Journal of Environmental Chemical Engineering 7 (2019) 103479

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Journal of Environmental Chemical Engineering

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

Adsorption of textile dyes with ultrasonic assistance using green reduced T

graphene oxide: An in-depth investigation on sonochemical factors
Rijo Rajumon, Jeswin Cyril Anand, Anu Mary Ealias, Devika Satish Desai, Giphin George*,
M.P. Saravanakumar*
Department of Environmental and Water Resources Engineering, School of Civil Engineering, Vellore Institute of Technology, Vellore Campus, India

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

Keywords: Green: This study reports adsorption of Methylene Blue (MB) and Basic Fuchsin (BF) on green reduced graphene oxide.
reduction Using modified Hummer’s method, Graphene Oxide (GO) was synthesised and reduced using Tamaridus Indica.
Reduced graphene oxide The synthesised GO and RGO were characterized using XRD, UV–vis spectroscopy, TEM, XPS, FT-IR and BET
Ultrasonication analysis. Through XRD result, the reduction in a peak corresponding to (001) plane and appearance of new peak
Dye adsorption
at (002) plane confirmed the reduction process. TEM results displayed a hexagonal SAED and lamellar structure
Isotherm-kinetics
Reusability
in RGO with a d-spacing of 0.346 nm in the (002) plane. Effect of variables such as pH, initial dye concentration,
dosage, temperature, sonication time, ultrasonic power and frequency were studied and optimum conditions for
the removal of MB and BF were found. From the Langmuir isotherm model, the maximum adsorption capacity
was noticed to be 238.095 and 243.90 mg/g respectively for MB and BF. Further, the presence of humic acid and
various ions decreased the removal efficiency for both the dyes. The experimental results indicated that the
pseudo second order suited well than other kinetic models. Among various error analysis, ARE model provided
minimum error for Langmuir isotherm (MB: 7.52, BF: 9.82) and kinetic study (MB: 10.47, BF: 6.04). FTIR and
XPS analysis indicated that electrostatic attraction, hydrogen bonding, n-π and π -π interactions played sig-
nificantly during adsorption process. The facile synthesis and higher adsorption capacity indicates that the
material could be a potential candidate for the removal of textile effluents.

1. Introduction Several remediation techniques are available today which include

During the past few decades, water pollution has become a seriously
challenging environmental issue because of the release of many kinds of
pollutants. Even though there are various reasons for the pollution, the
effluents from the industries have a primary role in aggravating the
issue. Industries like textile, chemical, plastic, leather, etc. are of great
environmental concern nowadays as they produce wastewaters and
discharge dyes and other compounds which are toxic in nature [1]. The
sudden growth of urbanisation and the rise of industrialisation has led
to a rapid enhancement in dye usage in several industries, particularly
the textile industries [2]. They have very high solubility in water but
are not aesthetically pleasing and consume more dissolved oxygen [1].
The wastewater having the presence of dyes is very tedious to treat due
to the complexity in their chemical composition, which consists of
polymers, toxic dyes, organic solvents, etc [3,4]. Therefore, it has be-
come a necessity to treat the wastewater consisting of dyes as they are
being discharged to natural water bodies.
membrane filtration, precipitation, ion exchange, adsorption, biological
oxidation, photocatalytic degradation and electrochemical treatment
for the removal of dyes [5,6]. Among all the available methods, the one
which is being regarded as the most effective and common method for
the process of water purification is adsorption, which can be attributed
to its flexibility, high adaptability, least amount of harmful substances,
eco-friendly technology, easy operation and low cost [7].
The efficiency of the adsorption process can be further modified by
adopting additional techniques like ultrasonication [8]. The agitation of
particles in a sample by the application of sound energy is known as
sonication and when the ultrasonic range of frequencies is used for the
same it is termed as ultrasonication. Mahmoodi et al. [9] conducted
ultrasonic-assisted adsorption of Malachite Green using GO-nano-
composites and obtained an adsorption capacity of 118 mg/g. Banerjee
et al. [10] performed adsorption of acid yellow 36 and acid blue 74
using chitosan–graphene oxide nanocomposites and achieved adsorp-
tion capacities of 29.25 and 29.61 mg/g respectively. Ultrasonication

⁎
Corresponding authors.
E-mail addresses: rijorajumon37@gmail.com (R. Rajumon), jeswincyril95@gmail.com (J.C. Anand), anumaryealias@gmail.com (A.M. Ealias),
deveekadesai27@gmail.com (D.S. Desai), giphingeorge@gmail.com (G. George), saravanakumar05@gmail.com (M.P. Saravanakumar).

