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Razi University, Membrane Research Center, Department of Chemical Engineering, Daneshgah Road, Tagh Bostan, Kermanshah 67149, Iran
Department of Chemical Engineering, Kermanshah University of Technology, Kermanshah, Iran
c
Faculty of Engineering, Department of Chemical Engineering, Arak University, Arak, Iran
d
Nano Science and Technology Research Center, Physics Department, Razi University, Kermanshah, Iran
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 2 March 2012
Received in revised form
26 April 2012
Accepted 1 May 2012
Available online 18 May 2012
A novel mixed matrix polymeric membrane was prepared from polyethersulfone (PES) and
self-produced polyaniline/iron(II, III) oxide (PANI/Fe3O4) nanoparticles by phase inversion method.
The core-shell structured PANI/Fe3O4 nanoparticles were veried and characterized using X-ray
diffraction (XRD), transmission electron microscopy (TEM) and fourier transform infrared spectroscopy
(FTIR). Three different amounts of nanoparticles were introduced into the casting solutions to obtain
the optimum value. According to the performance test, the membrane with 0.1 wt% nanoparticles
indicated the highest Cu(II) ion removal but the lowest pure water ux. This is caused by nanoparticles
located in the supercial pores of the membrane during preparation i.e., surface pore blockage.
Morphological analysis including eld emission scanning electron microscopy (FESEM) and atomic
force microscopy (AFM) as well as membrane performance tests revealed that adsorption is the most
possible separation mechanism by the membranes. For better investigation of the adsorption
mechanism, several isotherm models such as Langmuir, Freundlich and Redlich-Peterson were tested.
Based on the isothermal results, the Redlich-Peterson model offered superior tness indicating
relatively complex adsorption mechanism. The reusability of the nanocomposite membrane was
conrmed for several sequential adsorption-desorption processes using EDTA as regenerator.
& 2012 Elsevier B.V. All rights reserved.
Keywords:
PES
Nanocomposite membrane
PANI/Fe3O4 nanoparticles
Cu(II) removal
Adsorption isotherms
1. Introduction
Copper ion, as a toxic contaminant of potable water resources
at unauthorized dosages (more than 2 mg/l), should be eliminated
because of its dangerous risks for human being such as headache,
depression and learning problems [15]. Heavy metals including
copper are also toxic for plants and can affect the root growth [4].
There are several processes such as precipitation, coagulation,
adsorption, ion exchange, electro-dialysis, electro-coagulation,
and membrane separation processes for removing metal ions
from efuents [3,68]. Membrane processes offer several advantages compared with other separation methods such as high
removal efciency, low energy consumption, high ow rate, small
footprint and ease of scale up [9,10].
Elimination of copper ion by amphoteric polybenzimidazole
nanoltration hollow ber membrane has been reported [6]. The
removal of copper from efuents by Nanomax50 nanoltration
0376-7388/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.memsci.2012.05.007
2. Experimental
2.1. Materials
The chemicals used in the current study are presented in
Table 1. All reagents were used without further purication except
for aniline which was double-distilled to obtain pure aniline
monomers.
251
Table 1
Used chemicals identication.
Chemical
Supplier
Purication
FeCl3 6H2O
FeCl2 4H2O
NH4OH
Aniline
Merck,
Merck,
Merck,
Merck,
HCl
(NH4)2S2O8
DMAc
PES, Ultrason E6020P,
MW 58000 g/mol
PVP, MW 25,000 g/mol
EDTA
Merck, Germany
Merck, Germany
Merck, Germany
BASF, Germany
Twice
distillation
Germany
Germany
Germany
Germany
Merck, Germany
BDH Chemicals Ltd.,
England
Merck, Germany
NaOH
Table 2
Prepared membranes composition (values in wt%).
Name
PES
PVP
DMAc
PANI/Fe3O4
Pristine PES
FA0.01
FA0.1
FA1
18
18
18
18
1
1
1
1
81.00
80.99
80.90
80.00
0.01
0.1
1
252
C f C p
100
Cf
C 1 C e V
Mm
W w W d
100
Wd
W w W d
100
rf V m
253
FA0.01
FA0.1
FA1
Pristine PES
100
90
80
70
60
50
40
30
20
10
0
Pristine PES
20
40
60
Time (min)
80
100
120
FA0.01
FA0.1
FA1
55
50
45
40
35
30
25
20
15
10
5
0
0
10
20
30
50
40
Time (min)
60
70
80
90
100
3.1. Nanoparticles identication
The X-ray diffraction pattern of the powder sample is shown in Fig. 1. The
Bragg reection peaks at 2ys equal to 30.24, 35.64, 43.38, 53.84, 57.52, 63.02 and
74.53 are attributed to diffraction from the (2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1),
(4 4 0) and (5 3 3) planes of cubic inverse spinel Fe3O4, respectively, which are in
good agreement with the previously reported data (Magnetite: 011111). No
additional peak for other possible phases of iron oxide was observed (pure phase).
