Fabrication of Polyacrylonitrile/magnesium oxide activated carbon nanofibers and its

application to remove lead(II) from aqueous solution

N.Abdullah1, F.E.C.Othman1, N.Yusof1*, J.Jaafar1, A.F.Ismail1, N. Misdan2

1
Advanced Membrane Technology Research Centre (AMTEC), Faculty of
Chemical and Energy Engineering, Universiti Teknologi Malaysia,

81310 Skudai, Johor Bahru, Malaysia

2
Faculty of Engineering Technology, University Tun Hussien Onn Malaysia,
86400 Parit Raja, Johor, Malaysia

ABSTRACT

Keywords:Activated carbon; Activated carbon nanofiber; Adsorption

capacity; Lead adsorptionr4 ` ` `

1. Introduction

There is a very great concern of treating water contaminated by

heavy metals as these elements are non-degradable and tend to
bioaccumulate into body system. Lead, cadmium, arsenic, copper, iron
and manganese are some heavy metals which are commonly detected in
waterways. Among the heavy metals, the exposure of lead (Pb) has been
profound to be toxic and bring chronic effects. Dissimilar to other heavy
metals that play roles in biochemical processes at their trace level, few
studies are found in the literature on the effects of lead on human body or
ecosystem. The anthropogenic sources of lead disposal into water
streams might vary; from leaded gasoline, industrial processes such as
lead smelting and coal combustion, lead-based paints, lead containing
pipes, battery recycling and bearings [1]. Medical diagnoses have claimed
that exposure of lead could severely cause neurotoxicity and affect
hematopoietic system, renal dysfunctions, cardiac and vascular damages
as well as damages in reproductive systems that result in infertility and
abnormality of foetus [2]. To date, the maximum contaminant level (MCL)
of lead in drinking water set by World Health Organization (WHO) and US
Environmental Protection Agency (USEPA) is 15ug/L [3].

Due to the hazardous impacts of lead exposure, many methods are

being employed for its removal, such as precipitation [4], coagulation-
flocculation [5], flotation [2], ion exchange [6], membrane filtration [3]
and adsorption [7], and metal leaching [8]. In addition to the mentioned
techniques, adsorption is another feasible method to eliminate Pb ions
due to availability of a wide range of adsorbents either synthetic or
natural and high recovery of adsorbents [9]. Conventionally, activated
carbons (ACs) in powder or granular forms are used as the common
materials in adsorption method. Recently, activated carbon nanofibers
(ACNFs) have attracted much attention to be utilized as adsorbent due to
their excellent adsorption capacities attributed to their smaller fiber
diameters and more uniform pore size distribution [10]. Melt fibrillation,
electrospinning, island-in-sea, and gas jet technique are several methods
used to produce nanofibers [11]. It seems that electro-spinning provides
more advantages in term of high production rate and relatively low cost
as compared to the other forms of ACs [12].

To prepare electrospun ACNFs, polymer polyacrylnitrile (PAN) serves

as a good carbon precursor as it has high carbon yield [13]. Recently,
many researches have focused on incorporating various metal oxides
such as magnesium oxide, aluminium oxide and manganese oxide into
PAN-based polymer solution [14]. It is believed that impregnation of metal
oxides as additives could increase the specific surface area of ACNFs as
well as the pore volume of electrospun ACNFs. In addition, most metal
oxides such as iron oxide, titanium oxide, aluminium oxide and
manganese oxide serve as excellent materials that adsorb pollutants.

2
 This study aims to prepare polyacrylnitrile/manganese oxide
(PAN/MnO2) based ACNFs (called ACNFs/MnO 2 hereafter) for the removal of
lead (II) ions. It is expected that incorporation of MnO 2 may enhance the
sorption capacity of ACNFs towards Pb(II). Hence, this work will offer
another potential alternative adsorbent to be used for the sequestration
of lead (II) ion from water streams.

2.0 Materials and methods

2.1 Materials

Polyacrynitrile (PAN) with molecular weight of 150 kDa, N,N-

Dimethylformamide (DMF) and manganese (IV) oxide (MnO 2) powder with
99% purity were purchased from Sigma Aldrich (USA). Stock solution of
lead ions was prepared using lead nitrate (Pb 2(NO3)2) (Sigma Aldrich, USA)
and pH of the solution was adjusted by using 0.01mol/L of NaOH and HCl
solutions.