https://doi.org/10.1016/j.jece.2019.103479
Received 24 August 2019; Received in revised form 4 October 2019; Accepted 13 October 2019
Available online 24 October 2019
2213-3437/ © 2019 Elsevier Ltd. All rights reserved.
R. Rajumon, et al.
Nomenclature
Co Initial dye concentration (mg/L)
Ce Equilibrium dye concentration (mg/L)
qe Quantity of dyes adsorbed per unit mass of adsorbent (mg/
L)
m Adsorbent mass (g)
V Volume of dye solution (L)
MPSD Marquardt's Percent Standard Deviation
SD Standard Deviation
ARE Average Relative Error
qm Maximum dye adsorption capacity (mg/g)
Ka Adsorption energy constant in the reaction (L/mg)
KL Langmiur Constant (L/mg)
Kf Freundlich adsorption constant (mg/g)
n Freundlich adsorption exponent
RL Separation factor
qt Amount of dyes adsorbed at time t (mg/g)
B Temkin isotherm energy constant (J/mol)
AT Binding constant at equilibrium (L/g)
k1 Rate constant for pseudo first order equation (min−1)
k2 Rate constant for pseudo second order equation (g/mg/
min)
has been effectively applied even on non-nanomaterials for dye ad-
sorption process. Archin et al. [11] prepared activated carbon from
tobacco residues (TRAC) and obtained a removal efficiency above 90%,
while Askari et.al [12] attained a removal efficiency of around 98% for
activated carbon hybrid (AC-MOF-5). The benefits offered by the ul-
trasonic-assisted adsorption makes it more popular than the standard
adsorption process [13]. It considerably improves the efficiency and
reduces both adsorbent dosage and contact time required for the ad-
sorption process [2,14]. A wide range of adsorbent materials is avail-
able nowadays. The commonly used adsorbents like mesoporous silica
[15], fly ash [16], zeolite [17], activated carbon [18] and polymeric
materials possess certain limitations such as high cost, poor selectivity
and low adsorption capacity [19]. These drawbacks have encouraged
many researchers to investigate the possibilities of nanoparticles being
used as effective and non-hazardous adsorbent.
Due to the rapid development in the nanotechnology sector during
the past few years, researchers have been focussing on green synthe-
sised nanoparticles for pollutant removal. Graphene is one among the
carbon nanostructures which is made up of hexagonal two-dimensional
sheets of sp2 bonded carbon atoms [20]. It has been emerging as an
important part of nanoscale science and is a significant material in the
sector due to its wide range of applications. It is having widespread use
in numerous sectors owed to its outstanding characteristics like ex-
cellent optical, mechanical, thermal and electrical properties, porous
structure, chemical stability and high surface area [21]. It is commonly
used for applications such as purification of water, nanocomposites,
battery, supercapacitors, drug delivery and biosensors [22]. Graphene
can be prepared using various methods including reduction of GO [23],
epitaxial growth [24] and chemical vapour deposition [25]. Electro-
chemical [26], thermal and chemical [27] methods can be used to
achieve GO reduction. Chemical reduction is one of the most favourable
methods as it involves simple process, mass production capability, low
cost and low equipment demand. This method involves oxidation,
where graphite is oxidized to GO and reduction process, where the
synthesised graphene oxide is reduced using a strong reducing agent.
Modified Hummer’s method can be effectively used for the synthesis of
GO [28]. This method is simple and produces GO with reliable quality
consistently. More quantity of material can be synthesised with high
efficiency using modified Hummer’s method. The porosity, nature of
dyes, surface area, dye molecule interaction, etc determines the
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Journal of Environmental Chemical Engineering 7 (2019) 103479
kia,, kib Intra-particle diffusion constant for stage 1 and 2 (mg/g/
min1/2)
Ca, Cb Thickness of the boundary layer for stage 1 and 2 (mg/g)
R Universal gas constant
Kd Adsorption distribution coefficient
ΔS Change in entropy (KJ mol−1 K−1)
ΔG Change in free energy (KJ mol−1)
ΔH Change in enthalpy (KJ mol−1)
T Temperature (K)
f Frequency (kHz)
γ Heat capacity ratio of the gas at constant pressure and
volume
ρ Density of the surrounding medium (kg/m3)
α Initial adsorption rate (mg/g/min)
β Activation energy constant of surface coverage (g/mg)
σ Surface tension (N/m)
r Radius of resonant bubble (µm)
τ Decrease in collapse time (µs)
Pm Liquid pressure
Po Ambient pressure
Pv Pressure present in bubble during collapse at initial phase
t1/2 Half-life (min)
Ce ,1/2 Half-capacity concentration (mg/L)
suitability and efficiency of graphene based materials for the removal of
organic dyes [29]. They are particularly suitable for cationic dye re-
moval due to the presence of more oxygen functional groups having
negative charge and sufficient number of sites for adsorption to take
place. Proper diffusion of the dye molecules can occur throughout the
adsorbent which can be attributed to the high specific area and the
porous structure of the material [30]. RGO behaves as an excellent
adsorbent material for the removal of organic dyes from wastewater as
it is having several wrinkles in its planar structure along with the
presence of residual oxygen functionalities [31].
Several reducing chemicals were made use of in the reduction
process including hydroquinone [23], lithium aluminium hydride [32],
sodium hydride [33] and hydrazine [34] which are severely toxic,
hazardous and cause adverse impacts on the ecosystem [35]. The
chemicals used may contaminate the reduced GO by incorporating
harmful impurities which may cause negative effects on the environ-
ment [36]. These problems can be avoided to a certain extent by the
usage of environmental friendly green materials such as tea solution,
reducing sugars, glucose, carrot root and green tea [37]. Sugarcane
bagasse extract [38] and Chrysanthemum extract [39] were also used
by researchers for the green reduction of graphene oxide. Jin et al
carried out the removal of dyes using green reduced graphene oxide
prepared from Eucalyptus leaf extract [36]. Several phytochemicals are
present in plants including flavonoids, steroids, carbohydrates, sapo-
genins, etc which are capable of reducing the synthesised GO. Thus
plant extracts can be used effectively to replace the toxic chemical re-
ducing materials [40]. Till date in the literature, tamarindus indica ex-
tract was not used as a reducing agent during the synthesis of RGO.
Hence, in this study, tamarind extract was utilised as a green reducing
agent for the GO reduction without causing toxic or hazardous effects.
The textile dyes in wastewater cause several chemical reactions and
pose great threat to the aquatic systems even at very low concentrations
[5]. They can lead to severe damage to humans by causing damage to
kidney and reproductive disorders, sometimes even affecting the cen-
tral nervous system. Hence the removal of these dyes is of prime sig-
nificance. Two among the most commonly used toxic dyes include
Methylene blue (MB) and Basic Fuchsin (BF). Methylene blue is a
widely used cationic dye possessing applications in dyeing wood and
cotton. It can cause various side effects including shortness of breath
during inhaling, headache, enhanced heartbeat, nausea, high blood
R. Rajumon, et al.
pressure, vomiting, diarrhoea and cancer [7]. Basic Fuchsin dye is one
of the rare dyes that are naturally inflammable. They are used com-
monly as strong colouring agents in leather manufacturing industries
and textile industries. Irritation to skin and eye is caused by physical
contact with the BF dye [41,42]. Both the dyes are found to be toxic,
teratogenic and mutagenic [43]. This scenario points at the urgent need
for developing efficient removal and remediation strategies and iden-
tifying new materials for reducing the pollution being caused by the
dyes.
The aim of this research work is (i) to synthesise GO by modified
Hummer’s method and to reduce GO using Tamarindus indica (ii) to
perform comparative characterisation of the synthesised GO and RGO
(iii) to find the efficiency of RGO in ultrasonic-assisted BF and MB dye
removal (iv) to analyse the influence of several system constraints like
initial dye concentration, pH, temperature, ultrasonic frequency, ionic
strength, adsorbent dosage, sonication time, humic acid and ultrasonic
power on the dye removal.
2. Materials and methods
2.1. Materials
Basic Fuchsin (MW =337.85 g/mol, λmax =550 nm) and Methylene
Blue (MW =407.97 g/mol, λmax =668 nm) were the dyes used in this
study. The chemical reagents utilised in this research include NaNO3,
98% H2SO4, KMnO4, HCl and 30% w/v H2O2 which were of A.R grade.
Graphite powder (100 microns) was utilised for GO synthesis. All these
chemicals were bought from SDFCL, Mumbai.
2.2. Synthesis of GO
Modified Hummer’s method was used for performing the graphene
oxide synthesis [44]. Briefly, 5 g of graphite powder, 2.5 g of NaNO3 and
120 mL of conc. sulphuric acid (98%) were rigorously mixed using a
magnetic stirrer. The temperature was maintained during the reaction
below 20 °C using an ice bath set-up and agitation was continued ap-
proximately for 30 min. Further, 15 g of KMnO4 was added to this
mixture and stirring was done for 8 h maintaining the temperature less
than 20 °C. Later, 150 mL of double distilled water (DDW) was added
along with rapid mixing. The mixture was taken out from the ice bath
and was heated and agitated continuously. A rapid rise in the reaction
temperature up to 98 °C was achieved by heating the mixture and 50 mL
of H2O2 was then mixed with the solution. The product was cooled and
centrifuged at 5000 rpm to separate the particles. Afterwards, the par-
ticles were washed with 5% HCl solution followed by DDW many times.
Later, it was dried at 100 °C in a hot air oven for overnight. Finally, fine
graphene oxide particles were obtained and stored in desiccator for
further use [45].
2.3. Reduction of synthesised GO
Tamarind extract (tamarindus indica) was utilised as reducing agent
in this work. Initially, 100 mg of GO was added to 100 mL of DDW in a
250 mL beaker. The mixture was sonicated for one hour to accomplish
better dispersion. For the preparation of tamarind extract, 200 g of ta-
marind was added to 600 mL of DDW and heated for 1 h at 100 ℃.
Sufficient time was allowed for cooling and the extract was filtered out
from the solution obtained. This extract was mixed with the prepared
GO suspension and heating was done along with stirring for 30 min. The
reduced material was found to settle at the bottom of the beaker.
Washing was done for five times with DDW and centrifuged until the
supernatant becomes clear and colourless. The reduced GO was then
recovered and a hot air oven was used for drying the material. The RGO
obtained after drying was powdered and stored for further use [46].
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Journal of Environmental Chemical Engineering 7 (2019) 103479
2.4. Procedure for stock preparation
The preparation of stock solution was performed at room tem-
perature by dissolving 1 g of MB and BF separately in 1 L volumetric
flask and made up with DDW. Dilution of the stock solution was carried
out to the required concentrations (50, 75, 100 and 125 mg/L) so as to
obtain the solution to conduct the tests. UV–vis spectrophotometer was
utilised for the determination of initial and final dye concentrations
[47].
2.5. Adsorption procedure
Experiments of batch adsorption were carried out continuously
under ultrasonication by varying different parameters so as to de-
termine the maximum dye removal efficiency of RGO in both dyes. For
the purpose of optimising the pH, tests were performed at various pH
between 2 and 10. After pH optimisation, the optimum value was used
to carry out further experiments for the optimisation of other para-
meters. The tests for finding out the influence of various parameters
including dosage of adsorbent (0.01-0.09 g/50 mL), initial dye con-
centration (50–125 mg/L) and ultrasonication time (1–19 minutes) on
BF and MB dye adsorption were conducted at optimised pH value.
UV–vis Spectroscopy was used for estimating the removal efficiency of
all the samples tested using different combinations of parameters. The
percentage removal of the dye was estimated from Eq. (1).
C − Ce ⎞
% Dye Removal = ⎛ 0 ⎜ × 100⎟
⎝ C0 ⎠ (1)
where the initial concentration of both BF and MB dyes was represented
as ‘Co ’ (mg/L) and the equilibrium dye concentration was represented
as ‘Ce ’ (mg/L). The adsorbed dye quantity at equilibrium qe (mg/g),
adsorbent mass m (g) and dye solution volume V (L) can be obtained
from Eq. (2) [47].
V
qe = (C0 − Ce ) ×
m (2)
2.6. GO and RGO characterisation
A Merck Spectroquant Pharo-300 spectrophotometer was used to
analyse the UV–vis absorption spectra of GO and RGO within a range of
wavelength 200 and 700 nm. Characterisation was done using X-ray
diffraction (XRD-Bruker, D8 Advance) to investigate the crystallinity of
the material. Transmission Electron Microscopy (TEM-FEI Tecnai G2
T20 S Twin) was used so that the size of synthesised GO and RGO and
the surface morphology can be analysed. X-ray photoelectron spectro-
scopy (Kratos Analytical, Axis Ultra) was performed to obtain the ele-
mental structure of both GO and RGO. FTIR analysis was carried out for
GO and RGO using FTIR spectrometer (IR Affinity-1, Shimadzu) to find
existence of different functional groups. It was also performed on the
samples after adsorption to examine variations in the presence of
functional groups. Brunauer-Emmet-Teller (BET) analysis was per-
formed utilising a Quantachrome ASIQwin surface analyser for finding
the adsorbent surface area.
2.7. Point of zero charge (pHpzc)
pHpzc of synthesised RGO was assessed by carrying out a set of six
batch tests at several pH. NaOH and H2SO4 solutions were prepared and
were added to 0.01 M NaCl solution to adjust the initial pH between 2
and 12. To each of the pH adjusted solutions, 150 mg of the prepared
RGO was added and stirred continuously at a rate of 200 rpm for 24 h.
The final pH was obtained after filtration using Whatman #41 filter
paper. The variation in values among the initial and final pH was found
out for each set of experiments which can be represented as ΔpH. ΔpH
vs initial pH graph was plotted from which the pHpzc was determined
R. Rajumon, et al. Journal of Environmental Chemical Engineering 7 (2019) 103479

