Journal of Environmental Chemical Engineering 6 (2018) 2803–2811

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Journal of Environmental Chemical Engineering

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Adsorption kinetics of methylene blue dyes onto magnetic graphene oxide T

a,⁎ a a
Nur Hidayati Othman , Nur Hashimah Alias , Munawar Zaman Shahruddin ,
Noor Fitrah Abu Bakara, Nik Raikhan Nik Hima, Woei Jye Laub
a
Faculty of Chemical Engineering, Universiti Teknologi Mara, 40450 Shah Alam, Selangor, Malaysia
b
Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia

A R T I C LE I N FO A B S T R A C T

Keywords: Adsorption is one of the most effective methods for the treatment of wastewater containing dyes owing to its low
Magnetic separation operating cost, simplicity of process design and smaller amounts of harmful substances. In this work, graphene
Graphene oxide oxide- magnetic iron oxide nanoparticles (GO-MNP) was synthesized using sonomechanical technique and used
Fe3O4 as effective adsorbent for synthetic methylene blue (MB) dye removal. Batch adsorption experiments were
Adsorption
performed with the variation of initial MB dye concentration, pH solution, adsorbent dosage and contact time.
Methylene blue dye
The adsorbent showed significant removal efficiency around 99.6% for MB. It was found that the removal rate of
MB dye in the solution was higher when higher pH, larger dosage of adsorbent in solution and longer contact
time were used. A regenerative study was carried out and minor reduction in adsorption capacity of the re-
generated GO-MNP was observed after 2 cycles. Analysis of adsorption equilibrium revealed that the data is well
fitted with Langmuir and Freundlich adsorption isotherm model (R2 > 0.97), indicating multi layer adsorption
of dye on the surface of adsorbent. In the case of adsorption kinetics, the GO-MNP adsorbent follows pseudo-
second order kinetics model showing R2 > 0.999, whereas for pseudo-first order kinetics model, the value of R2
was significantly lower. The finding of the present work highlights simple fabrication of magnetic GO and its
application as efficient and magnetically separable adsorbent for environmental clean-up.

1. Introduction
One of the major problems concerning textile industry is the pro-
duction of large quantity of coloured effluent from its process. Most of
dyes in the effluent are toxic to organisms and direct discharge of the
effluent without proper treatment could affect the ecosystem in long
term [1]. The presence of pigments tends to block the passage of light
through water and decrease the efficiency of photosynthesis in aquatic
plants and hence create adverse impact on their growth [2]. Dyes also
can cause severe damage to human beings such as causing kidney
dysfunction and affecting reproductive system as well as central ner-
vous system. A great number of studies have been conducted to in-
vestigate the impact and toxicity of dyes on the ecosystem. People are
concerned on the improper textile effluent treatment as many dyes are
made of known carcinogens such as benzidine and other aromatic
compounds [2].
Methylene blue (MB), is the most commonly cationic dye used
substance for dying cotton, wood, and silk [3]. Although it is not
strongly hazardous, it still have various harmful effects such as diffi-
culty in breathing during inhalation or burning sensation, nausea, vo-
miting and diarrhoea if being ingested through the mouth [4]. Various
treatment that have been used to remove dyes from wastewater such as
physical (adsorption, irradiation and membrane process), chemical
(oxidative process, ozonation, ionic exchange, electrocoagulation and
coagulation-flocculation) and biological (aerobic and anaerobic) treat-
ment. Among them, conventional biological treatment methods are
reported to be efficient in the removal of suspended solids and reduc-
tion of chemical oxygen demand but are normally found to be in-
effective to achieve complete removal of colour from dye-bearing ef-
fluents. Besides, other disadvantages of the above methods are
generation of large amounts of toxic and carcinogenic by products,
energy intensive and high cost [5].
Recently, adsorption has displayed promising and effective results
for the removal of dyes from aqueous solution and is considered as an
attractive method due to its low cost, simplicity of design, ease of op-
eration, insensitivity to toxic pollutants and smaller amounts of harmful
substances [6]. Numerous adsorbents such as activated carbon, zeolite,
silica and natural-based (wheat, shells, fruit peels) have been studied
and applied. It is important to have an efficient adsorbent that have
rapid removal and fast adsorption of toxic impurities within few min-
utes of application. Many research groups have investigated the use of
nanoparticles as adsorbent. Nanoparticles are particles in the range of

