
99.56

1.2
98.85

mGO
Proportion of GO% mNickel
 100.
acetate

X. Rong et al. / Journal of Industrial and Engineering Chemistry 26 (2015) 354363

Fig. 2. XRD patterns of graphene (a), pure NiO (b) and NGNS-5 (c).

appeared in the inset. These results suggest that the adsorbent is

composed of graphene and NiO.
Raman spectroscopy is a powerful non-destructive technique to
study carbonaceous materials such as graphene and also for
examining the ordered and disordered crystal structures. Raman
spectra of graphene (a), NiO (b) and NGNS-5 (c) are shown in
Fig. 3. As can be seen from Fig. 3(a), the two strong peaks of the Dband (1350 cm1) and G-band (1592 cm1) were observed,
which corresponds to the diamondoid and graphitic graphene
structures, respectively [34]. It is well known that G-bands at
around 1592 cm1 could be attributed to the characteristic ordered
graphitic carbon, and conrmed the presence of sp2-bonded
carbon atoms in a two-dimensional hexagonal graphene layer. The
D-band at around 1350 cm1 could be assigned to the disordered
graphitic carbon and the presence of sp3 defects. From Fig. 3(b),
four Raman peaks located at about 378, 526, 695 and 1057 cm1
are observed, corresponding to the shaking peaks of NiO [25]. The

357

former two peaks could be attributed to the rst-order transverse

optical (1 TO) and longitudinal optical (1 LO) phonon modes of NiO
respectively, which is classied as NiO lattice vibration. The peaks
at 700 and 1090 cm1 could be assigned to two-phonon (2P)
modes (2 TO mode at 695 and 2 LO mode at 1057 cm1) of NiO
[35]. As shown in Fig. 3(c), all the peaks of graphene and NiO are
observed in the spectrum of NGNS-5, suggesting that the NiO/
graphene adsorbent were obtained and the result is consistent
with the XRD results.
The surface chemical states, composition change and interaction of NiO/graphene were investigated by X-ray photoelectron
spectroscopy (XPS). XPS spectrum of NGNS-5 (a), the XPS highresolution spectra at the C1s (b), O1s (c) and Ni2p regions (d) of
NGNS-5 are shown in Fig. 4. From Fig. 4(a), it can be seen that the
peaks shown in the spectrum arise from the spectral lines of C 1s, O
1s and Ni 2p. The corresponding peaks appear in the spectrum to
various element, indicating the formation of NiO/graphene. As can
be seen from Fig. 4(b), C 1s XPS spectrum of NGNS-5 adsorbent and
its tting curves with three deconvoluted peaks at 284.6, 286.8 and
287.8 eV, which are assigned to CC/C5
5C, CO and C5
5O
[36,37]. The peak at 284.6 eV represents the non-oxygenated
carbon (sp2 hybridized CC/C5
5C bonds) of the benzene ring. The
binding energies peaks at 286.8 and 287.8 eV deduce the carbon
atoms attached with oxygen atoms in the form of CO and C5
5O
respectively. As shown in Fig. 4(c), the peaks of tting curves for
O1s spectrum at 530.1, 531.3, 532.7 and 534.3 eV correspond to
NiO bonds, OH bonds, CO bonds and H2O adsorbed on the
surface of PNGA-5 [38]. Fig. 4(d) displays Ni 2p spectrum of NGNS5, from which the two main peaks were identied at 855.9 and
874.4 eV, corresponding to Ni (2p 3/2) and Ni (2p 1/2). In addition,
a satellite peak of Ni (2p 3/2) appears at 862.6 eV and the results
are all similar to the previous reported [34,39].
The morphology and microstructure of NGNS-5 was obtained
by TEM measurements. TEM image (a), a low magnication of
quasi-hexagonal structure (b), HRTEM (c) and SAED pattern (d) of
NGNS-5 are shown in Fig. 5. As shown in Fig. 5(a), the presence of
ring-like sheets for NiO and two-dimensional transparent sheet
structure with wrinkles for graphene can be seen. As can be seen
from Fig. 5(b), a low magnication of ring-like sheet is found
hexagonal and quasi-hexagonal structures of adjacent edges of
1208, liking benzene ring [40]. To further investigate the structure
and morphology of NGNS-5, HRTEM and SAED patterns were used.
As shown in Fig. 5(c), the lattice fringe is observed obviously, and
the lattice spacing (0.230.25 nm, 0.24 nm) which can be
indexed as the (2 0 0) plane of NiO [41]. From Fig. 5(d), the
selected area electron diffraction (SAED) pattern is attributed to
(1 1 1), (2 0 0), and (2 2 0) diffraction of NiO respectively
[30,42]. Existence of the (1 1 1) planes is also evident from the
high resolution image (Fig. 5(c)) of NiO showing the corresponding
lattice fringes.
TG curves of pure NiO (a), NGNS-1 (b) and NGNS-5 (c) are
shown in Fig. 6. As shown in Fig. 6(a) and (b), two steps are
observed obviously. For all samples, the rst mass loss of 0.30%
might be ascribed to the loss of the absorbed water and adsorbed
O2 from the room temperature to 200 8C. When the temperature
comes to 500 8C, the corresponding second mass loss of NGNS-1 (b)
and NGNS-5 (c) is 1.85% and 2.45%, respectively. This is mainly due
to the decompositions of graphene component in NGNS samples;
and the residual mass content is NiO component.
Adsorption applications

