Materials Today: Proceedings 47 (2021) 1173–1182

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Materials Today: Proceedings

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Removal of malachite green dye from aqueous solution using reduced

graphene oxide as an adsorbent
Dibya Ranjan Rout ⇑, Hara Mohan Jena
Department of Chemical Engineering, National Institute of Technology Rourkela, Odisha 769008, India

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

Article history: Adsorption of malachite green (MG) dye from wastewater was done by using reduced graphene oxide
Received 23 December 2020 (RGO) as an adsorbent. Batch adsorption experiments were carried out and the removal efficiency and
Received in revised form 1 February 2021 adsorption capacity were 96.3% and 279.85 mg/g respectively. This adsorption process was best
Accepted 12 March 2021
described by the Langmuir isotherm model (R2 = 0.993) and the dynamics analysis shows that the
Available online 8 April 2021
Pseudo-second-order model (R2 = 0.999), presents the best fitting to MG adsorption. Thermodynamic
analysis of equilibriums suggested that the adsorption process was spontaneous and endothermic in nat-
Keywords:
ure. Thus, the prepared reduced graphene oxide was a highly efficient adsorbent.
Adsorption
Malachite green
Ó 2021 Elsevier Ltd. All rights reserved.
Reduced graphene oxide Selection and peer-review under responsibility of the scientific committee of the International Confer-
Langmuir isotherm ence on the Global Challenges in Nanomaterials Research for Environmental and Healthcare Applications.
Endothermic

1. Introduction to its high removal efficiency, simplicity of design, easy to operate,

cost-effective, release a small amount of harmful substances,
Wastewater generated from different types of industries such insensitivity to toxic pollutants and availability of a wide variety
as; tanning, printing, leather, and textile industries contains differ- of adsorbent. Several types of adsorbents are available for the
ent types of coloured substances (dye), which are harmful to our adsorption of dye from wastewater. Among them, Carbon-based
environment, aquatic animals, and human beings. The dye which adsorbents have been considered versatile adsorbents during
is present in wastewater contains pigment that block the passage recent years in dye removal from wastewater.
of light through water and due to this photosynthesis of aquatic Graphene, the newest allotrope of carbon is considered a suit-
organisms decreases causing an adverse impact on their growth able adsorbent for the removal of dye from wastewater. Graphene
[1]. Malachite Green (MG) dye is one of the most used dyes for and its composites are used in several applications due to its
colouring cloth, wool, leather, jute, cotton, etc., and is also used unique two-dimensional nature [4–7]. The theoretical specific sur-
as an antimicrobial and antifungal agent in the food industry [2]. face area value of graphene is about 2630 m2/g and the structure of
The presence of MG dye in water decreases food intake, causes graphene is a carbon nanomaterial in which a single layer of sp2
damage to the kidney and liver, heart failure, decreases fertility hybridized carbon atoms are arranged in six-membered rings [8].
rate, causes mutagenic, carcinogenic, and teratogenic effects to It has a honeycomb lattice structure with a carbon–carbon bond
human cells [3]. Therefore, it is highly essential to remove MG length is of 0.142 nm [9]. Recently, graphene, graphene nanocom-
dye from wastewater discharge by industries. posites, graphene oxide (GO), reduced graphene oxide (RGO), and
There are various treatment methods available for the removal chemically-functionalized graphene have been used for the
of dye from wastewater such as Adsorption, Nanofiltration, photo- removal of dye from wastewater. In GO the oxygen functional
catalytic degradation, biological treatment, electrolysis, and oxida- groups such as carbonyl and carboxylic groups are placed at edges
tion. Out of these methods, adsorption is a highly effective and whereas the hydroxyl and epoxy groups are distributed on the
promising method for the removal of dyes from wastewater due basal plane of the surface [10]. The main characteristics of GO
and its composites are the negatively charged oxygen functional
groups and the presence of sufficient adsorption sites. On the other
⇑ Corresponding author. Tel.: +91 7978164686. hand, RGO is characterized by electrostatic interaction, structural
E-mail address: [email protected] (D.R. Rout).