n
[48]. 100 qe meas − qe cal
ARE = ∑
n i=1 qe meas (5)
2.8. Error analysis

The best suitable model for both isotherm and kinetics were chosen
depending on the coefficient of correlation value (R2 ). The calculated 3. Results and discussions
values of qe (qe, cal ) were found out from the linearised form of equations
of each model used in kinetics and isotherm studies. The calculated, as 3.1. GO and RGO characterisation
well as experimental values were fitted to various error models in-
cluding MPSD , SD , ARE and the least value obtained demonstrates the The UV–vis spectra for GO and RGO are represented in Fig. S1. The
minimum error. absorbance peak value for GO was obtained at ∼240 nm which might
The error analysis equations used are given below [49]. be due to π-π* transition of the C]C bonds similar to the outcomes
obtained from previous studies [50]. After reduction, the absorbance
n 2
1 ⎡ qe meas − qe cal ⎤ peak was found to be shifted to ∼290 nm signifying the revival of GO
MPSD = 100 ∑
n − p i=1 ⎢ qe meas ⎥ sheets and the network restoration of sp2 hybridised carbon caused by
⎣ ⎦ (3)
the removal of functional groups having oxygen [20].
n 2 Transmission Electron Microscopy was performed to identify and
qe meas − qe cal ⎤ 100
SD = ∑ ⎡⎢ qe meas ⎥ n−1 analyse the surface morphological characteristics and features of GO
i=1 ⎣ ⎦ (4) and RGO. TEM images (Fig. 1(a & b)) captured clearly shows the folds

Fig. 1. TEM images of (a), (b) GO and (c), (d) RGO at different magnifications; SAED pattern of (e) GO and (f) RGO; (g) interfringe distance of RGO.