⁎
Corresponding author.
E-mail address: nurhidayati0955@salam.uitm.edu.my (N.H. Othman).

https://doi.org/10.1016/j.jece.2018.04.024
Received 2 November 2017; Received in revised form 19 February 2018; Accepted 13 April 2018
Available online 16 April 2018
2213-3437/ © 2018 Elsevier Ltd. All rights reserved.
N.H. Othman et al.
1–100 nm with novel size-and shape-dependent properties, nanoma-
terials have been extensively used over a decade [7]. As compared to
conventional materials, nanostructure adsorbents show higher effi-
ciency and faster removal rate of pollutant from the wastewater [8,9].
This is because when the particle size is scaled down to nano scale,
considerable changes are observed in the chemical, physical, mechan-
ical and optical properties of the adsorbents. Nanomaterial possess
higher surface area, which can lead to higher adsorption capacity for
pollutant removal. Besides, the change in the pores structure is also an
important attribute that correspond to the faster transportation of the
pollutants to the internal active sites of adsorbents [10]. These changes
make nanoparticles as the potential adsorbent for the removal of pol-
lutant
Graphene is a two-dimensional carbon-based material possessing
atomic thickness and undoubtedly emerging as one of the most pro-
mising nanomaterials. Owing to its unique combination of excellent
properties that allow it to be exploited in a wide spectrum of applica-
tions ranging from electronics to optics, sensors, and environmental
application. Graphene oxide (GO) is the oxidized form of graphene. It
consists of various functional groups such as hydroxyl, carboxyl, and
epoxy groups. Thus, it is very hydrophilic and able to swell in the
presence of water. It also possesses high negative charge density due to
the oxygen containing functional groups [1,11]. GO can act as weak
acid cation exchange resin because of the ionizable carboxyl groups,
which allow ion exchange with metal cations or positively charged
organic molecules [12]. These functional groups can interact with po-
sitively charged species like metal ions, polymers, and biomolecules
[11].
In order to make adsorption to be completely adopted by industries,
few issues need to be addressed such as high capital cost and complex
synthesis processes [9]. Besides, the removal of suspend adsorbents in
wastewater from a continuous flow system remains a challenge. If the
spent adsorbent can be recovered efficiently, it can be regenerated and
re-used to minimise the capital investment. Therefore, a number of
studies have been carried out aiming at the incorporation of magnetism
in adsorbents to aid their recovery from wastewater [13–15]. Magnetic
separations are fast, scalable, easily automated and can achieve se-
parations that would be impossible or impractical to achieve by other
techniques. By using it in adsorbent, selective manipulation and se-
paration in the presence of other suspended solids can be carried out
[16,17]. As a results, it is possible to magnetically separate selected
target species directly out of crude biological process simply by binding
them on magnetic adsorbents before application of a magnetic field
[18].
Up until today, not many works that have been reported on the use
of magnetic-GO particularly as adsorbent for dye removal. Therefore,
the main objective of this work was to synthesize a novel adsorbent;
graphene oxide-magnetic iron oxide nanoparticle (GO-MNP) that ex-
hibits not only high adsorption rate and excellent regenerative ability
but also displays magnetic effect for easy separation after adsorption
process. The characteristic of the synthesized adsorbents was in-
vestigated and the possibility of using GO-MNP for the removal of
methylene blue from aqueous solution was then explored. The influ-
ences of adsorption parameters such as initial dye concentration, pH
solution, adsorbent dose and contact time were also reported. Finally,
the adsorption process was studied by the kinetic data and equilibrium
data on batch adsorption.
2. Materials and methods
2.1. Materials
Graphite powder (12.01 g/mol) was purchased from COMAK.
Sodium nitrate (84.99 g/mol), hydrogen peroxide (34.01 g/mol), iron
(III) chloride hexahydrate (FeCl3. 6H2O) (g/mol) and iron (II) chloride
tetrahydrate (FeCl2·4H2O) (g/mol) were purchased from SYSTERM.
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Journal of Environmental Chemical Engineering 6 (2018) 2803–2811
Sulfuric Acid (98.08 g/mol), potassium permanganate (158.04 g/mol),
methylene blue (MB) powder (319.86 g/mol), hydrochloric acid (HCl)
(34.65 g/mol) and sodium hydroxide (NaOH) (g/mol) were obtained
from R&M. All chemicals were of analytical grade and used without
further purification. The water used in this work was deionized water.
2.2. Preparation of adsorbent
2.2.1. Preparation of magnetic nanoparticle iron oxide (MNP-Fe3O4)
MNP-Fe3O4 was synthesized using modified co-precipitation
method using ferric and ferrous salts with the presence of N2 gas [19].
The N2 was used to provide an inert atmosphere, which prevents the
oxidative conversion of magnetite to maghemite. Firstly, 16.25 g of
FeCl3 and 6.35 g of FeCl2 were dissolved into 200 mL of deoxygenated
distilled water (Fe2+/Fe3+ ratio of 2:1). After stirring for 1 h, 2 M
NaOH solution was added drop wise until pH of solution reaches 12 to
initiate chemical precipitation. The solution was kept at 70 °C for 3 h,
before being cooled down to room temperature, followed by separation
of black precipitate using permanent magnet. The particles were re-
peatedly washed with deionized water to remove NaOH until the pH
turned to about 7. Fe3O4 was then washed with acetone and dried in
oven at 60 °C. Eq. (1) shows the chemical reaction for the formation of
MNP.
2FeCl3+ FeCl2+ 8NaOH → Fe3 O4 (s) + 4H2 O + 8NaCl (1)
2.2.2. Preparation of graphene oxide (GO)
GO was synthesized using modified Hummer’s method that involved
both oxidation and exfoliation of graphite. Firstly, 5 g of graphite
powder and 2.5 g of NaNO3 were added into 1000 mL beaker containing
ice cubes. 200 mL of concentrated H2SO4 were then added and the
mixture continued to stir for another 1 h. It was followed by adding 30 g
of KMnO4 slowly into the mixture. The mixture was continuously
stirred for another 2 h at temperature less than 15 °C After that, ice bath
was removed and the mixture was kept stirred for 20 h at room tem-
perature. Then, the mixture was heated to 70 °C and stirred for 2 h
followed by adding 100 mL of H2O slowly. Again, the mixture was
heated to 90 °C and kept stirred for 1 h. Additional 100 mL of H2O was
slowly added and kept stirred for 1 h. At last, 30 mL of H2O2 was added
to stop the reaction. The resulting mixture was repeatedly washed by
centrifugation using HCl and distilled water several times until it
formed gel like solution. The gel like solution was dried at oven for 24 h
at 60 °C to form GO powder
2.2.3. Preparation of graphene oxide-magnetic iron oxide nanoparticles
(GO-MNP)
200 mg of GO powder was added in 50 mL of distilled water fol-
lowed by addition of 200 mg of magnetic iron oxide nanoparticles
(MNP). The mixture was stirred continuously for 60 min before sub-
jecting to 30 min ultrasonication with 50% of power usage. It was fol-
lowed by another 15-min ultrasonication with 60% of power. The black
precipitation of the solution was then separated by centrifuge followed
by drying at 60 °C for 24 h [20].
2.3. Characterization of GO-MNP adsorbent
A Rigaku D/MAX 2550 X-Ray Diffractometer (XRD) with Cu-Kα
radiation was used to determine the crystal structure and average grain
boundary size of GO, MNP and GO-MNP. The scan was carried out at 2θ
of 5°–60° at speed angle of 2° min−1. The chemistry of adsorbent was
characterized using Fourier Transform Infrared Spectroscopy
(FTIR,Perkin Elmer) in the range of 500–4000 cm−1. Specific surface
area was obtained through Brunauer–Emmett–Teller analysis (BET)
using a Micromeritics ASAP 2020 system. The zeta potential measure-
ments of the adsorbents in an aqueous dispersion were performed on
Malvern Instruments. The microstructure of adsorbents was examined
N.H. Othman et al. Journal of Environmental Chemical Engineering 6 (2018) 2803–2811

