Journal of Water Process Engineering 35 (2020) 101185

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Journal of Water Process Engineering

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Synthesis and characterization of graphene shell composite from oil palm T

frond juice for the treatment of dye-containing wastewater
Yeit Haan Teowa,b,*, Siti ‘Aisyah Tajudinb, Kah Chun Hoa,b, Abdul Wahab Mohammada,b
a
Research Centre for Sustainable Process Technology (CESPRO), Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor,
Malaysia
b
Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia

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

Keywords: The discharges of dye-containing wastewater have predominantly been attributed to the textile industry, where
Oil palm frond methylene blue (MB) is the most commonly-used dye. The use of graphene-based adsorbents with sugar as the
Graphene shell composite natural carbon source has been reported as a new milestone; however, the sustainability of entailing sugar in
Adsorption such engineering practices is questionable. Considering the generation of agricultural waste from palm oil mills
Sustainable practice
in the context of Malaysia and the need of more sustainable carbon sources for the synthesis of graphene-based
Methylene blue
adsorbents, this study explored the synthesis of graphene shell composite (GSC), a new generation of graphene-
based adsorbents, with oil palm frond (OPF) juice as the natural carbon source and with oil palm kernel shell as
the base material. The synthesized GSC was characterized by scanning electron microscopy (SEM) and X-ray
diffraction (XRD). The adsorption performance was evaluated by studying the effect of synthetic MB solution
concentration and the GSC mass. 75.45%–99.13% removal of MB ions from synthetic MB solution after 20 h of
adsorption performance study suggested the applicability and effectiveness of the synthesized GSC in treating
dye-containing wastewater. Further kinetics analysis revealed that the interactions between GSC and MB ions
fitted the Freundlich isotherm (R2 = 0.9631-0.9689) and pseudo-second order isotherm (R2 = 0.9860-0.9980).
Such findings reflect that the uptake of MB ions by GSC was mechanistically a multilayer adsorption, in which
the MB ions approached the active sites on GSC surfaces and were continually adsorbed thereon through che-
mical bonding.

1. Introduction
Dyes are organic compounds used to impart colouration to materials
such as textiles, papers, and leather. The production of dye-containing
wastewater has predominantly been attributed to textile manu-
facturing: during the dyeing process in producing colored fabric, the
dye dissolved in water is imparted to the fabric whereas the remaining
dye-containing water is discharged into various water bodies as was-
tewater [1,2]. One of the common dyes in the textile industry is me-
thylene blue (MB) due to its deep-blue appearance [3,4]. The presence
of MB in water bodies has been known to be hazardous. The dark-co-
lored MB restricts the direct penetration of light into the water body,
hence prohibiting the growth of aquatic life [5,6]. Additionally, the
exposure of humans to MB may cause vomiting, chest pain, hard
breathing, and fast heartbeat [7]. Given such complications, it is im-
perative to treat MB wastewater before its discharge into the water
bodies.
The treatment of wastewater can be categorized into three groups:
biological treatment, chemical treatment, and physical treatment [8].
Biological treatment involving the use of microorganisms is the most
economical. However, the method is time-consuming, given the in-
evitably long retention time for microbial degradation. Moreover, its
efficiency is lacking due to the complex molecular structure of MB
[9,10]. As for chemical treatment, coagulation is widely used for was-
tewater treatment [11]. Although its relative effectiveness and shorter
operation time, chemical treatment suffers from drawbacks such as the
need for costly chemicals and difficulty in handling the resultant sludge
[12]. Lastly, physical treatment is the most feasible, effective, and
simplest wastewater-treatment method [13,14]. Adsorption, a physical-
treatment method with the use of activated carbon (AC), has been ap-
plied for decades in wastewater treatment. Efforts have been under-
taken to replace AC with a more sustainable adsorbent, such as one

⁎
Corresponding author at: Research Centre for Sustainable Process Technology (CESPRO), Faculty of Engineering and Built Environment, Universiti Kebangsaan
Malaysia, 43600 Bangi, Selangor, Malaysia.
E-mail address: yh_teow@ukm.edu.my (Y.H. Teow).