https://doi.org/10.1016/j.matpr.2021.03.406
2214-7853/Ó 2021 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on the Global Challenges in Nanomaterials Research for
Environmental and Healthcare Applications.
Dibya Ranjan Rout and Hara Mohan Jena Materials Today: Proceedings 47 (2021) 1173–1182

conjugation, and presence of a lot of defects, residual oxygen func- 2.3. Synthesis of reduced graphene oxide
tionalities, P-P interaction, and availability of large porosity.
Hence RGO is used as a potential adsorbent for adsorption of a Graphene oxide (5gm) was placed in a 1L beaker and 500 ml
wide variety of cationic as well as anionic dyes. deionised water was added into it, then the graphene oxide sus-
Numerous graphene-based adsorbents have been reported for MG pension was stirred for 30 min using a magnetic stirrer. After stir-
dye removal from wastewater which have low adsorption capacity ring, the pH of the above solution was adjusted to 10 by adding
and less removal efficiency. Zhang et al. have synthesized Graphene 0.1 N HCl or 0.1 N NaOH solution then added 20 ml Hydrazine
oxide (GO) caged in cellulose bead (GOBD) which has maximum monohydrate as reducing agent to the above solution at 95°C
MG adsorption capacity is 30.091 mg/g at MG dye concentration of and stirred for 4hr. The reduced GO was collected by using whatt-
10 mg/L, adsorption time of 1hr, pH 7.0, and Temperature 298 K man filter paper and then the collected residue was dried under
[11]. Kinani et al. have prepared graphene oxide–tannic acid vacuum in an oven at 90°C to obtain the black powder, which
nanocomposite which has MG dye adsorption capacity about was called reduced graphene oxide. Fig. 2 represents the schematic
283.4 mg/g calculated by pseudo-second-order kinetics at pH 8.0, presentation of the synthesis of reduced graphene oxide (RGO)
dye concentration 200 mg/L, time 2hr, and Temperature 298 K [12]. from graphene oxide (GO).
Roja et al. have fabricated graphene oxide as an adsorbent for MG
dye with a maximum removal of 80% at 700 mg/L dye concentration, 2.4. Characterization of reduced graphene oxide and graphene oxide
4 mg/L adsorbent dosage, pH 8.0, and 90 min of adsorption time [13].
As most of the works are focussed on graphene oxide-based A Rigaku D/MAX Model D-5000 XRD Siemens Diffractometer
adsorbents for the removal of MG dye from wastewater, few atten- with Cu Ka radiation (k = 0.14405n) was used to investigate the
tions have been given to the use of reduced graphene oxide as a crystal structure of GO and RGO. The scan was carried out for the
potential adsorbent. Therefore, the present work aimed to synthesize XRD pattern of GO and RGO with a scan rate of 5°/min from 5°-
reduced graphene oxide (RGO) from graphene oxide by using the 90°. Fourier transform infrared spectrum (FTIR Perkin-Elmer spec-
reducing agent Hydrazine monohydrate and used this as an adsor- trum 65) was used to identify the functional groups which are pre-
bent. The characterization of synthesized adsorbent was studied sent on the sample by using Nicolet 5700 Spectrometer in KBr
and the possibility of using RGO as an adsorbent for the removal of pellet at room temperature. The morphologies of GO and RGO were
MG dye from aqueous solution was then explored. The influence of analysed by FESEM model Jeol JSM-6010 LV at an accelerating volt-
various adsorption parameters such as adsorbent dose, solution pH, age of 15 kV and magnification of 100,000 X. Raman Micro-
initial dye concentration, contact time, and the temperature was also spectrometer (Renishaw) was used for the Raman spectra of GO
studied. Finally, for the batch adsorption process isotherm, kinetics and RGO at an excitation wavelength of 785 nm.
and thermodynamic parameters have been evaluated.