using an FEI Quanta FEG250 Field Emission Scanning Electron

Microscope (FESEM).

2.4. Preparation of methylene blue solution adsorbate

A stock solution with methylene blue concentration of 500 mg/L

was prepared by dissolving 0.1 g of dye powder in 200 mL beaker filled
with distilled water. Different dye concentration solutions (10, 30 and
50 mg/L) were prepared by diluting the stock solution accordingly. The
calibration curve of dye concentration and absorbance at wavelength of
655 nm was established in order to determine the amount of dye pre-
sent in the permeate samples.

2.5. Adsorption study

All the adsorption tests were carried out batch wise with constant
stirring at ambient conditions (30 °C). Concentrations of MB, dose of
GO-MNP and pH of MB solutions was varied from 10 to 50 mg/L,
5–15 mg and 3–9, respectively. In the first experiment, different dose of
GO-MNP (5 mg, 10 mg and 15 mg) was added into 100 mL of flask
containing 10–50 mg/L of MB solutions under stirring conditions. The
effect of pH (3, 7 and 9) was then investigated by mixing 5 mg of GO-
MNP into 100 mL of MB solution of different concentrations. The initial
pH of MB solution was adjusted to values in the range of 3–9 by adding
0.1 mol/L NaOH or 0.1 mol/L HCl solutions drop wisely. After certain
period of contact time, GO-MNP particles were separated from the so-
lution by a magnet that was placed at the side of the flask. The con-
centrations of MB left in supernatant solutions were determined at the
maximum adsorption wavelength of 655 nm using a Lambda 750
UV–vis spectrophotometer (Perkin Elmer).
To study the adsorption isotherms, the concentrations of MB left in
the solutions once the system reached adsorption equilibrium were
determined to calculate q at equilibrium. Kinetic experiments were then
performed at ambient temperature and MB solution at different con-
centrations of 10 mg/L, 30 mg/L and 50 mg/L. The concentrations of
MB left in the supernatant solutions after different time intervals
(5–180 min) were then determined using UV–vis. In analysis of the
adsorption data, removal percentage (R, %) and adsorption capacity
(qt) were calculated according to Eqs. (2) and (3), respectively:
C0 − Ct
Removal rate , R (%) = x100%
C0 (2)
where Co is the initial concentration of dye solution (mg/L) and Ct is the
final concentration (mg/L) after the adsorption process
C0 − Ct
Adsorption capacit y, qt (mg ) = xV
M (3)
where M is the dose of adsorbent (mg) and V is the volume of the MB?
solution (L). The data shown in the manuscript were the average data of
two independent runs and all results were reproducible with ± 5%
error.
2.6. Regeneration study
Effectiveness of regenerative adsorbents study was conducted by
regenerate the GO-MNP adsorbents after performing the adsorption
test. The used adsorbent firstly was washed by using 1 M acetic acid
followed by distilled water until the pH turned to neutral. The ad-
sorbent was then dried at temperature 60 °C for 24 h before reusing it.
3. Results and discussion
3.1. Characterization of GO-MNP
Fig. 1 compares the XRD patterns of graphite, GO, MNP and GO-
MNP prepared using sonochemical method. A typical single diffraction
Fig. 1. X-ray Diffraction (XRD) image of graphene oxide (GO), magnetic iron
oxide nanoparticle (MNP) and graphene oxide-magnetic iron oxide nano-
particle (GO-MNP).
peak was observed at 2θ = 9.6° (001) for GO, which corresponding to a
GO interlayer spacing of 0.80 nm. This value is usually larger than
graphite and is caused by loosely stacked GO [21]. Besides, the pre-
sence of many oxygen-based group that attached to the surface of GO
with some defects cause by oxidation process could also led to bigger
interlayer spacing. The XRD spectra of MNP shows significant peaks at
31.9°, 35.9°, 42.5°,53.0°, 57.5° and 62.6° that are consistent with the
XRD patterns of Fe3O4 nanoparticles (JCPDS card no. 19-0629) [9]. For
GO-MNP, the diffraction peaks were observed to match well GO and
MNP. Besides, the characteristic peaks of GO and MNP, no other dis-
tinctive peak was observed which confirms that the iron MNP com-
pound existed in the GO-MNP [22]. However, one should keep in mind
that the real composition of the nanoparticles may not be 100% Fe3O4
but contain a small amount of γ-Fe2O3.
FTIR analysis was used to identify the key functional groups of GO-
MNP. Fig. 2 shows the FTIR spectrum for GO, MNP and GO-MNP. The
spectrum of GO was in good agreement with previous work [need ci-
tation]. The broad adsorption peak at 3400 cm−1 was associated to
vibrational modes of bonded OH, which forms a hydrogen bond with an
oxygen atom of a neighbouring water molecule. The band at 1680 cm−1
was attributed to the stretching vibrations C]O (asymmetric) of car-
boxyl groups. Peaks discovered at 1368 cm−1, 1041 cm−1, and
1617 cm−1 were due to CeH, CH, and C]C aromatic, respectively. The
FTIR spectrum for GO-MNP was slightly difference than GO due to the
weakening of several bonds such as OH at 3400 cm−1 and CeO at
1100 cm−1. Additional vibration band was observed at around 1600
and 1400 cm−1, which might be assigned to the formation of either a
monodentate complex or a bidentate complex between the carboxyl
group and Fe on the surface of the MNP, supporting that the MNP are