2.2 Preparation of PAN-MnO2nanofiber mats by electrospinning

The dope solution with a composition of 10wt% of PAN and 2wt.%

of MnO2 (based on total weight solid) was prepared by mixing MnO2
powder in DMF followed by addition of 10wt% PAN. The mixture was
stirred for 5 h at room temperature to obtain homogenous solution. The
dope solution was stirred on a mechanical stirring plate to make the
suspension homogeneous. The suspension was subsequently electrospun
at a fixed electric field of 15 kV/20cm and suspension flow rate of 1.5
mL/h. The collected nanofibrous mats, called NFs/MnO 2 hereafter, were
allowed to dry for at least a day prior to carbonization and activation
process.

3
2.3 Carbonization and activation of nanofibers

The carbonization and activation of electrospun nanofibers were

carried out by following the procedures described by [15]. The nanofiber
mats were initially stabilized in air at 280 oC for 2 hours with heating rate
of 2oC/min, followed by carbonization in nitrogen gas at 600 oC for 1 hour
with heating rate of 5oC/min, and lastly heated under carbon dioxide gas
at 800oC for 3 hours. The procedures of fabricating nanocomposite
ACNF/MnO2 is illustrated in Fig. 1.

Fig. 1.Preparation of nanocomposite ACNFs/MnO2.

2.4 Characterizations

2.4.1 Specific surface area by BET analysis

The specific surface area of prepared ACNFs/MnO 2 was determined

by N2 adsorption at 130oC using automatic Tristar 3000 volumetric
system.

2.4.2 Functional group analysis by FTIR analysis

4
 The functional groups present in NFs/MnO2 and ACNFs/MnO2 were identified using
ATR-FTIR spectrometer (Model: IRTRACE100, Shimadzu). The samples were scanned by
single-reflectance ATR accessory with IRTRACER100. Each sample underwent a total of
600 scans at wavelength 500 cm-1 to 4000 cm-1 with scanning resolution of 0.25 cm-1.

2.4.3 Morphology studies by SEM-EDS analysis

The surface morphologies of nanocomposite ACNFs/MnO2 and neat

ACNFs were examined using Scanning electron microscopy (SEM) (Model:
TM 3000, Hitachi). All samples were sputter-coated with platinum to
prevent charging, reduce thermal damages and improve electron signal
needed for the SEM examination.

2.5 Sorption study of Pb (II)

The removal of Pb (II) from the aqueous solution by electrospun

nanocomposite ACNFs/MnO2 was compared with o granular activated
carbon (GAC) and neat ACNFs. For this purpose, 0.015 g of the adsorbent
was added to 15 mL of Pb (II) solution (an initial concentration of 3.5
mg/L) and the suspension was agitated for 48 hours at room temperature
on a rotary shaker until the adsorption equilibrium is reached. As most
studies reported the Pb adsorption on wide range of adsorbents
commonly reaches equilibrium below 24 h, therefore despite we did not
perform the contact time study, it is believed that 48 h is suffice for the
overall adsorption to reach equilibrium. The concentration of Pb(II) at the
equilibrium was then measured by subjecting the sample to Atomic
Absorption Spectroscopy (AAS) after removing the adsorbent by filtration
and the removal efficiency (%) of Pb (II) was calculated by

Removal efficiency (%) =(Co-Ce)/Co x 100 (1)

5
where Co and Ce are initial concentration and equilibrium concentration
(mg/L) of Pb(II), respectively.

The effect of the initial pH on the removal efficiency was further

studied for nanocomposite ACNFs/MnO2 by adjusting the initial pH using
0.01M NaOH or 0.01M HCl. The effect of the initial Pb(II) concentration on
the removal efficiency was also studied and the adsorption isotherm was
generated for nanocomposite ACNFs/MnO2. For this purpose,the amount
of Pb (II) adsorbed per unit gram of nanocomposite ACNFs/MnO 2 at the
equilibrium, qe (mg/g), was calculated by

qe = (Co-Ce)V/Mm (2)

where V is the total volume of (L) of the solution while Mm is the mass of
ACNFs/MnO2 used in the adsorption experiment (g).