4
R. Rajumon, et al.
Fig. 1. (continued)
and wrinkles present within the GO nanosheets. This can be attributed
to the structural defects in the nanosheets and the presence of oxygen
functionalities having sp3 sites [29]. A structure resembling a curved
sheet and having fairly smooth surface was obtained from the trans-
mission electron micrograph of RGO. The confirmation of the presence
of RGO was obtained by the presence of lighter and darker portions
observed from the TEM image in which the lighter region represents
graphene having few layers whereas multi-layered curling or stacking
nanostructure of graphene is represented by the region having darker
shade. From Fig. 1(c & d), it was visible that both GO as well as RGO
having multiple wrinkles and folds. The thermodynamic stability of the
2D membrane structure due to bending might be the reason for these
wrinkles and folds being part of the graphene’s intrinsic nature [51].
Cohesive interaction can be considered as the primary reason for the
aggregation of RGO nanosheets with each other. The nanosheets of
5
Journal of Environmental Chemical Engineering 7 (2019) 103479
RGO were also found to have a fluffy appearance which can be at-
tributed to the presence of folded edges and the elastic corrugations.
Fig. 1(e & f) indicates the selected area electron diffraction (SAED)
patterns attained from TEM analysis of GO and RGO. The RGO sheets
have crystalline nature and an atomic structure of hexagonal shape
which are identified from the SAED patterns obtained as represented in
Fig. 1(f). The six member rings found in the inner portion corresponds
to the [1100] plane and the six visible and bright diffraction points
were found to represent the diffractions of the [0001] plane [52]. These
six bright points retained the hexagonal symmetry shown by the dif-
fraction patterns of [0001] plane which agrees with the Bragg reflection
plane [53]. A lamellar structure was shown by RGO along with a d-
spacing value of 0.346 nm in the plane (002) (Fig. 1g). This complies
with the outcomes attained from XRD.
Fig. 2 depicts the elemental configuration of GO and RGO obtained
R. Rajumon, et al.
Fig. 2. XPS spectra of GO and RGO: (a), (b) wide spectra and (c), (d) C1s spectra respectively.
from XPS spectra. The wide spectra of both GO and RGO along with
their atomic percentage data of carbon and oxygen are demonstrated in
Fig. 2(a & b). The C/O ratio of RGO was obtained as 3.26 which found
to be higher than that of GO as 2.54. This indicates that reduction has
taken place by the elimination of functional groups having oxygen from
GO. The enhancement in C/O ratio from GO to RGO is similar to the
results obtained from the GO reduction using Eucalyptus leaf (C/O ratio
increased from 2.08 to 3.47) [36]. The C1s and O1s characteristic bands
were examined from the XPS spectrum of GO and RGO. The reduction
process of GO can be confirmed as the O1s composition of RGO was
found to decrease when compared to GO, which indicates that the
oxygen functional group removal has occurred. Fig. 2(c & d) displays
the C1s spectrum of GO and RGO respectively. Three major peaks were
acquired in the spectrum of GO at distinct binding energy values of
283.9 eV, 286.02 eV and 287.80 eV indicating the CeC, CeO and C]O
bonds respectively of hydroxyl oxygen and epoxide functional groups
[54]. The wide and small shoulders implicated the presence of C]O
groups. Even though there were slight differences in the binding
6
Journal of Environmental Chemical Engineering 7 (2019) 103479
energy, GO and RGO exhibited similar characteristics of C1s spectrum,
whereas significant reduction was there in the oxygen functional group
intensity. In C1s spectrum of RGO, peaks resembling the CeC, CeO and
C]O bonding were obtained at binding energy values 284.2 eV,
286.7 eV and 288.15 eV respectively. An additional peak indicating the
OeC]O appeared in the RGO spectrum corresponding to the binding
energy 289.91 eV.
The XRD characterisation was performed to identify and analyse the
type of crystal structure and the spacing between the planes. XRD
spectra of GO and RGO obtained from XRD analysis are displayed in
Fig. 3(a). A diffraction peak observed at a 2θ value of 10.55° was ex-
hibited by GO which corresponds to the crystal plane of (001) [55]. The
d-spacing (interplanar spacing) corresponding to the 2θ value of 10.55°
was obtained as 0.86 nm using Bragg’s equation. This peak value at
10.55° could be owed to the intercalation of functional groups having
oxygen and H2O molecules into space among the layers. While in RGO,
the peak value of the diffractogram shifted to a 2θ value of 26.36°
where a broad band was obtained, while the peak at 10.55° had a
R. Rajumon, et al.
Fig. 3. (a) XRD pattern of GO and RGO; (b) FTIR spectra of GO and RGO; (c) FTIR spectra of RGO after adsorption of MB and BF dyes.
significant reduction in intensity indicating the restacking of the gra-
phene sheets which would have taken place during the reduction pro-
cess. RGO d-spacing was obtained as 0.337 nm corresponding to the
(002) crystal plane [56]. The reduction in d-spacing might be owed to
the exclusion of functional groups containing oxygen after the reduc-
tion process. This indicates the formation of nanosheets of RGO having
several layers of thickness.
The functional groups available in the synthesised GO and RGO
were determined from the FT-IR spectroscopy as depicted in Fig. 3(b). A
band, which was wider and stronger in nature was noticed at
3386.36 cm−1 because of occurrence of OeH stretching vibration [57].
Certain peaks of low intensity were found at 1375.25 cm-1 (carboxyl)
and 1707.00 cm−1 (carboxyl and carbonyl) resulting from C]O
stretching by the COOH group on the surface of GO [58,59]. Certain
bands were also obtained at 1608.63 cm−1, 1045.42 cm−1 and
1217.08 cm−1 implying that the functional groups C]C, CeO and
CeOH are present. For RGO, peak intensities of OeH, C]O and C]C
bands were found to be lowered by a significant margin, which in-
dicates that the tamarind extract has reduced the material and deox-
ygenation process would have taken place [38,60]. Generally, the
presence of peaks in between 500-700 cm-1 indicates the metal oxides
[58]. In this study since there is no presence of metals, the peaks within
the range of 500–600 could be due to the stretching of C–H and C–O
[61]. The FT-IR spectrum of RGO after MB and BF dye adsorption is
7
Journal of Environmental Chemical Engineering 7 (2019) 103479
explained in Section 3.6.
The distribution of pore size and the porosity characteristics of GO
and RGO were identified from the analysis of nitrogen adsorption-
desorption BET isotherms and are represented in Fig. S2(a & b). A
distinct H4 hysteresis loop was followed and could be categorised under
the type IV isotherms. The pore structures having complexity in its
characteristics were analysed with the help of hysteresis loop [62]. The
percolation through the narrow pore necks or the pore blocking phe-
nomenon can be considered as the primary reason for the steepness of
the hysteresis loop in the desorption phase [29]. A completely enclosed
isotherm was not obtained for both GO and RGO. This can be attributed
to the generation of minute slip pores in the microporous region which
may have led to swelling. Even at a relative pressure (P/Po) less than
0.1, nitrogen adsorption was obtained indicating the micropore for-
mation [63]. The inset images of Fig. S2(a & b) also depicts the BJH
model for analysing the pore size distribution of GO and RGO. From this
model, the average pore diameter was determined to be 3.882 nm for
GO and 3.144 nm for RGO. The cumulative adsorption surface area of
GO and RGO was observed approximately as 41.44 and 24.16 m2/gm
respectively whereas the pore volume was obtained as 0.134 and 0.049
cc/g respectively. Majority of the pores (greater than 90%) lie in be-
tween 2–50 nm which corresponds to mesoporous range. The rest of the
pores were found to be in the microporous range.