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N.H. Othman et al. Journal of Environmental Chemical Engineering 6 (2018) 2803–2811

Table 1
BET analysis.
Samples BET surface area (m2/g) Pore volume (cm3/g)

Graphite 5.60 0.0263

GO 105.97 0.4606
MNP 53.57 0.1539
GO-MNP 84.63 0.1386

formed. From the higher magnification of SEM images, it can be seen

Fig. 2. Fourier transform infrared spectroscopy (FT-IR) spectrum of a) graphene
oxide (GO); b) magnetic iron oxide nanoparticle (MNP) and c) graphene oxide-
magnetic iron oxide nanoparticle (GO-MNP).
covalently bonded to GO [20].
The morphology of graphite, GO and GO-MNP are shown in Fig. 3.
GO was observed to have a smooth surface with a distinctive layered/
sheet appearance in compared to graphite. It can also be seen that MNP
were well dispersed in GO, which suggests that GO-MNP has been
that the MNP were decorated in bunches on the layer/sheet of GO.
Meanwhile, the average size of MNP was observed to be around
250–500 nm, which explained the low surface area of MNP.
The BET surface area of GO, MNP and GO-MNP calculated by using
the standard Brunauer–Emmett–Teller (BET) method are 105.97, 53.57
and 84.63 m2/g. The value of GO was much higher than graphite, in-
dicating that it has been oxidized and exfoliated into GO. By combining
GO with MNP, the surface area of GO-MNP increased by 40% in com-
pared to MNP. The main advantages of having high surface area of
adsorbent is the increased of contact between the adsorption sites of
GO-MNP and MB molecules, thus, improving the adsorption capacity of
GO-MNP for MB. Pandhi et. al.[23], have found that the efficiency of
cationic and anionic dyes removal was increased when high surface
area of GO was used as adsorbent (Table 1).

Fig. 3. SEM imags of Graphite, GO, P and GO-MNP at 10 and 50 μm scale bar.