2.6 Desorption of ACNFs/MnO2

Desorption of Pb (II) from ACNFs/MnO2 was performed to identify its

recovery rate. The ACNFs/MnO2 used for the batch adsorption study were
rinsed with distilled water to eliminate any residual solutions. Desorption
of metal ions was carried out by immersing the sample in 1M HCl solution
and the suspension was agitated at 30 oC and 100 rpm for 1 hour. The
concentration of Pb (II) in the solution was analyzed using atomic
absorption spectrometer (AAS) and the desorption ratio. D (%) was
calculated by:

6
D = (amount of metal desorbed (mg)/amount of metal ion adsorbed to
ACNFs/MnO2) x 100 (3)

3.0 Results and discussions

3.1 Characterizations of ACNFs and ACNFs/MnO2

3.1.1 Specific surface area

Table 1 shows the specific surface area (SSA) of neat and composite
ACNFs, before and after activation process. It can be seen that the
activation process increasing the surface area up to 52.4 times and 48
times for neat ACNFs and ACNFs/MnO2, respectively. It is also evident that
adding MnO2 increased the specific surface area from 478.2 m 2/g (neat
ACNFs) to 599.4 m2/g (ACNFs/MNO2). The improved SSA could be linked to
the improved microporosity and total pore volume as depicted in Table 2.
It is revealed that addition of MnO 2 led to micropore volume (0.25514
cm3/g) and higher total pore volume (0.299 cm3/g) as compared to the
neat ACNFs. The higher specific surface area, larger pore size and higher
total pore volume can be ascribed to ; 1) formation of additional pore
channel in the presence of MnO2 particles and 2) role of MnO 2 as a
catalyst that accelerates carbonization, thus causing the formation of a
larger amount of pores [14]. According to The IUPAC (International Unit of
Pure and Applied Chemistry), the pores of materials can be classified as
micropores (< 2nm), mesopores (2-50 nm) and macropores (> 50 nm). It
is observed that the pore size of NFs is larger as compared to the ACNFs
and ACNFs/MnO2. When the electrospun NFs were activated, the pore size
decreased, then which the ACNFs produced in this study has micropores.
In this study, the pore size of neat ACNFs and ACNFs/MnO 2 was not
significantly differ, and categorized as micropores.

7
 Table 1.Effect of MnO2 addition on SSA of nanofiber mats.

Sample Specific surface area (S.S.A) (m/g)

Before After activation

activation

Neat ACNFs 9.13 478.2

ACNFs/MnO 12.45 599.4

Table 2. Micropore volume and Total Pore Volume (T,P,V) before and after
activation.

Pore size (nm) Micropore T.P.V (cm3/g)

volume (cm3/g)

ACNFs 1.73 0.194 0.210

ACNFs/MnO2 1.75 0.285 0.299

3.1.2 Chemical structure

The FTIR spectra of NFs/MnO2 and ACNF/MnO2 are shown in Fig. 2. It can
be seen that the activation process removed nitrile groups (CN) and
methylene group (CH2). The absorption peaks are observed for
ACNF/MnO2 at 1097.5 cm-1, 1801.5 cm-1, 1990.54 cm-1, 2113.98 cm-1 and
2326.15 cm-1 representing C-O (strong stretching), C=O (strong
stretching), C=C (variable), C=C (variable) and CC groups (variable),
respectively, indicating the presence of some functional groups after
activation. Meanwhile, absorption peak at 528.5 cm-1 was identified as
Mn-O, indicating the presence of MnO2 in the ACNFs/MnO2.

8
 C
C

Fig. 2.FTIR spectra of NFs/MnO2 and ACNFs/MnO2.

9
3.1.3 Morphological structure

Fig. 3. SEM micrograph analysis of a) neat ACNFs, b)ACNFs/MnO 2;

i)2500x magnification and ii)10000x magnification.

Fig. 4.EDS mapping of Mn on ACNFs/MnO2.

10
 Fig. 3 exhibits the SEM images of neat ACNFs and ACNFs/MnO 2. It can
be observed that the nanofibers in neat ACNFs are straighter while
ACNFs/MnO2 are bent and more compactly packed. When comparing the
diameter of neat ACNFs and ACNFs/MnO 2, it is revealed that ACNFs/MnO 2s
diameter (433.7 nm) is smaller than neat ACNFs (669.0nm). It should be
noted that MnO2 may have dispersed as beads at the outer surface of
ACNFs/MnO2 as denoted by arrow in (bi). The morphology of electrospun
ACNFs obtained in this study is concurring to the study conducted by [16] in
which the ACNFs/MnO2 was observed to have compact nanofibers with
dispersion of beads containing MnO2 particles. This observation was further
supported by EDS mapping, as depicted in Fig. 4. It is presumed that during
electrospinning process, jet instability occurred in which polymeric PAN
solution was ejected first, followed by sputtering of MnO2 particles [13].
Nevertheless, EDS-mapping analysis indicated the dispersion of MnO 2 is
rather homogenous, despite of the formation of MnO2-contained beads
alongside the nanofibers.