R. Rajumon, et al.
3.2. Adsorption isotherms
The adsorption isotherm studies were performed utilising three
models like Temkin, Freundlich and Langmuir model. The constraints
like qm and K a values represented in Table 1 were obtained from the
graph plotted among 1/ qe and 1/ Ce (Fig. S3(a)) of the Langmuir model.
Both the MB and BF adsorption on to the surface of RGO in Langmuir
model showed a coefficient of correlation ( R2) of 0.935 & 0.942 re-
spectively. The maximum dye adsorption capacity ( qm) for MB and BF
dyes was observed as 238.095 and 243.90 mg/g respectively. The ad-
sorptive technique of MB and BF dyes using RGO was perceived to be
favourable based on the RL value. For Freundlich isotherm model, a
graph plotted between logqe and logCe yielded a linear line ( R2 = 0.915
& 0.921) for MB and BF with slope value of 1/ n and intercept value of
log Kf as represented in Fig. S3(b) The higher value of Kf (58.398 &
33.37) and n (1.45 & 1.705) indicates heterogeneous adsorption and
positive co-operative binding [64]. The slope value ( 1/ n ) falls in the
range of 0 to 1 indicating heterogeneity of surface and the slope getting
closer to zero denotes high heterogeneity [65]. For Temkin isotherm
model, plotting of a graph between lnCe and qe for both MB and BF dyes
showed a linear line ( R2 = 0.7792 & 0.8581) with intercept value
B lnAT and slope B as given in Fig. S3(c). A greater R2 value was
achieved for Langmuir isotherm model in case of both dyes which was
good enough to explain the dye adsorption onto the surface of RGO.
Only single layer of adsorption takes place in Langmuir model and after
equilibrium no more adsorption takes place, whereas in case of
Freundlich model adsorption was assumed to be heterogeneous which
does not limit the monolayer adsorption [66,67].
3.3. Adsorption kinetics
The kinetic models were utilised for adsorption rate calculation for
MB and BF dye removal. Pseudo-first-order, pseudo-second-order,
Elovich and intraparticle diffusion models were investigated in this
work. The values of coefficient of correlation ( R2 ) for MB and BF dyes
using pseudo-first-order model, were 0.8364 & 0.9558 respectively
(Table 2) which were obtained from the graph plotted between
log (qe − qt ) and t (Fig. S4a). The graph plotted between t / qt and t along
with the intercept 1/ k2 qe2 and slope 1/ qe gives pseudo-second-order
model (Fig. S4b) having more R2 value (0.953 for MB and 0.9801 for
BF) than pseudo-first-order model. The calculated qe values (qe, cal ) for
pseudo-second-order models were nearer to the experimental qe values
(qe, exp ) than pseudo-first-order kinetic models. This nearness in qe values
along with higher R2 values indicates that pseudo-second-order model
was best fitted with the experimental values [68]. The adsorption rate
(h = k2 × qe2 ) had a positive effect in the initial stage and the values of
rate constants were also higher. The h value for BF (140.6872 mg/g/
min) was greater than MB (55.5759 mg/g/min) denoting rapid rate of
adsorption in preliminary phase of BF than MB onto RGO. The k1, k2 ,
and h values were acquired at optimised experimental conditions (do-
sage of adsorbent - 0.03 g/50 mL for BF and 0.05 g/50 mL for MB; Co-
50 mg/L for both dyes; pH-8 for BF and pH 10 for MB). It can be in-
ferred that the ultrasonication process exerts a good positive effect on
quick attainment of equilibrium state. Similar studies were conducted
by Zhao et al [69] and Bojic Veljkovic [70] for adsorption process of
dyes with the aid of ultrasonication.
The coefficient of correlation (R2) for MB and BF was observed as
0.8641 & 0.8668 respectively (Table 2) which was obtained from the a
plot between qt and lnt of Elovich model (Fig. S4c). kia and kib re-
presents the diffusion rate constants for stage 1 and stage 2 respectively.
Fig. S4(d) was attained by plotting a linearised line of qt versus t . As
the line crosses through the origin it shows the limiting rate in-
traparticle diffusion [71]. The line was not passing via origin created a
multi-linear pattern, displaying the diffusion on boundary layers, which
contributes in MB and BF adsorption onto the surface of RGO. The first
stage of intraparticle diffusion shows macropore diffusion and the
8
Journal of Environmental Chemical Engineering 7 (2019) 103479
second one is micropore diffusion. The results of kia and kib implies that
adsorption does occur in two stages onto the surface of RGO. In the
primary stage of diffusion, the fitting line didn’t pass via origin, in-
dicating resistance in boundary layer during dye adsorption process
[72]. The intercept value (Table 2) was less with a sharp rise in value
for both the dyes. Further fit line deviation was perceived demon-
strating the variation in mass transfer with respect to time in both
stages. Hence for diffusion, the value of kib during second stage is
smaller when compared with the value of kia in first stage. The higher
value of kia in the initial stage for both dyes shows that mass transfer
occurs into the active sites due to the turbulence generated by ultra-
sound. The model indicates not only pore diffusion as the rate defining
step, but also has to consider bulk and intraparticle diffusion since it has
a substantial role in first phase and second phase of adsorption process.
The values of boundary layer thickness denoted as Ca and Cb enhances
after the first stage of MB and BF adsorption onto RGO as shown in
Table 2. In the later stage greater value of Cb was observed representing
higher intercept value and hence an enhancement in the thickness of
boundary layer.
Various error models were analysed for both kinetic and isotherm
data. From the comparison between each error model analysed, ARE
model does give less error for Langmuir and pseudo-second-order
model for both MB and BF dyes and is represented in Table S1. The least
error values obtained for Langmuir and pseudo-second-order models
indicates that they were best suited for adsorption studies.
3.4. Effects of various factors on ultrasonic assisted dye adsorption
3.4.1. Effect of pH
pH is a substantial variable that has considerable influence on ad-
sorption as it varies the charge existing on the surface of the adsorbent
[73]. This work was performed to observe the maximum removal ef-
ficiency by varying the pH from 2 to 10 for both the dyes as given in
Fig. 4(a). The removal efficacy of BF was improved from 78.24 to
86.63% after pH was raised from 2 to 8 and reduced to 83.73% at pH
10. For MB, as the pH was changed from 2 to 10, the percentage re-
moval was increased from 21.89 to 98.64%. This result states that the
adsorption of BF and MB has significant removal at alkaline condition
as residual oxygen functional groups are available over the surface of
RGO which transmits the negative charge. The adsorption was occurred
because of electrostatic attraction among dye molecules having a po-
sitive charge and the negatively charged adsorbent. At acidic condition,
RGO surface attains positive charge leading to strong electrostatic re-
pulsion amongst RGO surface and dye molecules attributed to the
protonation of several functional groups, which results in a significant
reduction of percentage removal. A substantial removal of BF and MB
was achieved at alkaline pH through electrostatic attraction and H
bonding, which leads to deprotonation of adsorption sites [74]. The
pHpzc was used to represent the active spots existing on RGO and sur-
face adsorption which is explained in detail in Section 3.6.
3.4.2. Effect of adsorbent dosage
The influence of adsorption of BF and MB dyes which was
Table 1
Langmuir, Freundlich and Temkin isotherms constants for the adsorption of MB
and BF on RGO.
Langmuir Freundlich Temkin
qm KL RL R2 Kf n R2 AT B R2
(mg/g) (L/mg) (mg/g) (L/g) (J/mol)
MB
238.09 0.34 0.05 0.93 58.39 1.45 0.91 2.13 75.48 0.78
BF
243.90 0.10 0.15 0.94 33.37 1.75 0.92 0.70 66.66 0.86
R. Rajumon, et al. Journal of Environmental Chemical Engineering 7 (2019) 103479