2.5. Preparation of malachite green stock solution

2. Materials and methods
A stock solution with malachite green (MG) dye concentration
2.1. Chemicals and materials 500 mg/L was prepared by dissolving 0.5 g of dye in a 1L beaker
filled with distilled water. Standard MG dye solutions of different
H2SO4 (98% Sigma Aldrich), Graphite powder (<20 mm, Moly- concentrations (20, 30, 40, 50, and 60 mg/L) were obtained by
chem), H2O2 (30% aqueous solution), H3PO4 (Molychem), KMnO4 diluting the stock solution having a concentration of 500 mg/L.
(99% Fisher scientific), Molychem) and hydrazine monohydrate The concentration of MG dye was measured by using UV–VIS spec-
(50–60% solution, Molychem were used. Malachite green dye was troscopy (Shimazu UV-3150 spectroscopy) at 616 nm, at first cali-
purchased from Hi-Media Laboratories Pvt. Ltd. India. All chemicals bration plot of MG dye at different concentration was made and
were of analytical grade and utilised without further purification. the amount of dye present in permeate samples was determined
In this work the water used was deionised one. using the plot.

2.2. Synthesis of graphene oxide 2.6. Batch adsorption experiments

Graphene oxide (GO) was synthesized by modified hummers Batch adsorption studies were carried out for MG dye by using
method from pure graphite powder which involved both oxidation RGO as an adsorbent. The adsorption experiments were performed
and exfoliation of graphite[14]. In a 1L beaker 40 ml of phosphoric in 250 ml conical flasks with 50 ml of MG dye solutions. The effect
acid (H3PO4) and 360 ml of sulphuric acid (H2SO4) in the ratio of of parameters such as solution pH, adsorbent dosage, initial con-
1:9 were mixed with 10 g of graphite powder and stirred for centration, adsorption time, and the temperature were varied from
45 min. It was followed by the addition of 18 g of potassium per- 5 to 10, 10–50 mg, 20–60 mg/L, 0–180 min, and 20°C
40°C
manganate (KMnO4) very slowly (took 5 min to add). This reaction respectively. The initial pH of the solution was adjusted from 5
was exothermic, so to reduce the temperature below 20°C the bea- to 10 either by adding 0.1 M HCl or 0.1 M NaOH solution drop wise.
ker was placed on an ice bath. The mixture became a dark green The percentage removal and adsorption capacity of MG dye
solution after stirred for 6 h. To stop the reaction 0.675 ml of Hydro- solution was calculated according to the formula: -
gen peroxide (H2O2) was added to the solution and then stirred for
ðC0 -Ct Þ
15 min and after that 400 ml of deionized water (DIW) was added %R ¼  100 ð1Þ
C0
to the mixture. After the addition of DIW, the temperature rises
above 100°C and the solution became yellowish-brown in colour,
ðC0 -Ct ÞV
kept the solution overnight for cooling, and then centrifuged at qt ¼ ð2Þ
10000 rpm for 5 min. After the centrifugation, the residuals were w
washed with DIW repeatedly till the pH reaches 7, and the super- Where C0 is the initial concentration of MG dye solution (mg.
natant was removed. After that, the filtered GO solution was put in L
1), w is the amount of adsorbent (g), V is the volume of dye solu-
an oven overnight at 90°C to produce GO powder. Fig. 1 represents tion, qt is the adsorption capacity of the adsorbent (mg. g
1), and Ct
the schematic presentation of the modified hummer’s method. is the concentration of MG dye (mg. L
1) at time t.
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Dibya Ranjan Rout and Hara Mohan Jena Materials Today: Proceedings 47 (2021) 1173–1182

Fig. 1. Schematic diagram for synthesis of graphene oxide (GO).

layer spacing (d-spacing) about 0.84 nm and for RGO the diffrac-
tion peak shifts towards the right and observed at 2h = 26.82°
with interlayer spacing (d-spacing) about 0.38 nm. It was con-
firmed from the XRD diffractograms, that the d-spacing of GO is
more as compared to RGO due to the reestablishment of the sp2
network during the reduction of GO [15].

3.1.2. Fourier transform infrared analysis

Fig. 4 shows the FTIR spectrum of GO and RGO. GO shows
stretching of hydroxyl group (3210 cm
1) [16], CC stretching
(2357 cm
1), carbonyl stretching C = O (1730 cm
1), sp2 -
hybridized C = C in-plane vibrations (1620 cm
1), epoxide group
stretching (1235 cm
1, 1072 cm
1) and C–H stretching
(794 cm
1) [17]. The presence of these functional groups confirms
the oxidation of graphite to graphene oxide. The FTIR spectra of
Fig. 2. Schematic diagram for synthesis of reduced graphene oxide (RGO). RGO show the hydroxyl group and carboxylic groups are disap-
pearing. The peaks at 2361 cm
1 are for CC stretching,
1620 cm
1 for C = C phenol ring stretching, 1192 cm
1 for C-O
3. Result and discussion epoxide stretching, and C–H stretching (950 cm
1). Hence in
RGO, the intensities are small as compared to GO, which suggests
3.1. Characterization of adsorbent that GO has successfully reduced to RGO.