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N.H. Othman et al.
Fig. 4. Calibration curve for concentration of MB dye solution.
3.2. Dye adsorption study
Various concentrations of MB were prepared ranging from 5 mg/L
to 50 mg/L. The value of absorbance at the wavelength of 655 nm in a
UV–vis spectrophotometer was referred as the specific concentration of
MB. The experiments were repeated five times and the average data
were used to plot the resultant graphs. A calibration curve of absor-
bance against MB concentrations was then plotted. The experimental
data reported in Fig. 4 were fitted by a straight line with a high re-
gression coefficient value (R2 = 0.9949). This allow us to consider that
the molar absorptivity is constant over the concentration and therefore,
the concentration of MB can be determined with good precision.
In order to determine the influence of GO-MNP as adsorbent dosage
and initial MB concentration, the amount of GO-MNP was varied from
10 to 15 mg and the initial MB concentration was varied from 10 to
50 mg/L for 10 min at pH 9. The result is shown in Fig. 5. In general, the
removal percentage of MB is higher than 80%. This might be attributed
to high surface area of GO-MNP, which can provide massive active sites
for adsorption of MB. The removal percentage of MB was also found to
increase when higher adsorbent dosage was used. When lower con-
centration of MB (10 mg/L) was used, the removal percentage of MB
increased significantly from 86.8% to 98.9%. However, for 30 mg/L
and 50 mg/L of MB solutions, the effects of adsorbent dosage were not
significant. Beside the dosage of adsorbent, the initial concentration of
MB dye solution could also affect the adsorption capacity greatly. The
adsorption capacity relies on the amount of MB transported from bulk
solution to the surfaces of the GO-MNP at lower initial dye
Fig. 5. Effect of adsorbent dosage on MB dye removal percentage (pH = 9,
contact time = 10 min, concentration 50 mg/L).
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Journal of Environmental Chemical Engineering 6 (2018) 2803–2811
Fig. 6. Removal percentage of MB dye at various adsorbent dosage (5, 10,
15 mg) and initial MB concentrations (10, 30, 50 mg/L).
concentrations. As the adsorption sites of GO-MNP adsorbent getting
diminished and reach to saturation, the MB adsorption capacity reached
a plateau and achieves equilibrium when the MB concentrations were
increased from 30 mg/L to 50 mg/L even though 10 mg and 15 mg of
GO-MNP were used. This indicates that the removal of MB was highly
depended on the initial dye concentration. Besides, this results also
could be attributed to the increase in driving force of concentration
gradient as the increase of MB concentration could accelerate the dif-
fusion of dye molecules onto the adsorbent.
In order to determine proper equilibrium time of the adsorption
progress, the effect of contact time on the adsorption of GO-MNP was
also studied for a period of 3 h (180 min) as shown in Fig. 6. The contact
time curve shows that the MB removal was rapid at the beginning and
then slowing down continuously leading to surface saturation at high
concentrations. These curves indicate that most vacant surface sites are
available for adsorption during the initial stage and after 10 min, the
surface of GO-MNP has monolayer coverage of MB, resulting in the
decrease of vacant site for adsorption to occur [24,25]. The adsorption
of MB can reach equilibrium within 10–30 min and this could be at-
tributed to the absence of internal diffusion resistance and the good
solubility of GO-MNP [26].
3.3. Regenerative of GO-MNP adsorbent study at various pH solutions
A number of studies have reported that pH of MB is one of the
important influencing factor in adsorption process. MB is basic in
nature and only releases coloured dye cations in the solution. In order
to investigate the effects of pH on the adsorption of MB on GO-MNP, the
adsorption was carried out at 10 mg/L of initial MB dye concentration
and varying pH (3,7,9) and adsorbent dosage (Fig. 7). The adsorption
capacity of GO-MNP increased with the increase of MB solution pH,
where the maximum MB removal was observed at pH 7 and 9 (neutral
and basic conditions). The basic dye gives positively charged ions when
dissolved in water. Thus, at lower pH values, hydrogen ion competes
with MB cation and as most of GO exist in the form of GO-H species, the
adsorption amount of MB was reduced. However, at higher pH values,
the surface of GO-MNP acquires negative charge and more species of
GO− occur. As a result, the adsorption of MB increased due to the
enhancement of electrostatic attraction between positively charged MB
dye and negatively charged GO-MNP adsorbent [26–28]. Lower MB dye
concentration gives higher removal rate due to the increase of active
sites for MB adsorption on GO-MNP.
In order to evaluate the possibility of GO-MNP adsorbent, a re-
generative study was carried out. The regeneration of GO-MNP was