3.2 Removal of Pb (II) ions from aqueous solution

3.2.1 Comparative study of GAC, neat ACNFs and ACNFs/MnO2

Fig.5. Comparison of removal efficiency between three types of

activated carbon.

11
 Comparison of the efficiency of Pb(II) removal was made between
conventional GAC, neat ACNFs and ACNFs/MnO2 and the results are
displayed in Fig. 5. Interestingly, both ACNFs showed complete removal of
Pb(II) while removal efficiency of GAC was slightly less, demonstrating the
potential of ACNFs as the adsorbent for heavy metals sequestration. Further
parameters such as effect of initial pH and concentration were studied and
discussed in the next section.

3.2.2 Effect of pH

The Pb(II) removal by ACNFs/MnO2 was further investigated at different

pH (1.0 to 6.0) and the results shown in Fig. 6. The test was not done at pH
values higher than 6.0 due to precipitation of Pb(II) ions with OH-ions to form
lead hydroxides that might cause inaccuracy of data analysis [17]. Referring
to the figure, low removal efficiency was observed at the acidic condition.
Increasing of the pH gradually increased the removal efficiency from 3.4%
(pH 1.0) to 94% (pH 5.0). Thus, the optimum pH for this study was identified
to be at pH 5.0. From the trend shown in the figure, it is evident that
removal of Pb (II) is strongly related to pH, linking to the protonation of
related functional groups present in ACNFs/MnO 2 [18,19]. In acidic condition,
low adsorption efficiency achieved is mainly due to the competition between
H+ and metal ions for active sorption sites [20]. At higher pH value, the
surface was negatively charged thus allowed attraction between surface of
adsorbent and positive metal ions.

12
 100

80

60
Removal efficiency (%) 40

20

0
1 2 3 4 5
pH

Fig. 6.Effect of pH on removal of Pb (II).

3.2.3 Effect of initial concentration

Fig. 7 depicts the removal efficiency of Pb(II) by ACNFs/MnO 2 with

respect to different initial concentrations (10 - 200 mg/L) of Pb(II). The results
indicate that the removal efficiency decreases with initial Pb(II)
concentration. The figure also shows the adsorption capacity (the same as qE
obtained by equation 2) increases with initial Pb(II) concentration. The
highest adsorption capacity achieved was 120.3 mg/g. Further increment of
metal uptake was not observed owing to the saturated binding sites of the
adsorbent [19]. For carbon-based adsorbents, the adsorptive capabilities are
contributed surface area, pore volume as well as minor role of surface
functional groups which adsorb the ions. For the adsorption process,
enhancing the former features is necessary as higher SSA and pore volume
facilitate the adsorption process due to the availabillity of more binding sites.
In this study, the satisfactory adsorption of Pb(II) ions are ascribed by the
high SSA and pore volume of the ACNFs/MnO 2. In addition, the uptake of Pb
(II) ions may also be attributed to the amount of surface total acidity related
to the surface functional groups as detected by FTIR analysis [21,22].

13
Another possible reason could be ascribed by the present of MnO 2 itself that
has higher affinity towards metallic ions and thus assisting the adsorption
process [23].

100 140
90
120
80
70 100
60 80
50
40 60
Removal efficiency Adsorption capacity
30 40
20
20
10
0 0
10 20 50 100 200
Initial concentration (mg/L)

Fig. 7.Effect of initial Pb(II) concentration on removal efficiency and adsorption capacity.

3.2.4 Adsorption isotherm

In order to evaluate the adsorption mechanism, the Langmuir and

Freundlich isotherm models were applied. The linear equations of Langmuir
and Freundlich models are given by Equation 4 and 5, respectively:

Ce 1 C
= + e
q e Qmax b Qmax

(4)

14
where Qmax is the maximum adsorption capacity (mg/g) and b is related to
binding energy of the sorption system (L/g).

log q e=log K F + ( 1n ) log C e

(6)

where KF is the Freundlich constant ((mg/g/mg/L) 1/n) and 1/n is the

heterogeneity parameter corresponding to the adsorption intensity.

15
a)
b)

0.8
2.5

0.6
2

0.4 1.5
C/q
Log q
1
0.2 Fig, 8.Linearized graph of a) Langmuir; b) Freundlich model.
0.5
0
0 10 20 30 40 50 60 70 80 90 0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
C (mg/g)
Log C

Table 3.Langmuir and Freundlich isotherm parameters.