Table 2
Pseudo-first order, Pseudo-second order, Elovich and Intra-particle diffusion constants for the adsorption of MB and BF on RGO.
Dye (mg/L) qe, exp (mg/g) Pseudo-first order Pseudo-second order Elovich Intra-particle diffusion

qe, cal (mg/g) k1 R2 qe, cal (mg/g) k2 R2 α β R2 kia , kib C a, C b Ra2, Rb2
(min−1) (g/mg/min) (mg/g/min) (g/mg) (mg/g/min1/2) (mg/g)

MB
50 224.55 334.27 0.31 0.84 263.16 1.10 × 10−3 0.95 276.43 0.02 0.86 31.64, 43.75 69.32, 56.41 0.92, 0.97
BF
−3
50 175.65 141.15 0.25 0.96 196.07 2.36 × 10 0.98 510.45 0.03 0.87 22.84, 12.84 73.34, 125.29 0.87, 0.87

investigated by varying RGO dosage from 0.01 to 0.09 g/50 mL re-
spectively is represented in Fig. 4(b). The percentage removal of BF was
enhanced from 70.47% at 0.01 g/50 mL to 91.02% at 0.03 g/50 mL and
then reduced to 78.23% at 0.09 g/50 mL of RGO dosage. Also, the
percentage removal for MB dye adsorption was increased from 95.30%
at 0.01 g/50 mL to 98.67% at 0.05 g/50 mL and then reduced to 95.46%
at 0.09 g/50 mL. Generally, the dye removal efficacy of dyes enhances
with an enhanced RGO dosage ascribed to higher surface area and more
amount of surface reactive center [75]. This results in the adsorbent
particles getting diffused efficiently in the solution with the aid of
acoustic waves, thereby leading to the improvement in the adsorbent
area, diffusion coefficient and the surface atoms. When adsorption
dosage greater than optimum value, the molecules of dye cannot
quickly access the adsorption sites until it achieves equilibrium. Also,
the generation of screening effect and the adsorbent particle aggrega-
tion was caused by the enhancement of adsorption dosage ensuing in a
reduction in RGO surface area and hence the removal efficiency [76].
3.4.3. Effect of initial dye concentration
The concentration of BF and MB dyes was varied from 50 mg/L to
125 mg/L to achieve the maximum dye removal which is displayed in
Fig. 4(c). For BF adsorption, the maximum percentage removal was
detected as 91.02% at 50 mg/L, whereas the minimum removal effi-
ciency was 32.56% at 125 mg/L. Similarly, for MB dye adsorption, the
maximum percentage removal was 98.64% at 50 mg/L, whereas the
minimum removal efficiency was 35.29% at 125 mg/L. This result de-
monstrates that at lower dye concentration, the RGO removal efficacy
was higher, which could be ascribed to more active spots on adsorbent.
Also, the accumulation of dye molecules over the RGO surface was
proposed to be higher. This may be due to insufficient driving force
generated by ultrasound waves for overcoming mass transfer resistance
of dye molecules at solid as well as aqueous phase [77]. Hence the
percentage removal of BF and MB was gradually reduced at higher
concentration as active spot saturation of RGO takes place.
3.4.4. Effect of sonication time
The influence of sonication time on BF and MB adsorption was
observed by varying the time from 1 to 19 min as displayed in Fig. 4(d).
The results of these experiments specify that the dye adsorption capa-
city improved by an enhancement in sonication time up to 15 min,
whereas the adsorption capacity of RGO was considerably reduced after
15 min of sonication time. This is due to the mass transfer which takes
place in short period of sonication time. The rapid adsorption was the
result of higher surface area and more adsorption spots on adsorbent
which would have taken place due to adsorbent scattering or mass
transfer produced by acoustic waves [78]. For BF, the percentage re-
moval was gradually enhanced from 43.17% to 91.31% as the time was
enhanced from 1 to 15 min, whereas the percentage reduced to 80.02%
at 19 min. Likewise, for MB, the removal efficacy was improved from
31.84% to 98.68% as the time was enhanced from 1 to 15 min and was
reduced to 87.63% at 19 min of sonication time. Intense ultrasonica-
tion, accumulation of the dye molecules, non-retention and thermal
decay of dyes would have led to increase in the desorption process
which can be considered as the cause for the gradual decrease in
efficiency of dye removal after optimum time of sonication [79].
3.4.5. Effect of temperature
The temperature was varied from 10 ℃ to 40 ℃ to carry out the
thermodynamic study for BF and MB dyes. The experimental outcomes
depicted the gradual enhancement in removal efficacy of BF from
85.60% to 91.63% at 10 ℃ and 30 ℃ respectively, whereas the removal
efficiency was reduced to 84.60% at 40 ℃ as displayed in Fig. S6(a).
Similarly, the percentage removal for MB was increased from 91.95% to
98.50% at 10 ℃ and 30 ℃ respectively which was then reduced to
95.37% at 40 ℃. The determination of various thermodynamic factors
like change in entropy (ΔS), change in free energy (ΔG) and change in
enthalpy (ΔH) were estimated using Van’t Hoff equation.
ΔG = −RTln (55.5K d) (6)
ΔS ΔH
ln (55.5K d) = −
R RT (7)
where, T refers to temperature, R denotes universal gas constant
(8.314 J/mol/L) [80], K d denotes adsorption distribution coefficient
[81].
qe
Kd =
Ce (8)
where, qe represents adsorption capacity at equilibrium and Ce refers
the solution concentration at equilibrium [82]. The thermodynamic
constraints like ΔS, ΔH were determined from the graph plotted be-
tween ln (55.5K d) and 1/T available in Van’t Hoff plot displayed in Fig.
S6(b). From Table S2, the positive values of ΔS (0.129 for BF and 0.287
for MB) and ΔH (21.857 for BF and 66.481 for MB) indicates that both
the dye adsorption processes are endothermic whereas the ΔG values
indicate spontaneous and feasible adsorption [83]. The disorderness at
the interface among liquid and solid was better designated by the
standard entropy which implies that the increased adsorbent random-
ness was the reason behind the positive ΔS value. Thermodynamically
spontaneous and effective dye adsorption was taken place can be ver-
ified from the negative ΔG values at various temperatures. The higher
adsorption capacity due to the greater driving force of adsorption which
is evident from the higher negative charge of ΔG [84]. During the en-
dothermic process, with an enhancement in temperature, the number of
adsorption spots increases and hence the dye molecule mobility en-
hancement takes place. The enhancement of dye molecule diffusion rate
into active sites and quick production of cavity bubbles can be con-
sidered as the reason for the increase in dye adsorption at high tem-
peratures. This results in lowering of liquid viscosity and development
of fewer new adsorption pores. As the weakly bound adsorbate tends to
escape at the high temperature from the adsorbent surface, an evident
decrease in the efficiency of removal was observed after optimum
temperature [85].
3.4.6. Effect of ultrasound frequency
An increase in the ultrasonic frequency caused substantial en-
hancement in the adsorption of dye molecules as represented in
Fig. 4(e). For BF and MB dyes, the ultrasound frequency was carried out
at 37 and 80 kHz. The removal efficacy for BF and MB was 90.81% and

9
R. Rajumon, et al. Journal of Environmental Chemical Engineering 7 (2019) 103479

Fig. 4. Effects of (a) pH (for MB and BF: m =0.05 g, C0= 50 mg/L, t = 15 min); (b) adsorbent dosage (for MB: pH = 10, C0= 50 mg/L, t = 15 min & for BF: pH = 8, C0=
50 mg/L, t = 15 min) ; (c) initial dye concentration (for MB: pH = 10, m= 0.05 g, t = 15 min & for BF: pH = 8, m= 0.03 g, t = 15 min); (d) sonication time (for MB:
pH = 10, m= 0.05 g, C0= 50 mg/L, & for BF: pH = 8, m= 0.03 g, C0= 50 mg/L); and (e) frequency and power (for MB: pH = 10, m= 0.05 g, C0= 50 mg/L, t = 15 min &
for BF: pH = 8, m= 0.03 g, C0= 50 mg/L, t = 15 min) on MB and BF adsorption.