3.1.1. X-ray diffraction (XRD) analysis

3.1.3. Field emission scanning electron microscopy analysis
Fig. 3 compares the X-Ray diffraction pattern of GO and RGO.
Fig. 5 shows the surface morphology of GO and RGO. It is
The diffraction peak of GO was observed at 2h = 12.18° with inter-
observed that in the GO (Fig. 5a) the interaction between the

Fig. 3. XRD pattern of GO (a) and RGO (b).

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gen weight percent is lower in RGO than GO because the oxygen

functional groups break when reduction°C curs.

3.1.4. Raman spectra analysis

Fig. 6 shows the Raman spectra of GO and RGO. The character-
istic bands D band at 1336 cm
1 and G band at 1598 cm
1 for GO
are shifted to D band at 1343 cm
1 and G band at 1595 cm
1 for
RGO after reduction. This shift is attributed to the recovery of a
hexagonal network of carbon atoms with defects [18]. The ratio
of the D-band intensity, ID, to the G-band intensity, IG, indicates
sp2/sp3 carbon ratio and for RGO it was 0.851 as compared to GO
(0.836) due to the increase in defect and the removal of functional
groups in RGO. The increase in defects refers to disorders in the
structure of the graphene backbone [19].

3.2. Adsorption studies

Fig. 4. FTIR spectra of GO and RGO.
3.2.1. Effect of solution pH
Solution pH plays an important role in the adsorption process
sheets is less crumbled, thin, wrinkles, and they are randomly
since variation in pH leads to the change in surface properties of
aggregated and in RGO (Fig. 5b) the sheets are less aggregate, irreg-
the adsorbent and the degree of ionization of the adsorptive mole-
ular structure, highly wrinkle, and the surfaces are corrugated. This
cule [20]. Fig. 7 shows the effect of pH on the removal percentage
change in surface morphology from GO to RGO°C curs due to the
(%) (Fig. 7a) and the adsorption capacity (Fig. 7b) of MG dye. The
reduction of functional groups from the surface. Fig. 5(c, d) shows
adsorption experiments were carried out by varying the solution
the EDAX analysis of GO and RGO and it is observed that the oxy-
pH from 5 to 10 either by adding 0.1 N HCl or 0.1 N NaOH solution.

Fig. 5. FESEM and EDAX analysis of GO (a.c) and RGO (b,d).

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Dibya Ranjan Rout and Hara Mohan Jena Materials Today: Proceedings 47 (2021) 1173–1182

with an increase in the initial concentration of MG dye the equilib-

rium time increases. The equilibrium time for an initial concentra-
tion of 20 mg/L is 60 min, whereas for a concentration of 60 mg/L it
is nearly 120 min. With an increase in the initial concentration of
dye, the removal percentage decreases, due to the saturation of
adsorbent sites on the surface of the adsorbent. And at the same
time, the adsorption capacity increases with an increase in initial
concentration (Fig. 9b) of the dye because of the higher driving
force. The adsorption capacity increased from 98.39 mg/g to
262.58 mg/g for an initial concentration of 20 mg/L to 60 mg/L, this
is because more dye molecules are available for adsorption.