https://doi.org/10.1016/j.jwpe.2020.101185
Received 19 December 2019; Received in revised form 2 February 2020; Accepted 11 February 2020
2214-7144/ © 2020 Elsevier Ltd. All rights reserved.
Y.H. Teow, et al.
synthesized from agricultural waste [15,16].
The palm oil industry is the largest agricultural industry in
Malaysia; its 4.7 million hectares of palm oil plantations and 416 op-
erating oil mills are estimated to produce 13.97 million tonnes of oil
palm frond (OPF), constituting to the largest biomass in the industry
[17]. OPF is produced during the pruning of oil palm fresh fruit bunch.
It is left in palm oil plantations for soil conservation. Structurally, OPF
has been found to comprise a high carbohydrate-rich in simple sugars
[18]. In this regard, Gupta et al. [19] have proposed a new graphene-
based adsorbent with superior adsorption capacity with sugar as the
natural carbon source. Besides, Khan et al. [20] had synthesized gra-
phene sand hybrid stacked on inorganic sand support as adsorbent
using date syrup as a carbon source. It was reported that the adsorbent
had successfully removed > 99 % methyl violet and > 93 % congo red
dye with an initial dye concentration of 200 mg L−1. Even though these
adsorbents have shown much potential in the adsorption-based treat-
ment process, the sustainability of entailing sugar and date syrup for
such engineering practices remains questionable.
Considering the generation of agricultural waste from palm oil mills
in the context of Malaysia and the need of more sustainable carbon
sources for the synthesis of graphene-based adsorbents, OPF, a biomass
waste from palm oil industry with high sugar content has the potential
to be used as the carbon source for the synthesis of graphene-based
adsorbent, transferring the graphene-based adsorbent synthesis process
into a more sustainable engineering practice. The objective of this study
is to explore the feasibility of OPF juice as a natural carbon source for
the synthesis of graphene shell composite (GSC), a new generation of
graphene-based adsorbents using oil palm kernel shell as the base
material. The effect of synthetic MB solution concentration and GSC
mass towards the adsorption performance was studied in which the
synthetic MB solution concentration was varied from 1 mg L−1 to 20
mg L−1. Whereas, the mass of GSC was manipulated from 5 g to 20 g.
Subsequently, equilibrium isotherm and kinetic isotherm were used to
understand the adsorption mechanism pathways and to explain the
dependence of adsorbent’s surface properties towards the adsorption
performance.
2. Materials and methods
2.1. Materials
Fresh OPF was collected from the East Mill, Sime Darby Plantation,
Carey Island, Malaysia. The fresh OPF was stored at 4 °C to prevent
microbial biodegradation prior to the adsorption studies. Sulphuric acid
(H2SO4) was procured from R&M Marketing, UK, while MB was pur-
chased from Merck, Germany.
2.2. GSC synthesis from OPF
OPF was squeezed with the sugarcane machine to extract the OPF
juice. Around 10 L of OPF juice was obtained through the pressing of 25
kg fresh OPF. Pressed OPF juice was filtered with 0.2μm Whatman
membrane nylon filter to produce extracted OPF juice for GSC synthesis
[21]. Then, 1 L OPF juice and 60 mL H2SO4 were mixed in a beaker and
heated at 260 °C for 6 h to concentrate the mixture. This resultant
concentrated mixture was then mixed with 300 g oil palm kernel shell
(300 μ m-600 μ m) and stirred well. Subsequently, the coated oil palm
kernel shell was laid in the crucible and dried in the furnace with a
programmed thermal setting as described in our previous research
study [22]. The synthesized shell composite was then cooled to room