10
R. Rajumon, et al. Journal of Environmental Chemical Engineering 7 (2019) 103479

97.45% respectively at 80 kHz which might be ascribed to the impact of relation amongst the frequency and radius of the bubble is represented
bubble cavitation, resonance size and collapse time. By changing the in Eq. (9).
ultrasonic frequency, variation in bubble size takes place and the

Fig. 5. Schematic representation of possible interactions between (a) MB-RGO, (b) BF-RGO.

11
R. Rajumon, et al.
1 3γ 2σ 2σ
f= ⎛ Po + ⎞−
2πr ρ ⎝ α ⎠ αρ (9)
where, γ denotes heat capacity ratio of the gas at constant pressure and
volume (For air- 1.39), ρ represents density of the surrounding medium,
r denotes radius of resonant bubble, σ represents surface tension which
is ignored and Po is the ambient pressure. At 37 kHz and 80 kHz of ul-
trasound frequency, the free air bubble resonance size in water is
87.8 μm and 40.6 μm respectively (Table S3). The decrease in collapse
time (τ ) of the free air bubble has occurred when the resonant bubble
radius was reduced and is represented by the following equation.
ρ ⎛ P RGO which was more rapid than the dye molecules. Moreover, at
τ = 0.915r 1 + m⎞
⎜ ⎟
Pm ⎝ Pv ⎠ (10)
where, Pv is the pressure present in bubble during collapse at initial
phase, Pm is the liquid pressure [2,86]. At 37 kHz and 80 kHz of ultra-
sound frequency, the collapse time of bubble was observed as 8.03 μ s
and 3.71 μs respectively. The generation of large number of smaller
cavitation bubbles results in the decrease in collapse time [2,87] which
leads to more acoustic cycle formation at higher frequencies, resulting
in higher cavitation per unit time [88]. Higher interface mixing effi-
ciency was obtained from cavitation than that obtained through con-
ventional mixing. The surface area of RGO increased due to the scat-
tering of converging magnetic powder under ultrasonication. As the
larger bubble has more stability and severe collapse than smaller bub-
bles, the equilibrium of the stable acoustic bubbles is affected, hence
blocking the active sites [89]. At lower frequency, the percentage re-
moval of both dyes was found to be less due to low mass transfer. At
higher frequency, more percentage removal was obtained as a result of
the deterioration of dyes and consecutive generation of species [90].
3.4.7. Effect of ultrasonic power
Power is a substantial variable having influence on cavitation. The
ultrasonic power was varied as 30, 50, 70 and 90 W at the frequencies
37 and 80 kHz as given in Fig. 4(e). The experimental outcomes re-
present that the removal efficiency of BF and MB were significantly
enhanced as an increase in power was provided from 30 to 50 W. The
enhancement in the number of cavities is caused because of rise in the
degree of power dissipation, hence the enhancement of accumulative
pressure wave takes place [91].
At the optimum ultrasonic power, the dye adsorption rate attained
its maximum value. Generation of void spaces may take place within
the solution when the ultrasonic power applied is more than the op-
timum value, which might result in the scattering of the sound waves
on the vessel sides leading to degeneration of very less energy within
the solution. This can bring about a decrease in dye adsorption rate
along with the reduction in the ultrasound utilisation efficacy [92].
3.4.8. Effect of ionic strength
The NaCl concentration was varied to analyse the effect of ionic
strength on BF and MB removal. The removal efficacy of dyes rises with
increase in NaCl concentration. As depicted in Fig. S7, percentage re-
moval for BF was slightly increased as 70.27% at 0.1 mol/L and 73.29%
at 0.4 mol/L. Also, for MB, the percentage removal was gradually in-
creased as 64.30% at 0.1 mol/L and 77.20% at 0.4 mol/L. Though the
increase in removal efficiency was observed as the concentration of
NaCl increases, the efficiency in the absence of NaCl was much higher
(91.31% for BF and 98.68% for MB) at optimum conditions. This could
be due to three different possibilities: (1) The electrical double layer
would have generated on the surface of adsorbent in the presence of
NaCl. The increase in ionic strength leads to the compression of double
layer resulting to electrostatic repulsion of the adsorbent surface and
dye molecules; (2) competition among cationic dye molecules and Na+
ions which may leads to decrease in the electrostatic potential on the
adsorbent surface [93]; (3) The reduction behaviour could be due to the
smaller ionic radius of Na+ (0.102 nm) than the dimensions of the
12
Journal of Environmental Chemical Engineering 7 (2019) 103479
tested dyes. From BET results, the average pore diameter was found to
be 3.144 nm. The smaller size of the sodium ions might comfortably
occupy the active sites of the adsorbent than the dye molecules.
3.4.9. Effect of humic acid
Fig. S8 illustrates that the concentration of humic acid has sig-
nificant effect on dye adsorption. The results demonstrate a slower re-
duction in percentage removal of both dyes over RGO surface as con-
centration of humic acid increases resulting in the adsorptive spot
saturation on RGO surface. The greater attractive force among the
humic acid and RGO is responsible for the humic acid adsorption by the
higher concentration of dyes, humic acid adsorption had higher com-
petition with the dye molecules due to the strong driving force of humic
acid [94].
3.5. Half-life and half-capacity concentration
The equation used to denote the solute equivalent equilibrium
concentration (Ce ,1/2) in the aqueous phase as soon as half the capacity
of adsorption is reached ( qe = 0.5 qm ) is represented in Eq. 11.
1
Ce,1/2 =
KL (11)
The half-capacity concentration (Ce ,1/2) which is represented above
is the reciprocal of Langmuir constant (K a) . During the adsorption
process qt changes to qt = 0.5 qe , when the half-life becomes t = t1/2 .
1
t1/2 =
k2 qe (12)
Half-life is inversely proportional to k2 qe in the adsorption process.
Table S4 shows the half-capacity and half-life values of MB and BF dye.
Higher rate of adsorption is disclosed by a minimum value of t1/2 at-
tained as 3.45 min and 2.16 min for MB and BF respectively. The Ce ,1/2
values of MB and BF adsorption were obtained as 2.94 mg/L and
9.43 mg/L respectively, having lesser value than the other dyes. The
least values of Ce ,1/2 specifies the requisite of least amount of RGO
dosage and least number of stages during the ultrasonic-assisted ad-
sorption procedure (Table S4). It is vital to provide the connection
between operational experiment conditions and kinetic parameters.
The rapid uptake and less amount of adsorbent dosage denoted by low
half-life and low half-capacity concentration values disclose the ability
of RGO to a greater extent. Similar results were obtained by other re-
searchers also and mentioned in Table S4. From calculations, higher
Ce,1/2 values were observed in silent adsorption in addition to high half-
life values. The higher value of half-life shows slow adsorption process
as it will not be economically feasible for industrial applications. On the
contrary, in ultrasonic assisted adsorption process, half-capacity con-
centration and the half-life values were much smaller when compared
with silent adsorption process (Table S4). The above results indicate
that the use of ultrasonication for the removal of dyes could be highly
viable at large scale applications.
3.6. Adsorption mechanism
The mechanism behind the adsorption of MB and BF onto RGO was
studied using both XPS and FT-IR spectrum and is schematically dis-