3.2.4. Effect of temperature

The effect of temperature on the percentage removal and
adsorption capacity of MG dye onto RGO is investigated from
Fig. 6. Raman spectra of GO and RGO. 293 to 313 K and shown in Fig. 10. It is confirmed from the figure
that with an increase in temperature up to 303 K the percentage
removal (Fig. 10a) and the adsorption capacity (Fig. 10b) both
In the above pH range, it is observed that when the pH increased
increase, and then no such increase is observed. This is because
from 5 to 7 the removal percentage (%) and the adsorption capacity
of a decrease in viscosity of dye solution with an increase in tem-
are increased slowly and after that, it increases sharply to a maxi-
perature which leads to an increase in the rate of diffusion of MG
mum value for pH 8 and then remains the same. Because for acidic
dye molecules through the external boundary layers to the internal
medium the H+ ions of the solution and the cationic dye molecules
pores of the RGO adsorbent. So for this experiment, the optimal
repel each other so less adsorption will°C cur, but for basic pH, the
temperature for the adsorption process is considered as 303 K
OH– ions of the solution and the positive ions of dye molecules
(30°C).
attract each other other causing more adsorption. Also at higher
pH, the surface of the adsorbent is negatively charged which
3.3. Adsorption isotherm study
favours the adsorption of cationic dye molecules on the surface
of the adsorbent through electrostatic force of attraction [21].
To study the adsorption equilibrium and to optimize the design
of an adsorption system, it is necessary to correlate the equilibrium
3.2.2. Effect of adsorbent dosage data of each adsorption study. The distribution of adsorbed mole-
The effect of adsorbent dosage on the percentage removal and cules between the solid phase and the liquid phase is explained
adsorption capacity was investigated by varying the dosage from by the adsorption isotherm at the equilibrium state. There are sev-
10 to 50 mg and is shown in Fig. 8. The removal percentage of MG eral adsorption isotherm models available to evaluate the adsorp-
dye is increased from 80.64% to 96.32% when the dosages increase tion phenomena and to predict the maximum adsorption capacity
from 10 mg to 40 mg (Fig. 8a) and then it remains the same for of the adsorbent. The most widely used isotherm models for
50 mg. But the adsorption capacity decreases from 205.4 mg/g to adsorption are Langmuir, Freundlich, and Temkin.
40.65 mg/g (Fig. 8b) when we increase the adsorbent dosage from
10 to 40 mg. As we increase the adsorbent dose initially more pollu- 3.3.1. Langmuir isotherm model
tants are adsorbed on the surface of the adsorbent as more active The Langmuir isotherm model is valid for homogeneous sites
sites are available on the adsorbent, but gradually the adsorption and monolayer adsorbent surfaces with a uniform distribution of
reaches its saturation and no further adsorption takes place. energy levels [22]. The linearization form of the Langmuir isotherm
model is given by:
3.2.3. Effect of initial MG concentration and contact time Ce 1 Ce
The dependency of adsorption of MG dye onto RGO on the ini- ¼ þ ð3Þ
qe q m KL q m
tial concentration of MG dye is shown in Fig. 9. It is observed that

Fig. 7. Effect of pH on the (a) MG removal %, and (b) adsorption capacity (qt) (C0 = 60 mg/L, V = 50 ml, w = 40 mg, T = 30°C, and time = 2hr) by using RGO.

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Dibya Ranjan Rout and Hara Mohan Jena Materials Today: Proceedings 47 (2021) 1173–1182

Fig. 8. Effect of adsorbent dosage of RGO on the (a) MG removal %, and (b) adsorption capacity (qt) (C0 = 60 mg/L, V = 50 ml, pH = 8, T = 30°C, and time = 2hr).

Fig. 9. Effects of contact time on the (a) MG removal %, and (b) adsorption capacity (qt) at different initial concentrations of MG dye solution: (w = 10 mg, V = 50 ml, pH = 8,
T = 30°C, and time = 0–3 hr) by using RGO.

Fig. 10. Effect of temperature on (a) MG removal %, and (b) adsorption capacity (qt) (C0 = 60 mg/L, V = 50 ml, w = 10 mg, and time = 2hr).

Where, qm is the maximum monolayer adsorption capacity, qe is The important characteristic of Langmuir isotherm is called sep-
the equilibrium adsorption capacity (mg. g
1), KL is the Langmuir aration factor (RL) which is a dimensionless constant and is given
constant (mg. g
1), and Ce is the equilibrium concentration of by the following equation[23]:
MG dye solution (mg. L
1) respectively. Fig. 11 shows the Langmuir
1
isotherm model of adsorption of MG dye onto RGO adsorbent RL ¼ ð4Þ
1 þ KL C0
obtained by plotting Ce/qe versus Ce at a constant temperature.
The values of KL and qm are calculated from the slope and intercept
and are reported in Table 1.