temperature. The GSC was rinsed with distilled water to obtain neutral
pH before drying in the oven.
2.3. Characterization of the GSC
The surface morphology of the synthesized GSC was examined
2
Journal of Water Process Engineering 35 (2020) 101185
through scanning electron microscopy, SEM (ZEISS, SIGMA). Prior to
the SEM analysis, a thin layer of gold was coated on the synthesized
GSC. The SEM micrograph was captured at an accelerating voltage of 3
kV and at the magnification of 2.5 k×. The chemical composition on
the surface of GSC was analyzed using energy dispersive X-ray spec-
troscopy (EDX), Oxford INCA PentaFETX3 (Oxford, UK). Meanwhile,
the crystallinity of the synthesized GSC was examined through the X-
ray diffraction, XRD (Bruker, German). The XRD spectrum was com-
pleted at a 2θ scan range of 5° – 80°.
2.4. Adsorption performance study
2.4.1. Effect of synthetic MB solution concentration
Synthetic MB solutions were prepared at different concentrations:
1.00 mg L−1, 1.50 mg L−1, 5.00 mg L−1, 10.00 mg L−1, 15.00 mg L−1,
and 20.00 mg L-1 [22]. For each concentration, a working volume of
250 mL was added into a conical flask, to which 20 g of GSC was then
added. The conical flask with the mixture was placed on an isothermal
shaker and shaken at 200 rpm for 20 h under room temperature. The
synthetic MB solution was sampled and analyzed at 20-min intervals for
the first 1 h, then at 1-h intervals for the next 7 h, and lastly at 2-h
intervals for the following 12 h. The concentration of the solutions was
analyzed through a UV–vis spectrophotometer at the wavelength, λmax,
of 664 nm. The amount of MB adsorbed onto GSC at time, t, (Qt) (mg
g−1) was evaluated through Eq. (1) [23].
(Co − Ct ) V
Qt =
W (1)
where Co is the initial concentration of the synthetic MB solution (mg
L−1), Ct is the concentration of the synthetic MB solution at time t (mg
L−1), W is the weight of GSC (g), and V is the volume of the synthetic
MB solution (L).
2.4.2. Effect of GSC mass
Four conical flasks were prepared, each with 250 mL of the syn-
thetic MB solution with a concentration of 20 mg L−1. For each of the
flasks, different masses of GSC were added: 5 g, 10 g, 15 g, and 20 g
[22]. Each flask with the mixture was placed on an isothermal shaker
and shaken at 200 rpm for 20 h under room temperature. The synthetic
MB solution was sampled and analyzed at 20-min intervals for the first
1 h, then at 1-h intervals for the next 7 h, and lastly at 2-h intervals for
the following 12 h. The concentration of the synthetic MB solution was
analyzed through a UV–vis spectrophotometer (λmax =664 nm). Si-
milarly, the amount of MB adsorbed onto GSC at time, t, was evaluated
through Eq. (1).
2.5. Adsorption model
2.5.1. Equilibrium isotherm
Two equilibrium isotherms (Langmuir isotherm and Freundlich
isotherm) were used in this study as most of the adsorption of organic
pollutants –MB dye follows the Freundlich model (47 %) and Langmuir
model (36 %). The remaining followed Temkin model (2.4 %), Sips
model (1.57 %), Dubinin-Radushkevich (D-R) model, and GAB model
[24]. The Langmuir isotherm characterises the development of a mono-
layer adsorbate on the surface of an adsorbent, in which further ad-
sorption will not occur when the active sites on the surface have been
occupied by the adsorbate. The linear Langmuir isotherm is expressed
by Eq. (2) [25].
Ce 1 C
= + e
qe qo K c qo (2)
where Ce is the concentration of the adsorbate solution at equilibrium
(mg L−1), qe is the amount of the adsorbate adsorbed per unit mass of
the adsorbent (mg g−1), qo is the adsorption capacity of the adsorbent
(mg g−1), and Kc is the Langmuir constant (L mg−1).
Y.H. Teow, et al. Journal of Water Process Engineering 35 (2020) 101185