achieved by acetic acid washing, followed by distilled water until the
N.H. Othman et al.
Fig. 7. Regeneration of adsorbent at various pH of 1st = fresh GO-MNP,
2nd = regenerative (GO-MNP).
pH of adsorbent was neutral. Fig. 7 compares the regenerative ability of
GO-MNP adsorbent. The regenerated GO-MNP was tested again for MB
adsorption under the same conditions as mentioned above. It was found
that the regenerated GO-MNP still showed considerable adsorption
capacity for MB. The decreasing of adsorption percentage was between
5- 13%, in which the lowest percentage was observed when the MB
solution was in basic conditions. Among the possibility of lower MB
adsorption removal was because the reduction of adsorption vacant site
of the GO-MNP. It is believed that further optimization of regeneration
method, would possibly lead to full recovery of GO-MNP for MB ad-
sorption.
3.4. Isotherm of adsorbent at various dosage GO-MNP
Adsorption isotherm is the relationship between the amount of a
substance adsorbed per unit mass of adsorbent at constant temperature
and its concentration in the equilibrium solution. The equilibrium
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Journal of Environmental Chemical Engineering 6 (2018) 2803–2811
adsorption isotherm is studied in detail as developing an appropriate
isotherm model that can describe the interaction of solutes with the
sorbent is important when designing and optimising an adsorption
process. Adsorption equilibrium is a dynamic concept achieved as the
rate of dye adsorption is equal to the desorption rate. A
number of isotherm models have been used for evaluation of equili-
brium adsorption such as Langmuir, Freundlich, Redlich–Peterson,
Dubinin–Radushkevich, Sips, and Temkin [29]. As Langmuir and
Freundlich equations are the most common models used to investigate
the adsorption isotherm, the experimental equilibrium data of MB ad-
sorption onto various dosage of GO-MNP at pH = 9 were fitted with
these two models. The Langmuir isotherm theory is valid for monolayer
sorption on a surface with a finite number of identical sites (homo-
geneous surface) and the interaction among adsorbed substance can be
negligible. It assumes that after monolayer adsorption, the adsorbent
surface is saturated. The linearized form of Langmuir isotherm equation
is expressed as follows.
1 1 1
= +
qe KL Qm Ce qm (4)
where qm (mg/g) is the maximum amount of MB dye per unit weight of
adsorbent for complete monolayer coverage and KL is the Langmuir
adsorption constant. A plot of 1/qe against 1/Ce should be linear if the
adsorption follows Langmuir behaviour, with a slope of 1/KLqm and
intercept of 1/qm are obtained. Another important characteristic of
Langmuir isotherm can be expressed in terms of dimensionless se-
paration factor RL, which is calculated as:
1
RL =
1 + KL xCo (5)
The value of RL indicates the shape of Langmuir isotherm to be either
irreversible (RL = 0), favourable (0 < RL < 1), linear (RL = 1) or
unfavourable (RL, > 1). The Freundlich isotherm model is an empirical
relationship describing the adsorption of solutes from a liquid to a solid
surface, and assumes that different sites with several adsorption en-
ergies are involved and the multilayer of the adsorption process occurs
on a heterogeneous surface. The linear form of the Freundlich equation
is:
1
logqe = log Ce + log Kf
nf (6)
where Kf is adsorption capacity of the adsorbent and n indicates how
favourable the adsorption process. Both are Freundlich constants. The
slope 1/n ranging between 0 and 1 is a measure of adsorption intensity
or surface heterogeneity and as its value gets closer to 0, the surface
becomes more heterogeneous [30]. Fig. 8 and Table 2 shows the
Langmuir and Freundlich isotherm plots for MB on GO-MNP and cor-
responding constant for MB on different isotherm, respectively. It can
be seen that the data on MB adsorption fit Langmuir and Freundlich and
were observed to be linear over the range of adsorbent used in this
study with extremely high values of R2. In general, the correlation
coefficient (R2) provides an idea about the best model that can be se-
lected to give the best fit. RL values for MB dye were calculated and its
value was less than 1 and greater than zero indicating favourable ad-
sorption.
3.5. Kinetics of GO-MNP adsorption
Adsorption mechanism depends on the physical and/or character-
istic of the adsorbent and the mass transport process. In order to de-
termine the controlling mechanism of the adsorption process, the
pseudo-first- and the pseudo-second order model were used to analyze
the experimental data of the adsorption of MB dye onto GO-MNP at
different initial MB concentrations (10, 30 and 40 mg/L) and pH 9. The
best-fit model was selected based on the linear regression coefficient,
(R2) values. The linear form of the pseudo first-order model is
N.H. Othman et al. Journal of Environmental Chemical Engineering 6 (2018) 2803–2811