Fig. 3. Raman spectra of graphene (a), NiO (b) and NGNS-5 (c).

A series of adsorption studies on the effect of proportion of GO,

adsorbent dose, contact time were conducted on NGNS samples
while the CR dye solution was xed at CR concentration of 20 mg/L,
pH of 7 and temperature of 25 8C.

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X. Rong et al. / Journal of Industrial and Engineering Chemistry 26 (2015) 354363

Fig. 4. XPS spectrum of NGNS-5 (a), XPS high-resolution spectra at the C1s (b), O1s (c) and Ni2p regions (d) of NGNS-5.

The effect of proportion of GO on the adsorption efciency was

obtained at the xed temperature of 25 8C, time of 180 min and
adsorbent dose of 50 mg. The results are listed in Table 1. As can be
seen from Table 1, the adsorption efciency of all NGNS samples is
better than that of pure NiO, suggesting that NGNS has a higher
removal ability of CR dye solution. This can be explained that
graphene exhibits huge surface area, good chemical stability and
graphitized basal plane structure, thus providing strong pp
interactions with the aromatic moieties present in many dyes
[43]. The BET specic surface area of NiO, NGNS-1, NGNS-2, NGNS3, NGNS-4, NGNS-5 and NGNS-6 is 19.21, 21.42, 22.69, 24.12,
25.34, 26.13 and 26.10 m2/g, respectively. The result indicates that
the surface area of sample increases with the increasing graphene
content, which could be attributed to the huge surface area of
graphene. When the proportion of GO is 1.0%, the adsorption
efciency reaches the maximum value, which shows the highest
removal performance of CR. However, when proportion of GO is
1.2%, the adsorption efciency of NGNS-6 has a little decrease
compared with that of NGNS-5, this is mainly because the higher
content of GO, the more content of GR could exit in the NGNS
composite, which would decrease the surface area of NiO. Hence,
the NGNS-5 was chosen for further experiments.
The effect of adsorbent dose on the adsorption efciency was
obtained at the xed sample of NGNS-5, temperature of 25 8C and
time of 180 min. The results are shown in Fig. 7. As can be seen
from Fig. 7, the adsorption efciency increases with the increasing
the amount of NGNS-5 and remains almost constant (99.56%) after

increasing up to 50 mg. This can be attributed to increasing

adsorbent surface area and availability of more adsorption sites
[44], which is positively charged and CR is an anionic dye [45,46]. It
is considered that the adsorption efciency has reached 99.56%
with the adsorbent dose of 50 mg, but there is an extremely small
distance to 99.75% with the adsorbent dose of 60 mg. For
comprehensive consideration, the adsorbent dose of 50 mg was
chosen as the optimized parameter.
Fixed the sample of NGNS-5, temperature of 25 8C and
adsorbent dose of 50 mg, the effect of contact time on adsorption
efciency is shown in Fig. 8. From Fig. 8, it can be seen that the
adsorption efciency increases rapidly in the initial stages with an
increase of the contact time, especially for the former 20 min, and
then gradually increases until equilibrium. This change in
adsorption efciency is attributed to the fact that more vacant
adsorption sites are available at the initial stage, while after a
period of time, the remaining vacant adsorption sites become less
and are difcult to occupy because of repulsive forces between the
solute molecules on the solid and bulk phases [47]. At the time of
180 min, the adsorption process reaches a dynamic equilibrium
and the adsorption efciency remains approximately a constant
(99.56%), and the color of CR aqueous solution changes from red to
colorless and transparent, as shown in the inset of Fig. 8. Therefore,
time of 180 min was chosen for the further research.
In addition, Fig. 9 shows absorption spectra of a solution of CR
(20 mg/L, 100 mL) in the presence of NGNS-5 (50 mg) at different
time. According to the absorption spectra of CR solution at 0 min,