The Freundlich isotherm characterises a heterogeneous adsorption

in which an adsorbate can be continuously adsorbed onto the surface of
an adsorbent, even when its active sites have been previously occupied
by an adsorbate. The linear Freundlich isotherm is expressed by Eq. (3)
[26].
1
log qe = log K + log Ce
n (3)
where qe is the amount of the adsorbate adsorbed per unit mass of the
adsorbent (mg g−1), Ce is the concentration of the adsorbate solution at
equilibrium (mg L−1), K is the adsorption capacity, and 1/n is the ad-
sorption intensity.

2.5.2. Kinetic isotherm

The pseudo-first order isotherm characterises the adsorption of an
adsorbate onto the surface of an adsorbent by physisorption. Such ad-
hesion is attributed to the surface contact between the adsorbate and
the adsorbent: greater surface contact contributes to stronger adhesion.
The linear pseudo-first order isotherm is expressed by Eq. (4) [27].
K1
log (qe − qt ) = log qe − t
2.302 (4)
where qe is the amount of the adsorbate adsorbed per unit mass of the
adsorbent (mg g−1), qt is the amount of the adsorbate adsorbed at time
t (mg g−1), and K1 is the rate constant.
The pseudo-second order isotherm characterises the adsorption of
an adsorbate onto the surface of an adsorbent by chemisorption. Such
adhesion is attributed to the formation of chemical bonding between
the adsorbate and the adsorbent. The linear pseudo-second order iso-
therm is expressed by Eq. (5) [28].
t 1 t
= +
qt K2 qe2 qt (5)
where qe is the amount of the adsorbate adsorbed per unit mass of the
adsorbent (mg g−1), qt is the amount of the adsorbate adsorbed at time
t (mg g−1), and K2 is the rate constant. Fig. 1. SEM image of GSC under (a) 2.5 k × magnification and (b) 10 k ×
magnification.
3. Results and discussion
Table 1
3.1. GSC characteristics
Elemental weight percent of GSC obtained from EDX analysis.

The SEM micrograph reveals the rough and irregularly-shaped Element Weight percent (%) Atomic percent (%)

surfaces of the GSC under 2.5 k × magnification and 10 k × magni- Carbon 46.7 0.3
fication (Fig. 1). Such roughness and irregularity of the surfaces are Oxygen 30.1 0.2
advantageous for an adsorbent: they promote not only the adhesion of Silica 12.9 0.1
the adsorbate onto the active sites, but also the subsequent removal of Aluminium 4.0 0.1
Potassium 3.4 0.1
the MB ions from the synthetic MB solution [29]. Besides, the cluster
Sulfur 1.8 0.0
structure and porous nanosheet structure were observed on the GSC Sodium 1.1 0.0
surface at higher magnification. It is hypothesized that cluster structure
and porous nanosheet structure would provide higher adsorption ac-
tivity, which in good agreement with the findings obtained by Farghali
et al. [30]. Table 1 presents the elemental weight percent (wt%) ob-
tained from EDX analysis. The synthesized GSC indicated the presence
of mainly carbon, oxygen and silica with 46.7, 30.1, 12.9 wt%, re-
spectively. The EDX analysis shows a high content of carbon owing to
the conversion of carbon source in the OPF juice into graphene during
carbonization and is in agreement with the literature reported [31].
The XRD spectrum of the GSC reveals a noticeably high spike at 25°
(Fig. 2). This observation suggests that the carbon source in the OPF
juice has been converted into graphene for the synthesis of the GSC.
This finding corroborates that by Dubey et al. [23], who found that the
peak representing graphene in the XRD spectrum was observed between
20° and 27°. Besides, Fig. 2 indicates that the diffraction peaks are low
and broad, probably due to small GSC particle size and incomplete Fig. 2. XRD spectrum of GSC.
inner structure formation [32]. In addition, a small peak at 43° in-
dicates the presence of amorphous carbon with a less ordered structure,