concentrations of solute. The results show that the experimental qe was

not in agreement with calculated qe and the value of R2 are low for most
of the adsorption data. This shows that the adsorption process of MB
onto GO-MNP does not follow the pseudo-first order kinetic model. The
linear form of the pseudo second order model is given by:

1 1 1
= + t
qt K2 qe2 qe (8)

where K2 is the pseudo-second order rate constant (g/mg min) and can
be determined from the intercept of the plot of t/qt versus t (Fig. 9). The
rate of pseudo second order reaction is known to be dependent on the
amount of solute adsorbed on the adsorbent surface and the amount
adsorbed at equilibrium. The plots show good agreement between ex-
perimental and calculated qe values and the R2 was higher than 0.99
and closer to unity for all the adsorption data. The values of kinetic
parameters were listed in Table 3. Based on the comparison of the
predicted best fitted time dependencies, it was assured that the pseudo-
second order kinetic equations describe the MB dye sorption more ac-
curately. A number of works have observed similar phenomenon on
adsorption of MB onto various adsorbent such as sepiolite [24], lignite
[31], GO/MgO [32], GO/Agar [33]. According to the pseudo-second
order, boundary layer resistance is not the rate limiting step. The ex-
ternal resistance model cannot adequately describe the adsorption
mechanism and the rate controlling step was chemical adsorption in-
volving valence forces through exchange and share of the electrons
between MB molecules and the GO-MNP adsorbent.