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plotting ln qe versus ln Ce at a constant temperature. The values

of n and KF are calculated from the slope and intercept and are
reported in Table 1.

3.3.3. Temkin isotherm model

The Temkin isotherm is valid only for an intermediate range of
ion concentration [24]. The linear form of the Temkin isotherm
model could be expressed as:
RT RT
qe ¼ lnKT þ lnCe ð6Þ
b b
Fig. 13 shows the Temkin isotherm model of adsorption of MG
dye onto RGO obtained by plotting qe versus ln Ce at a constant
Fig. 11. Langmuir isotherm for the adsorption of MG dye onto RGO. temperature.
The relative parameters for the three isotherm models (Lang-
muir, Freundlich, and Temkin) are calculated by using the plots
Table 1
and the data are listed in Table 1. The determination coefficient
Langmuir, Freundlich, and Temkin isotherm parameters for the adsorption of MG.
(R2) for the Langmuir isotherm is found to be maximum that is
Adsorption Isotherm Isotherm Parameters 0.993, whereas the same for Freundlich is 0.9066 and for Temkin
Langmuir isotherm model qm (mg/g) KL (L/mg) R2 0.796. This value suggests that the Langmuir isotherm model bet-
279.85 0.7292 0.993 ter describes the adsorption of MG dye onto RGO than other iso-
Freundlich isotherm model N KF (L/mg) R2
therm models with a maximum adsorption capacity of
0.205 129.024 0.9066
Temkin Isotherm model B KT (L/mg) R2
279.85 mg/g at 303 K.
51.569 16.284 0.796
3.4. Adsorption kinetic study

Where, KL is the Langmuir constant (mg. g
1), and C0 is the ini- The adsorption kinetic study is required for the design and
tial concentration of MG dye solution (mg. L
1) respectively. The RL modeling of the full-scale batch process by selecting optimum
value tells about whether the isotherm model is favourable or not. operating conditions and also to determine the controlling mecha-
For an irreversible model (RL = 0), favourable (0< RL <1), unfavour- nism of the adsorption process. The adsorption experiments were
able (RL >1), and linear (RL = 1). In the present study, the RL value performed at 303 K with an adsorbent dosage of 10 mg and a con-
lies in the range of 0.0223–0.0641, which confirms the adsorption tact time of 180 min. Various kinetics models such as pseudo-first-
of MG dye onto RGO is a favourable process. order [25], Pseudo-second-order [26], and Elovich model [27] were
used to investigate the adsorption mechanism of MG dye onto
RGO.

3.3.2. Freundlich isotherm model 3.4.1. Pseudo-first-order model

Freundlich isotherm model applies to adsorption processes that The pseudo-first-order kinetic model is widely used to predict
°C cur on heterogeneous surfaces and are valid for multilayer pollutant adsorption kinetics. The linearized form of the pseudo-
adsorption. The linear form of the Freundlich model could be first-order model is given by:
expressed as:
ln ðqe
qt Þ ¼ ln qe
k1 t ð7Þ

1 Where, k1(min
1) is the rate constant of the pseudo-first-order

ln qe ¼ ln K F þ lnC e ð5Þ reaction, qe is the equilibrium adsorption capacity which is the
n
amount of adsorbate on the adsorbent surface at equilibrium
Where KF is adsorption capacity (mg.g
1), qe is the equilibrium (mg. g
1), qt is the adsorption capacity (mg. g
1) at time t (min),
adsorption capacity (mg.g
1), and n1is the adsorption intensity; Fig. 14 shows the plot of ln (qe-qt) vs t and the slope and intercept
which indicates the heterogeneity of the adsorbate sites and the gives the values of rate constant (k1) and equilibrium adsorption
relative distribution of the energy. Fig. 12 shows the Freundlich capacity (qe) are reported in Table 2. From Table 2 it is confirmed
isotherm model of adsorption of MG dye onto RGO obtained by that the calculated qe is not in agreement with the experimental

Fig. 12. Freundlich isotherm for the adsorption of MG dye onto RGO. Fig. 13. Temkin isotherm for the adsorption of MG dye onto RGO.