3
Y.H. Teow, et al.
Fig. 3. Amount of MB adsorbed at different times during adsorption.
supports the observation in Fig. 1 [33]. The XRD analysis has confirmed
the successful synthesis of GSC, a new generation graphene-based ad-
sorbents, with OPF juice as the natural carbon source and oil palm
kernel shell as the base material.
3.2. Adsorption performance study
3.2.1. Effect of the concentration of the synthetic MB solution
To elucidate the effect of the concentration of the synthetic MB
solution, two parameters were examined: the amount of MB adsorbed
onto the GSC at different times during adsorption (Fig. 3) and the
percentage of MB removal at different times during adsorption (Fig. 4).
Fig. 3 illustrates the duration taken for the GSC to be saturated with MB
ions hence desorption/regeneration of GSC is needed as the adsorbent
has no longer affective in adsorption beyond saturation. As seen, rapid
adsorption occurred in the initial stage, given the abundance of active
sites available on the GSC surface [34,35]. This postulation is reflected
by the steep gradient in the adsorption profile in the initial stage of the
process. With time, the active sites on the GSC surface were progres-
sively occupied by the MB ions. The gradient of the adsorption profile
was thus reduced and reached a plateau when equilibrium was attained
for the adsorption. The adsorption capacity is the amount of MB ions
adsorbed onto the GSC upon equilibrium [29,36]. As presented in
Fig. 3, the adsorption capacity improved with increasing concentrations
of the synthetic MB solution: the highest adsorption capacity is ex-
hibited by the adsorption with the use of 20 mg L−1 synthetic MB so-
lution (the highest concentration). Two reasons underlie this. Firstly,
the high concentrations of the synthetic MB solution implies more MB
ions, and thus a stronger driving force for occupying the active sites of
Fig. 4. Percentage of MB removal at different times during adsorption.
4
Journal of Water Process Engineering 35 (2020) 101185
the GSC surface [37,38]. Additionally, the strong driving force offsets
the resistance between the solid phase (GSC surface) and the aqueous
phase (synthetic MB solution) to a greater extent. On the other hand,
the time needed to attain equilibrium in the adsorption becomes pro-
gressively longer with increasing concentrations of the synthetic MB
solution [4]: 7 h for 1.00 mg L−1, 8 h for 1.50 mg L−1 and for 5.00 mg
L−1, 9 h for 10.00 mg L−1 and for 15.00 mg L−1, and 12 h for 20.00 mg
L−1. This was because the greater amount of MB ions in the synthetic
MB solutions with high concentrations necessitated a longer time for
the ions to bind and occupy the active sites available on the GSC surface
[39,40]. At the end of the 20-h adsorption, more than 80 % of the MB
ions in the synthetic MB solution were removed (Fig. 4), regardless of
the concentration of the synthetic MB solution in use. This result has
demonstrated the effectiveness of the GSC in treating dye-containing
wastewater at different concentrations. For visual inspection, photo-
graphs of the synthetic MB solutions before and after the 20-h were
taken (Fig. S1). The synthetic MB solution changed into a transparent
solution after 20 h of adsorption, further suggesting the effectiveness of
the GSC in removing MB ions from the synthetic MB solution.
3.2.2. Effect of the GSC mass
To elucidate the effect of the GSC mass, two parameters were ex-
amined: the amount of MB adsorbed onto the GSC at different times
during adsorption (Fig. 5) and the percentage of MB removal at dif-
ferent times during adsorption (Fig. 6). As illustrated in Fig. 5, the
lower adsorption capacity was attained through the higher GSC mass
for the adsorption, probably due to the greater number of active sites
which competed for the adhesion of MB ions [41,42], given the higher
GSC mass. As seen, that the amount of MB being adsorbed at time t, qt
(mg/g) for 10 g has reached stagnant stage at 14 h indicate adsorption
equilibrium was achieved [31]. The lower adsorption capacity for
higher GSC mass was observed probably due to the agglomeration of
GSC at high adsorbent concentration [43]. Additionally, the majority of
the active sites were not fully occupied by MB ions even at the end of
the 20-h adsorption. As with the effect of the concentration of the
synthetic MB solution, the time needed to attain equilibrium in the
adsorption becomes progressively shorter with increasing GSC masses:
16 h for 5 g, 14 h for 10 g and for 15 g, and 10 h for 20 g. This was
because the MB ions in the synthetic MB solution could be adsorbed on
the greater number of available active sites for higher GSC masses
within a shorter time, giving rise to a shorter equilibrium time. Higher
percentages of MB removal were achieved with increasing GSC masses
used in adsorption [44]. This could be attributed to the greater avail-
ability of active sites for the removal of MB ions from the synthetic MB
solution. Photographs of the solutions before and after the 20-h ad-
sorption (Fig. S3) corroborated the analytical results presented in Fig. 6.
The deep blue color of the synthetic MB solution was greatly reduced by
Fig. 5. Amount of MB being adsorbed at different times during adsorption.
Y.H. Teow, et al. Journal of Water Process Engineering 35 (2020) 101185

Table 3
Pseudo-first order parameters, pseudo-second order parameters, and correlation
coefficients for the adsorption performance study in examining the effect of
concentrations of the synthetic MB solutions.
Kinetic isotherm Co (mg L−1) R2 K1 qeq,exp qeq ε%

Pseudo-first order 1.00 0.791 0.794 0.010 0.163 602.28

1.50 0.891 0.544 0.015 0.179 380.72
5.00 0.682 0.261 0.046 0.248 255.16
10.00 0.793 0.325 0.084 0.337 149.79
15.00 0.702 0.506 0.146 0.379 92.49
20.00 0.643 0.445 0.163 0.395 81.70
Pseudo-second order 1.00 0.681 420.614 0.010 0.005 52.53
1.50 0.015 470.320 0.015 0.010 94.18
5.00 0.974 27.326 0.046 0.049 6.69
10.00 0.899 51.207 0.084 0.052 38.08
15.00 0.997 1.107 0.146 0.396 171.87
20.00 0.993 5.158 0.163 0.222 35.60