played in Fig. 5(a & b). Electrostatic attraction is a property which relies
on the nature of charge possessed by dye molecules and adsorbent.
Electrostatic attraction occurs when the dye molecule and adsorbent
particles having opposite charges, whereas the dye molecules and ad-
sorbent particles having similar charge lead to electrostatic repulsion.
The maximum dye removal for BF and MB was obtained at pH 8 and 10
respectively. Electrostatic attraction could happen among the nega-
tively charged RGO surface and the cationic dyes having positive
charge. The presence of O = C–O (carboxyl) functional group was
R. Rajumon, et al.
affirmed from FT-IR and XPS results. The electrostatic attraction might
be due to the existence of this negatively charged O = C–O group which
attracts the positively charged nitrogen atoms present in both BF and
MB dyes [29].
pHpzc of synthesised RGO was obtained as 7.26 as displayed in Fig.
S5. The adsorption capacity and pHpzc is related to each other relying
on the surface charge of synthesised RGO. Adsorption of anions is fa-
voured for pH less than pHpzc while higher pH than pHpzc favours cation
adsorption. As the pH at which maximum dye removal efficiency was
obtained is greater than pHpzc for both dyes, a strong electrostatic at-
traction could have occurred among dye molecules and RGO surface
[81].
There are two possible hydrogen bondings which can take place in
the system. The hydrogen bonding among hydrogen donating OH
groups on RGO surface and oxygen or nitrogen atoms in the dye which
are hydrogen acceptors is termed as dipole-dipole hydrogen bonding.
Another possible hydrogen bonding interaction is the Yoshida bonding
which exists among the aromatic rings present in BF and MB and OH
groups present on RGO surface [95]. The adsorptive mechanism could
be proposed effectively by analysing FT-IR spectra of RGO before and
after adsorption. For both BF and MB adsorption, the peak intensity
corresponding to OeH group was reduced after adsorption and a shift
in wavelength was found from 3360.03 cm−1 to 3321.48 cm-1 and
3317.04 cm-1 respectively as represented in Fig. 3(c). This confirms the
presence of yoshida bonding as well as dipole-dipole bonding in the
adsorption of BF and MB onto RGO [96,97].
Mattson et al. [98] conducted adsorption studies between activated
carbon and phenolic compounds in which he proposed the n-π inter-
actions for the first time in 1969. The presence of electron accepting
aromatic rings in both BF and MB dyes and the electron donating
oxygen groups on RGO surface gives rise to the n-π interaction. The
intensity peak corresponding to C–O functional group was reduced after
adsorption for both BF and MB. The peak intensity wavelength was
shifted from 1024.15 cm−1 to 1016.59 cm−1 for BF and to
1019.50 cm−1 in case of MB adsorption (Fig. 3c), consistent with pre-
vious literature reports [99,100]. The shift in peak which corresponds
to C–O confirms the n-π interactions between RGO and dye molecules.
The mechanism of adsorption involved in organic molecules con-
taining benzene rings or C]C bonds can be explained by π -π inter-
action. The RGO contains benzene rings which interact with the π
electrons of the organic dye molecules through π -π coupling [101]. As
both the BF and MB have benzene rings, π -π interaction can be re-
garded as an intermolecular force of attraction between RGO and dye
molecules. The aromatic C]C bonds in RGO were obtained at a peak
1614.58 cm−1 which shifted towards lower wavenumbers to
1582.63 cm−1 and 1553.01 cm−1 for BF and MB adsorption respec-
tively as displayed in Fig. 3(c). The corresponding peak intensities were
also found to decrease after adsorption which indicates the occurrence
of π -π interaction among the RGO surface and benzene rings of BF and
MB [95]. Moreover, the π -π interaction between dye molecules and
graphitic compounds could be due to the planar structure of dyes. The
interaction among RGO and aromatic molecules were investigated by
Wang et al [102]. It was revealed that the intramolecular π-π stacking
was also found to favour the adsorption process between graphitic
compounds and dye molecules along with π-π interactions. Hence,
electrostatic attraction, hydrogen bonding interaction, n-π and π -π
interactions had more significance in MB and BF dye adsorption onto
RGO.
3.7. Adsorbent reusability
The potential of adsorbent applications can be determined by an
important parameter called adsorbent reusability. Centrifugation pro-
cess was used to separate the used RGO after the adsorption process.
The adsorbent was stirred for 15 min along with ethanol solution.
Filtration of the mixture was done utilising #Whatman 41 filter and
13
Journal of Environmental Chemical Engineering 7 (2019) 103479
then the separated RGO was dried at 70 °C [103]. UV–vis spectrometer
was utilised for estimation of both dye concentrations after each re-
cycling process. The same procedure was conducted five times which
proved that the efficient recovery and reuse of RGO are possible
without causing a substantial decrease in its mass (Fig. S10). Even after
continuously performing five cycles, BF and MB dyes showed a per-
centage removal of 82.19% and 90.79% respectively [104].
4. Conclusion
This study explored the utilisation of low cost green reduced GO for
effective removal of MB and BF dyes by ultrasonic assisted adsorption.
The characterisation of the synthesised GO and RGO was performed by
UV–vis spectroscopy, XRD, TEM, XPS, BET and FT-IR. For both MB and
BF adsorption, the Langmuir and pseudo-second order models suited
well with experimental data and the corresponding least error was
obtained for ARE model. The optimised values for pH, sonication time,
RGO dosage and initial dye concentration for MB dye adsorption were
obtained as 10, 15 min, 0.05 g/50 mL and 50 mg/L respectively with a
maximum removal efficiency of 98.68%, while for BF dye adsorption,
the obtained values were 8, 15 min, 0.03 g/50 mL and 50 mg/L re-
spectively with a maximum removal efficiency of 91.31%. The ΔH
values for MB and BF adsorption were obtained as 66.481 and 21.857
KJ mol−1 whereas the ΔS values were found to be 0.287 and 0.129 KJ
mol−1 K-1 for MB and BF. The ΔH and ΔS values are indicated the ad-
sorption of MB and BF onto RGO was endothermic in nature. The in-
creased concentration of humic acid caused a gradual reduction in the
percentage removal of both dyes on RGO surface as the greater at-
tractive force between RGO and humic acid hinders the adsorption of
dye molecules. In addition to electrostatic attraction, FTIR and XPS
analysis designated the roles of hydrogen bonding, n-π and π -π inter-
actions between the surface of the adsorbent and both the dye mole-
cules. The adsorbent reusability tests revealed that it is feasible to reuse
RGO as an adsorbent even after five adsorption cycles. The results ob-
tained from various experimental analysis proves the significance of
RGO as an adsorbent for the effective toxic dyes removal from the
discharged effluents of textile industries.
Acknowledgements
We would like to extend our sincere gratitude to VIT, Vellore for
helping us to conduct this study by providing the lab facilities, essential
materials, instruments, samples and infrastructure. The author Anu
Mary Ealias acknowledges the University Grants Commission (UGC),
for the Maulana Azad National Fellowship (MANF), Government of
India (F1-17.1/2017-18/MANF-2017-18-KER-80434).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jece.2019.103479.
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