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Fig. 14. Pseudo-first order kinetic plot for the MG dye adsorption by RGO at Fig. 15. Pseudo-second order kinetic plot for the for the MG dye adsorption by RGO
different concentrations. Experimental conditions: (pH = 8.0; T = 30°C; and at different concentrations. Experimental conditions: (pH = 8.0; T = 30°C; and
w = 10 mg). w = 10 mg).

qe and the value of R2 is low for most of the adsorption data which 1 1
qt ¼ lnðabÞ þ lnt ð9Þ
indicates the pseudo-first-order model is not suitable for adsorp- b b
tion of MG dye onto RGO.
Where, a represent the initial adsorption rate (mg g
1 min
1)
and ß represent the desorption coefficient (g mg
1 min
1) respec-
3.4.2. Pseudo-second-order model tively. Fig. 16 shows the plot of adsorption capacity (qt) vs lnt and
The linearization form of the pseudo-second-order model is the values of a and ß are calculated from the slope and intercept
given by: and are tabulated in Table 2. Higher values of a calculated from
t 1 t the plot reveal faster adsorption kinetics°C curred.
¼ þ ð8Þ The relative parameters for the three kinetic models are calcu-
qt k2 q2e qe
lated by using the plots and the data are listed in Table 2. The R2
Where qt is the adsorption capacity at time t (mg. g
1), qe is the value for the pseudo-second-order is found to be maximum that
equilibrium adsorption capacity (mg. g
1), andk2 is the overall is 0.999, whereas the same for pseudo-first-order is 0.921 and for
pseudo-second-order rate constant. Fig. 15 shows the plot of t/qt Elovich 0.985. This value suggests that the pseudo-second-order
versus t and from the plot, the values of rate constant (k2) and model better describes the adsorption of MG dye onto RGO than
the equilibrium adsorption capacity (qe) are calculated by using other kinetic models with a maximum adsorption capacity of
the slope and intercept and are tabulated in Table 2. The value of 263.15 mg/g very close to the experimental adsorption capacity
R2 was obtained as 0.999 for the pseudo-second-order model with of 262.58 mg/g at 303 K.
an adsorption capacity of 263.15 mg/g very close to the experimen-
tal adsorption capacity of 262.58 mg/g thus the pseudo-second- 3.5. Thermodynamic study
order model is best fitted to the adsorption process.
The effect of temperature on the adsorption of MG dye onto
3.4.3. Elovich kinetic model RGO has been investigated, and the thermodynamic parameters
In this model, there will be no interactions among the adsorbed such as a change in enthalpy (DH°), Gibbs free energy (DG°), and
species and the actual solid adsorbent surfaces are energetically change in entropy (DS°) are determined by using the following
heterogeneous. These energetically heterogeneous adsorbent sur- equations[29]:
faces present different kinds of activation energies based on a
DG0 ¼
RTlnK d ð10Þ
second-order reaction mechanism. This model was developed by
Zeldowitsch [28] and the linearization form of the Elovich kinetic
model is given by:

Table 2
Pseudo-first order, Pseudo-second-order, and Elovich kinetic model parameters for the adsorption of MG dye onto RGO at pH 8 and 30°C.

Parameters Concentrations, C0 (mg/L)

20 30 40 50 60
qexp (mg g
1) 98.389 140.32 180.3 229.55 262.58
Pseudo first order
k1 (min
1) 0.0516 0.0479 0.0578 0.0485 0.0405
qcal (mg g
1) 19.965 150.355 226.76 289.397 156.8
R2 0.7784 0.886 0.921 0.828 0.859
Pseudo second order
k2 (g mg
1 min
1) 0.0025 0.00098 0.0009 0.00058 0.0008
qcal (mg g
1) 98.995 141.1 181.3 230.6 263.15
R2 0.9997 0.9998 0.9996 0.9997 0.9995
Elovich model
a (mg g
1min
1) 4.9103 1.8103 7.2103 6.2103 112.8103
b (g mg
1) 0.113 0.0703 0.0614 0.047 0.052
R2 0.8151 0.9597 0.956 0.9856 0.977