X. Rong et al. / Journal of Industrial and Engineering Chemistry 26 (2015) 354363

359

Fig. 5. TEM image (a), a low magnication of quasi-hexagonal structure (b), HRTEM (c) and SAED pattern (d) of NGNS-5.

20 min, 100 min and 180 min, it can be seen that the there is a huge
change between the absorbance at 0 min and 20 min, and there is
no obvious absorption peak at 180 min. The respond of absorption
spectra is consistent with relationship of between adsorption
efciency of CR and contact time.
Based on the above studies of experimental factors, the
optimum conditions of adsorption Congo Red dye from aqueous
were obtained as follows: the proportion of GO of 1.0%, adsorbent
dose of 50 mg and time of 180 min at room temperature of 25 8C.
Under the optimal conditions, the result indicates that prepared
NGNS-5 has adsorption efciency of 99.56%, and has potential
application for the wastewater treatment containing CR.

Adsorption kinetics study

In order to examine the diffusion mechanism involved during
the adsorption process, various kinetic models were tested i.e.
pseudo-rst order model, pseudo-second-order model, the Elovich
model and the MorrisWeber model, respectively.
The pseudo-rst order equation [48] described liquidsolid
phase adsorption systems, and it is the earliest known kinetic
model describing the adsorption rate based on the adsorption
capacity. The pseudo-rst-order kinetic equation is expressed as
the following Eq. (4):
logqe  qt logqe 

Fig. 6. TG curves of pure NiO (a), NGNS-1 (b) and NGNS-5 (c)


k1
t
2:303

(4)

Fig. 7. Effect of adsorbent dose (NGNS-5, mg) on the adsorption efciency.

X. Rong et al. / Journal of Industrial and Engineering Chemistry 26 (2015) 354363

360

The MorrisWeber equation [51] is generally applied to

evaluate the intra-particle rate constant, and expressed as the
following Eq. (7):
p
qt Rid  t ci
(7)
where qt is the sorption capacity at equilibrium (mg/g) at time t
(min) and Rid is the rate constant of intra-particle transport.
Linear t of kinetics models of Pseudo-rst-order kinetic model
(a), Pseudo-second-order kinetic model (b), Elovich model (c) and
MorrisWeber model (d) are shown in Fig. 10 and the corresponding kinetic parameters are listed in Table 2. As can be seen from
Fig. 10, the pseudo-second-order kinetic model gives the best t to
the experimental data. The correlation coefcient (R2, 0.999) of the
pseudo-second-order kinetic model is higher than those of pseudorst-order, Elovich and MorrisWeber kinetic models. Meanwhile,
the qe value (40.160 mg/g) calculated from pseudo-second-order
model is more consistent with the experimental qe value
(39.82 mg/g). The obtained results indicate that the adsorption
is well represented by a pseudo-second-order kinetic model.

Fig. 8. Effect of contact time on the adsorption efciency.

Adsorption isotherm study

where qe and qt are the sorption capacity at equilibrium (mg/g) and
at time t (min), respectively. k1 is the rate constant of pseudo rstorder adsorption (min1).
The pseudo-second-order kinetic model [49] represented by
the linear equation is used to describe chemisorption, as well as
cation exchange reactions. The pseudo-second-order kinetic
equation is expressed as the following Eq. (5):
t
1
t

qt k2 q2e qe

(5)

where qe and qt are the sorption capacity at equilibrium (mg/g) and

at time t (min), respectively. k2 is the rate constant of pseudosecond-order for the adsorption (g/mg min).
The Elovich equation [50] has a found general application in
chemisorption kinetics and has been found useful in covering a
wide range of slow adsorption rate. The Elovich kinetic equation is
expressed as the following Eq. (6):
q A 2:303 B log t

(6)

where q is the amount of sorbate per unit mass (mg/g) of sorbent at

time t (min), and A and B are Elovich constant.