Langmuir model Freundlich model

KF
Qmax b n
2
Adsorbent R R2
((mg/g/
(mg/g) (L/g)
mg/L)1/n)

ACNF/MnO2 107.5 0.198 0.8803 22.7 2.78 0.9261

16
 The linear plots according to the Langmuir and Freundlich model are
shown in Fig. 8, while the related parameter values are tabulated in Table 3.
The Langmuir constants Qmax (mg/g) and b (L/g) were calculated from the
slope and intercept of the linear plot of Ce/qe versus Ce (Fig. 7a). Meanwhile
the Freundlich model constants KF (mg/g/mg/L)1/n) and n were calculated from
the slope and intercept obtained from the linear plot of log qe versus log Ce,
respectively. As seen from Table 3, the R2 value from the Freundlich model
(0.9261) is higher than the Langmuir model (0.8803). Thus, the Freundlich
isotherm model is better fitted to the experimental adsorption data.
Dissimilar to Langmuirs sorption which is based on the chemisorption at a
specific homogenous surface with a finite number of identical sites [24,25],
Freundlich model suggests that the sorption occurs on a heterogenous
surface. The value n> 1 (2.78) indicates the favorability of sorption on the
surface of ACNFs/MnO2 [26]. In our case, the n value is 2.78 which may due
to the distribution of surface sites and increment of surface density that
decrease the interaction of adsorbate-adsorbent. Despite the R2 indicated
that Freundlichs model is best to describe the isotherm, it is believed
mechanism of adsorption occurred in this study correlates to Langmuirs
model. As stated previously, micropores were formed in the ACNFs/MnO 2.
Therefore, it is possible that co-operative pore filling mechanism plays role in
the adsorption process where monolayer adsorption occurs followed by pore
filling at the reduced pores diameter. Table 4 depicts the maximum
monolayer capacity of different carbon fiber-based adsorbents and herein
this study. From the table, the adsorption capacity of ACNFs/MnO 2 towards Pb
(II) is satisfactory which was 107.5, showing its great affinity to heavy metal
ions.

Table 4.Adsorption capacity of different adsorbents on Pb (II).

Adsorbent Amount of Maximum Ref.

adsorbent (g/L) capacity (mg/g)

17
Activated carbon fiber/carbon 0.6 40.0 [27]
nanofiber

Iron oxide-alumina nanocomposite 2.5 63.69 [10]

fiber

Carbon nanofiber grown on 0.1 100 [28]

powdered activated carbon

Aminated nanofiber mats 5.0 60.6 [24]

Activated carbon 1.0 107.5* In this present

nanofiber/manganese oxide study

Carbon nanofiber on macroporous NA 211.1 [29]

kaolin

*Maximum monolayer adsorption capacity obtained from

Langmuir
3.2.5 Desorption study

From the desorption study, it was found that ACNFs/MO 2 had a

desorption ratio more than 95%. This high reusability exhibits its potential as
another promising adsorbent for heavy metal adsorption.

4.0 CONCLUSION

This present study reports the production of electrospun ACNFs/MnO 2

for removal of lead (II) ions by adsorption. In this study, ACNFs shows
promising adsorption capacity upon adsorbing Pb (II) as compared to the
commercial granular activated carbon. The specific surface area, pore size
and total pore volume were increased attributed by the role of MnO 2 as
catalyst. Under SEM analysis, the ACNFs/MnO 2 the ACNFs incorporated by
MnO2 has found to be more compact and possessed smaller diameter with
dispersion of Mn beads. Adsorption study demonstrated that the sorption
process was highly dependent on pH. The mechanism of sorption was best

18
fitted to be described by Freundlich model while Langmuir model disclosed
that the maximum monolayer uptake was 107.5 mg/g on heterogeneous
surface of ACNFs/MnO2. The high adsorption capacity and recovery obtained
in this study indicated the potential of ACNFs incorporated MnO 2 as
adsorbent for removing target pollutants, not only from aqueous solution as
well as for removing heavy metals from industries.

5.0 ACKNOWLEDGEMENTS

The authors would like to acknowledge the financial support from

Malaysian Ministry of Education and Universiti Teknologi Malaysia under
Grant No. R.J130000.7842.4F279 and Q.J130000.2542.05H46. The authors
would also like to acknowledge the technical and management support from
Research Management Centre (RMC), UniversitiTeknologi Malaysia.

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