Fig. 6. Percentage of MB removal at different times during adsorption.

masses were 1.2085 and 1.7486, respectively. As the resultant value of
adsorption with the use of 20 g GSC. n was in the range of 1 < n < 10, it is suggested that the adsorption
through GSC has been feasible and efficient for MB removal from the
dye-containing wastewater.
3.3. Adsorption model

3.3.1. Equilibrium isotherm 3.3.2. Kinetic isotherm

Two isotherms – the Langmuir isotherm and Freundlich isotherm – Kinetic data for the adsorption in this study were verified with the
were used in this study to characterise the interactions between the use of the pseudo-first order isotherm and pseudo-second order iso-
solid phase (the adsorbent: GSC) and the aqueous phase (the synthetic therm. Table 3 outlines the parameters related to both isotherms and
MB solution) at equilibrium. Experimental data attained from the ad- correlation coefficient (R2) in examining the effect of the concentrations
sorption performance study in examining the effect of synthetic MB of the synthetic MB solutions. Table 4 outlines the parameters related to
solution concentration and the effect of GSC mass were respectively both isotherms and correlation coefficient (R2) in examining the effect
fitted into both the Langmuir isotherm (Fig. S3) and Freundlich iso- of the GSC masses.
therm (Fig. S4). Table 2 outlines the isotherm-related constants and the For both parameters (concentrations of synthetic MB solutions and
correlation coefficient (R2) of both isotherms for the adsorption per- GSC masses), the kinetic data for adsorption exhibit a better fit with the
formance study. pseudo-second order isotherm (as reflected by its larger R2 value) than
The linear plots (Fig. S3 and Fig. S4) demonstrate the good fit be- its pseudo-first order counterpart. The pseudo-second order isotherm
tween the experimental data and the isotherms. The findings as sum- explains that adsorption mechanistically involves the GSC as the ad-
marised in Table 2 suggest that, for the effect of the concentrations of sorbent for the removal of MB ions through chemisorption [47,48].
the synthetic MB solutions, the Freundlich isotherm fit better to the Chemical bonds formed as soon as MB ions approached the active sites
experimental data, as reflected by its larger R2 value. On the other on the GSC surface [22]. Such strong bonding through the sharing or
hand, for the effect of the GSC masses, both the isotherms fit the ex- exchange of electrons makes GSC an ideal adsorbent for dye-waste-
perimental data with similar R2 values. Accordingly, it can be con- water treatment. The rate constants (K2) of the pseudo-second order
cluded that the adsorption involving interactions between the GSC and isotherm increased from 0.771 g mg−1 min−1 to 3.544 g mg−1 min−1
the MB ions at equilibrium was supported by the Freundlich isotherm with an increase in GSC mass indicating that the sorption system pro-
[45]. cess reached equilibrium faster at high adsorbent. This may be due to
As implied by the Freundlich isotherm, the uptake of the MB ions by an increase in the probability of collision between active surface
the GSC was due to the multilayer adsorption, in which MB ions ap- binding sites and the adsorbate at high adsorbent [49]. In addition, the
proaching the active sites on the GSC surface would continually be calculated values of qeq for GSC (0.773 mg g−1) in the pseudo-second
adsorbed onto it until equilibrium was achieved. This result was sup- order isotherm is closer to their experimental values (0.755 mg g−1).
ported by Dubey et al. [23] who suggested that the majority of the The results confirmed the pseudo-second order isotherm is more ap-
natural adsorbents were attached onto the surface through multilayer propriate for adsorption kinetic data.
adsorption. Additionally, the constant for the Freundlich isotherm, n,
denotes the favorability of adsorption. it is favorable when the value of
n is in the range of 1 < n < 10 [46]. based on computation from the
Table 4
Freundlich isotherm, the values of n for examining the effect of the
Pseudo-first order parameters, pseudo-second order parameters, and correlation
concentrations of the synthetic MB solutions and the effect of the GSC
coefficients for the adsorption performance study in examining the effect of
GSC masses.
Table 2
Isotherm-related constants and correlation coefficients of both the Langmuir Kinetic isotherm W (g) R² K2 qeq,exp qeq ε%
model and Freundlich model for the adsorption performance study.
Pseudo-first order 5 0.968 0.250 0.677 0.748 3.05
Study parameter Langmuir Model Freundlich Model 10 0.991 0.519 0.443 0.661 16.42
15 0.977 0.234 0.295 0.570 26.87
R2 Kc qo R2 K n 20 0.981 0.357 0.237 0.485 26.90
Pseudo-second order 5 0.986 0.771 0.677 0.773 3.54
Concentration of the 0.6405 0.3384 0.1360 0.9689 0.2405 1.2085 10 0.998 2.108 0.443 0.499 3.14
synthetic MB solution 15 0.980 1.151 0.295 0.343 4.04
GSC mass 0.9752 1.0604 0.2762 0.9631 0.5404 1.7486 20 0.996 3.544 0.238 0.235 1.67