Adsorption capacity at different aqueous equilibrium concentration can be illustrated by the adsorption isotherm. In this work,
various isotherm models were studied, such as Langmuir,
Freundlich and RedlichPeterson isotherm model [47].
Langmuir adsorption isotherm [52] is applicable in many
adsorption processes. The basic assumption is the formation of a
monolayer of adsorbate on the outer surface of the adsorbent and
no further adsorption thereafter. Langmuir isotherm is expressed
as the following Eq. (8):
qe

qm K a C e
1 K aCe

(8)

where Ce is the equilibrium concentration of dyes in solution (mg/

L), qe is the adsorbed value of dye at equilibrium concentration
(mg/g), qm is the maximum monolayer adsorption capacity (mg/g),
and ka is the Langmuir binding constant which is related to the
energy of adsorption (L/mg).
Freundlich isotherm [53] is an empirical equation describing
that the adsorption surface becomes heterogeneous during the
adsorption process. The Freundlich isotherm is commonly
presented as the following Eq. (9):
1=n

qe K f Ce

(9)

where Ce is the equilibrium concentration of dyes in solution (mg/

L), qe is the adsorbed value of dye at equilibrium concentration
(mg/g), Kf and n are the Freundlich constants characteristics of the
system, respectively, indicating the adsorption capacity and the
adsorption intensity.
The RedlichPeterson isotherm model [47] is an empirical
isotherm that combines the elements from both the Langmuir
model and the Freundlich model, and it approaches the Freundlich
isotherm at high concentrations and is in accordance with the low
concentration limit of Langmuir model. The RedlichPeterson
isotherm can be expressed as the following Eq. (10):
qe

Fig. 9. The evolutions of absorption spectra of CR in the presence of NGNS-5 (CR

solution: 100 mL, 20 mg/L; NGNS-5: 40 mg).

aC e
b

1 bCe

(10)

where Ce is the equilibrium concentration of dyes in solution (mg/

L), qe is the adsorbed value of dye at equilibrium concentration
(mg/g), a is the RedlichPeterson isotherm constant (L/mg), and b
b
b
is a constant with the unit of (L /mg ). b is an exponent that lies
between 0 and 1, when b = 1, the equation becomes Langmuir
model.

X. Rong et al. / Journal of Industrial and Engineering Chemistry 26 (2015) 354363

361

Fig. 10. Linear t of kinetics models of pseudo-rst-order kinetic model (a), pseudo-second-order kinetic model (b), Elovich model (c) and MorrisWeber model (d).

The tted parameters and the theory data obtained by

nonlinear equations are listed in Table 3, and nonlinear t curves
are shown in Fig. 11. As can be seen from Fig. 11, correlation
coefcient (R2) of RedlichPeterson isotherm model is higher than
those of other models, indicating the removal process is better
modeled by RedlichPeterson isotherm model. The result also
shows that the adsorption process of CR on NGNS adsorbent is not
only monolayer adsorption. However, the value of b is 0.740, which

suggests that the ratio of monolayer adsorption is larger than that

of multilayer adsorption in the adsorption process.
Regeneration experiment
It is well known that the stability and regeneration ability of the
adsorbent during the adsorption process is crucial to its practical
application. In this work, the adsorbent containing CR molecular
after adsorption process was treated by washing with water and
calcination at 300 8C for 4 h [54]. The effect of recycle times of
NGNS-5 on the adsorption efciency is shown in Fig. 12. As can be
seen from Fig. 13, the adsorbent (NGNS-5) after treatment has a
high adsorption efciency of 96.02%, and 96.44% of the regeneration efciency (D(n)/D(0), D(0) = 99.56%) can be obtained after
4 cycles. The obtained results indicate that the prepared NGNS-5
adsorbent can be separated from system effectively and easily, and
maintained high adsorption efciency performance after being
used for four cycles.

Table 2
Kinetic parameters of the pseudo-rst-order model, the pseudo-second-order
model, the Elovich equation and the MorrisWeber equation analysis.