4. Conclusions

This study investigated the adsorption of MB dye from aqueous

Fig. 8. Langmuir and Freundlich isotherms for MB dye onto various dosage of
GO-MNP.
represented by:
K dosage dependent. The adsorption isotherms and kinetics were then
log (qe − qt ) = log qe + ⎛ 1 ⎞ t
⎝ 2.303 ⎠ (7)
where K1 is the rate constant of adsorption (1/min), qe and qt are the
amounts of MB adsorbed (mg/g) at equilibrium and at time t (min). The
values of qe and K1 can be computed from the slope and intercept of the
plot, respectively. This model is usually more suitable for lower
solution using magnetic graphene oxide (GO-MNP) adsorbent. The GO-
MNP was successfully synthesized using sonochemical method. Several
factors such as MB dye concentration, pH solution, adsorbent dosage
and contact time were investigated. It was found that the initial pH MB
solution plays a significant role, in which the adsorption of MB was
more favourable at basic conditions. Based on the removal rate of MB,
GO-MNP shows good adsorbent characteristics for cationic MB dye,
with removal efficiency up to 98%. Overall, it could be concluded that
adsorption rate is pH, contact time, MB concentration and adsorbent
investigated in detail at pH 9. Langmuir and Freundlich isotherm
models were employed to discuss the adsorption behaviour. The equi-
librium data were well-modelled by both isotherms. The kinetic study
revealed the adsorption process was well fitted the pseudo-second order
kinetic model. This finding demonstrates the potential of using GO-
MNP for effective removal of MB dye from aqueous solution.

Table 2
Isotherm parameters for removal of MB dye onto GO-MNP at various MB concentrations.
Adsorbent dosage 5 mg 10 mg 15 mg

Langmuir isotherm
KL (L/mg) 14.33 0.46 0.35
qm (mg/mg) 232.56 1666.67 1428.57
RL 0.007 0.067 0.054
Y = mX ± C Y = 0.0043X + 0.0003 Y = 0.0006X + 0.0013 Y = 0.0007X + 0.0020
R2 0.9798 0.977 0.9762

Freundlich isotherm
Kf 225.63 289.13 402.25
1/n 0.80 0.40 0.41
Y = mX ± C Y = 0.8031X + 2.3534 Y = 0.3979X + 2.4611 Y = 0.4141X + 2.6045
R2 0.9649 0.9641 0.9679

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N.H. Othman et al. Journal of Environmental Chemical Engineering 6 (2018) 2803–2811

Table 3
Pseudo-second order results for removal of MB dye onto GO-MNP at various MB
concentrations.
Amount GO-MNP Y = mX ± C R2 Qm (mg/mg) k2

10 mg/L
5 Y = 0.0076X + 0.0086 0.9998 131.6 0.0067
10 Y = 0.0051X + 0.0053 0.9998 196.1 0.0049
15 Y = 0.003X + 0.0019 1 333.3 0.0047

30 mg/L
5 Y = 0.0028X + 0.0008 0.9997 357.1 0.0098
10 Y = 0.0019X + 0.0026 0.9997 526.3 0.0014
15 Y = 0.0011X + 0.0004 0.9998 1000.0 0.0025

50 mg/L
5 Y = 0.0017X + 0.0005 1 588.2 0.0058
10 Y = 0.0011X + 0.0021 0.9997 909.1 0.0006
15 Y = 0.0006X + 0.0012 0.9998 1666.7 0.0003

Acknowledgements

The authors would like to acknowledge Abdul Aziz Ismail for as-
sistance during the experiments and Malaysia Ministry of Higher
Education (MOHE) for the FRGS research funding (600-IRMI/FRGS 5/3
(087/2017)).

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