5
Y.H. Teow, et al.
Table 5
Comparison of MB adsorption capability using various graphene-based ad-
sorbent.
Graphene-based adsorbents Maximum adsorption capacity (mg Reference
g−1)
Alkali-activated MWCNTs 399 [52]
Graphene 761.3 [53]
Sulfonated graphene 906 [54]
GO 769.23 [55]
Sulfonated GO 2500 [55]
POME-derived GSC 0.247 [22]
OPF-juice GSC 0.773 This study
3.4. Comparison of graphene-based adsorbent
Table 5 compares the MB adsorption capability using various gra-
phene-based adsorbent. As seen, GSC synthesized from this study has
higher adsorption capability compared to the previous study using palm
oil mill effluent (POME) as carbon source probably due to higher
carbon content and lower impurity [22]. However, GSC synthesized
from this study has relatively low adsorption capacity compared to
other graphene-based adsorbents such as multi-walled carbon nano-
tubes (MWCNTs), pristine graphene, and graphene oxide (GO). This
could be due to the clustered structure of GSC adsorbent that has a
comparatively lower effective surface area for adsorption compared to
the graphene sheet that has more open-up surfaces for adsorption [50].
Hence, less amount of MB can be accommodated by the bundled
structure of the graphene layer coated on the oil palm kernel shell. In
order to reduce the clustered structure of the graphene layer, it is
suggested to use oil palm kernel shell of smaller particle size to allow
complete wrapping and interlinked network of graphene layer covering
the shell particles [51]. Besides, it is observed that functional groups
play a vital role in adsorption performance; the adsorption capacity of
sulfonated graphene and sulfonated GO improved for 19 % and 225 %
from its pristine forms, respectively. The functional groups help in the
binding of the dye molecules through weak electrostatic interaction or
Van der Waals forces. Therefore, it is suggested to improve the ad-
sorption capacity of GSC through surface functionalization.
4. Conclusion
A new generation of graphene-based adsorbent, with OPF juice as
the natural carbon source and oil palm kernel shell as the base material,
was successfully synthesized in this study. The fade-off of the synthetic
MB solution from deep blue towards the completion of the adsorption
performance study confirmed the applicability and effectiveness of the
synthesized GSC in treating dye-containing wastewater. The study
showed that the superior adsorption capacity of GSC could be attained
through increasing the concentration of the synthetic MB solution and
decreasing the GSC mass: the highest adsorption capacity was realized
through the use of a 20 mg L−1 synthetic MB solution and 20 g GSC.
The resultant Freundlich isotherm fitted well with the equilibrium ad-
sorption data, suggesting that the uptake of MB ions by the GSC was due
to multilayer adsorption in which the MB ions approaching the GSC
surface would continually be adsorbed onto the active sites until the
equilibrium was achieved. Upon approaching the active sites on the
GSC surface for the removal of MB ions from the dye-containing was-
tewater, chemical bonds were formed, as described by the pseudo-
second order isotherm. In conclusion, the GSC synthesized from a
natural carbon source and agricultural biomass was an adsorbent with
promising potential for sustainable engineering practices for waste-
water treatment. Future studies should focus on the optimization of
GSC through particle size and surface functionalization as well as ad-
sorption parameters.
6
Journal of Water Process Engineering 35 (2020) 101185
Declaration of Competing Interest
None.
Acknowledgements
The authors wish to gratefully acknowledge the funding for this
work by Geran Universiti Penyelidikan (GUP-2017-098) and Dana
Modal Insan Universiti (MI-2019-017). The authors would also like to
express gratitude to the members from the UKM Membrane Technology
Laboratory for assisting us during the research project.
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.jwpe.2020.101185.
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