Fig. 11. Equilibrium adsorption isotherms and different model plots for CR
adsorption onto NGNS-5 adsorbent.

Kinetic model

Parameters

Pseudo-rst-order
Pseudo-second-order
Elovich
MorrisWeber

k1 = 0.0276/min, qe = 8.620 mg/g, R2 = 0.8192

k2 = 0.00868 g/(mg min), qe = 40.160 mg/g, R2 = 0.999
A = 34.931, B = 0.940, R2 = 0.996
Rid = 0.223 mg/g min1/2, ci = 26.941 mg/g, R2 = 0.973

X. Rong et al. / Journal of Industrial and Engineering Chemistry 26 (2015) 354363

362

Table 3
Adsorption isotherms parameters of Langmuir isotherm, Freundlich model and
RedlichPeterson isotherm model.
Isotherms model

Langmuir

Freundlich

RedlichPeterson

Parameters

ka = 0.302 L/mg
qm = 123.89 mg/g
R2 = 0.935

Kf = 38.501 mg/g
1/n = 0.339
R2 = 0.982

a = 124.460 L/g
b
b
b = 2.437 L /mg
b = 0.740
R2 = 0.989

Fig. 12. The effect of recycle times of NGNS-5 on the adsorption efciency.

Conclusion
In this work, a novel NiO/graphene nanosheets adsorbent
(NGNS) was prepared using nickel acetate as precursors of NiO,
urea as precipitating agent, PEG-200 as template agent and
graphene oxide (GO) as precursors of graphene by a facile
hydrothermal method. The obtained adsorbent can be used for
the removal of Congo Red azo-dye from aqueous solutions. The
surface morphology, chemical structure and thermal property of
NGNS were investigated by UVvis, XRD, Raman, TG, HRTEM, SAED
and XPS methods. The optimum conditions of adsorption CR from
aqueous solutions were obtained as follows: proportion of GO of
1.0%, adsorbent dose of 50 mg and time of 180 min at room
temperature of 25 8C. Under the optimal conditions, the prepared
NGNS-5 has an adsorption efciency of 99.56%. The different
adsorption kinetic and isotherm models were investigated; and the
result indicates that adsorption is well represented by a pseudosecond-order kinetic model and RedlichPeterson isotherm model.
The NGNS-5 adsorbent can be separated from system effectively
and easily, and maintained high adsorption efciency performance
after being used for four cycles. The maximum adsorption capacity
of NGNS-5 is superior to the reported activated carbon or
adsorbent based on activated carbon for the removal of CR. The
obtained results indicate that the prepared NGNS has potential
application for the wastewater treatment containing CR azo-dye.
Acknowledgements
This project was supported by the Innovation Program for
Graduate Education of Jiangsu Province (KYLX_1063), the Natural
Science of Jiangsu Province (BK20141298) and the Society
Development Fund of Zhenjiang (SH2013020).

Comparison with other adsorbent for removal of CR

Comparison of adsorption capacity of other adsorbents
reported in literature, especially for activated carbon and
adsorbent based on activated carbon for the removal of CR
[11,26,5557], the results are given in Table 4. From the results, it
can be seen that the maximum adsorption capacity of NGNS-5 is
superior to the literatures, which shows perfect adsorption
property and satisfactory performance for removal of CR. So,
NGNS-5 would be an effectively novel adsorbent.

Table 4
Comparison of adsorption capacities of various adsorbents for removal of CR.
Adsorbent
Activated carbon
from Myrtus
communis (AC-MC)
Palladium nanoparticles loaded
on activated carbon
(Pd-NPs-AC)
Silver nanoparticles loaded
on activated
carbon (Ag-NPs-AC)
Activated carbons of
commercial grade (ACC)
Activated carbons of
laboratory grade (ACL)
Activated carbon
prepared from coir pith
Reagent NiO nanoparticles
NiO/graphene
nanosheets (NGNS)

qm (mg/g)

Isotherm
model

References

19.231

Langmuir

[11]

76.900

Langmuir

[55]

66.700

Langmuir

[55]

0.635

Langmuir

[56]

1.875

Langmuir

[56]

6.720

Langmuir

[57]

39.700
123.89

Langmuir
Langmuir

[26]
This work

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