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whether the adsorption process is spontaneous or non-

spontaneous. From Table 3 it is confirmed that with temperature
increase in the range of 293–313 K the negative values of DG°
are decreased from
7.537 to
12.52 kJ/mol. This indicates the
MG adsorption process is spontaneous and more favourable at
higher temperatures [30]. The DG° value in the range of 0–15 kJ
mol
1 suggests the adsorption is Physiosorption [31]. From
Fig. 17 the thermodynamic parameters like change in enthalpy
(DH°) and entropy (DS°) are calculated from the slope and inter-
cept of the plot and are given in Table 3. The positive value of
DH° implies that the MG dye adsorption process is endothermic.
The positive values of (DS°) indicate the decreased affinity of
RGO toward the MG dye and randomness at the solid/solution
interface increased during the adsorption process.
Fig. 16. Elovich kinetic plot for the MG dye adsorption by RGO at different
concentrations. Experimental conditions: (pH = 8.0; T = 30°C; and w = 10 mg).
4. Comparison with some previously used adsorbents

To show the advantage of RGO as a potential adsorbent over

previously reported adsorbents, the adsorption capacity of MG
dye was calculated from the Langmuir Isotherm model for all the
adsorbents is listed in Table 4. It can be seen that the adsorption
capacity of RGO is maximum among all the adsorbents with a
value of 279.85 mg/g, which suggests that RGO is a potential adsor-
bent with higher adsorption capacity for MG dye removal.

5. Conclusion

In this paper, GO was synthesized by the modified Hummers

method followed by successful synthesis of RGO by using Hydra-
zine monohydrate as a reducing agent. It was characterized using
XRD, FTIR, FESEM and RAMAN. The prepared RGO adsorbent exhib-
Fig. 17. Thermodynamic study of MG dye adsorption onto RGO. ited an excellent adsorption capacity for MG dye. The MG dye
adsorption fitted well with the Langmuir isotherm model and
pseudo-second-order kinetics model and the maximum adsorption
DS0 DH0 capacity of MG dye onto RGO was 279.85 mg/g at 303 K. The neg-
ln Kd ¼
ð11Þ
R RT ative values of DG° and positive value DH° indicated that the
Where Kd (L.g
1) is the Langmuir isotherm constant, T (K) is the adsorption of MG dye onto RGO was a spontaneous and an
absolute solution temperature, and R (8.314 J mol
1 K
1) is the uni- endothermic process and it occurs due to Physiosorption. The max-
versal gas constant. Gibbs free energy (DG°) value gives the idea of imum MG dye removal efficiency of 96.3% is attained in 120 min.
Therefore, RGO was expected to be a potential adsorbent for the

Table 3
Thermodynamic parameters for the adsorption of MG dye onto RGO.

Adsorbent Temperature (K) DG° (kJ/mol) DH° (kJ/mol) DS° (J/mol.K)

RGO 293
7.537 65.46 249.137
298
8.783
303
10.028
308
11.274
313
12.52

Table 4
Comparison of adsorption capacity of RGO adsorbent with other adsorbents to adsorb MG dye.

Adsorbent Adsorption capacity (mg/g) Condition References

pH Concentration (mg/L) Temp. (K)
Thiourea-Modified Poly (acrylonitrile-co-acrylic acid) 270 8 100 298 [32]
Zeolitic Imidazole Framework-8 224.114 7 200 303 [33]
Activated carbon (lignite) 200 7 200 303 [34]
Bentonite 178.6 5 125 298 [35]
Chitosan bead 93.55 8 100 303 [36]
Lignin sulfonate-based mesoporous materials 121 7 100 308 [37]
Magnetic metal–organic framework composite 114 – 50 303 [38]
Reduced graphene oxide (RGO) 279.85 8 60 303 This work

1181
Dibya Ranjan Rout and Hara Mohan Jena Materials Today: Proceedings 47 (2021) 1173–1182

removal of MG dye from wastewater. The optimum conditions water-based exfoliation and reduction methods, Adv. Mater. Sci. Eng. 2013
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to influence the work reported in this paper. [21] A.S. Sartape, A.M. Mandhare, V.V. Jadhav, P.D. Raut, M.A. Anuse, S.S. Kolekar,
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