The average grain size (D) was calculated using DebyeScherrers equation:
Kl
bcosy
where D is the grain size of the crystal (nm), K is the Scherrer constant (0.89),
l and b are the X-ray wavelength and the peak width of half-maximum, and y is
the Bragg diffraction angle of the XRD spectra. The calculation revealed the
average grain size of about 14 nm.
Fig. 2 shows the TEM microphotograph of PANI/Fe3O4 nanoparticles with a
core-shell structure, which proved that iron oxide nanoparticles was successfully
entrapped in the polyaniline shell. The resulted core-shell PANI/Fe3O4 nanoparticles
retained their spherical structure with the average diameter of the magnetic core
about 1228 nm. The thickness of the polyaniline shell was determined around
8 nm (obtained from several microphotographs).
With respect to FTIR spectra of F3O4 and PANI/Fe3O4 depicted in Fig. 3, the
peaks at 1149, 1280 (CN), 1307 (QBB, QBQ), 1494 (NBN) and 1589 (NQN) cm
verify formation of PANI on iron oxide nanoparticles.
95
90
85
80
75
70
5 mg/l
65
10 mg/l
60
55
50
0
20
40
60
Time (min)
80
100
120
Fig. 6. Rejection of copper ions versus time at low concentrations (5 and 10 mg/l)
of feed solution for FA0.1.
254
Fig. 7. AFM images of (a) pristine PES, (b) FA0.01, (c) FA0.1 and (d) FA1.
Table. 3
Roughness parameters, water content and porosity of prepared membranes.
Membrane
PES
FA0.01
FA0.1
FA1
a
Sq
Sz
12.4
11.6
5.9
10.3
17.2
15.5
7.6
13.1
286.4
187.3
51.2
136.7
Water content
(wt%)
Porosity
(v/v%)
285 7 2
293 7 2
3077 3
328 7 3
62
68
71
77
255
256
Fig. 9. Comparison of top-layer thickness between (a) pristine PES, (b) FA0.01, (c) FA0.1 and (b) FA1.
Fig. 10. FESEM images of cross section of (a) pristine PES, (b) FA0.01, (c) FA0.1 and (d) FA1.
86
85
85
1.8
1.6
84
1.4
83
83
82
82
Qe (mg/g)
257
82
81
1.2
1
0.8
0.6
80
1
y vs. x
langmuir
0.4
Run number
0.2
0
0
10
15
Ce (mg/l)
20
25
30
1.6
1.4
Qe (mg/g)
1.2
1
0.8
0.6
Fig. 12. Scheme of octahedral complex.
0.4
Qe a
bC e
1 bC e
0.2
0
10
15
Ce (mg/l)
20
25
1.6
Figs. 1315 indicate Langmuir, Freundlich and R-P isotherms tted to the
equilibrium adsorption data, respectively. Based on the tting results (Table 4),
Freundlich isotherm conformity with the equilibrium data was somewhat better
than that of the Langmuir indicating multilayer adsorption coverage on the
membrane surface. Besides, being m-value higher than unity indicates that
physical adsorption occurred on a relatively heterogeneous surface. It is obvious
that Redlich-Peterson offers superior accordance with the equilibrium data on the
basis of the coefcient of determinations (R2 0.99). This suggests relatively
1.4
1.2
Qe (mg/g)
Q e kUC e m
y vs. x
Freundlich
1
0.8
0.6
0.4
y vs. x
R-P
0.2
0
0
10
15
Ce (mg/l)
20
25
258
Table 4
Isotherms tting parameters and goodness of the ts.
Isotherm model
Parameters
a 1.632
Langmuir
b 1.525
k 0.9233
Freundlich
m 5.403
a 1.08
b 9.691
R-P
m 0.8662
Goodness of t
SSE 0.101
R-square 0.9659
Adjusted R-square 0.9617
RMSE 0.1123
SSE 0.06167
R-square 0.9792
Adjusted R-square 0.9766
RMSE 0.0878
SSE 0.03112
R-square 0.9895
Adjusted R-square 0.9865
RMSE 0.06668
4. Conclusion
Novel nanocomposite polymeric membrane was prepared by
PES and PANI/Fe3O4 nanoparticles. Characterization of nanoparticles using XRD and TEM proved that the prepared core-sell
structured particles had mean size of 1228 nm for iron(II,III)
oxide core and thickness of about 8 nm for the polyaniline shell.
The FTIR result of prepared nanoparticles veried formation of
PANI on iron oxide NPs. Copper ion removal was tested and the
results revealed that proper amount of nanoparticles in casting
solution and signicant dispersion of NPs are responsible for
efcient Cu(II) elimination. The membrane with 0.1 wt%NPs
(FA0.1) showed the highest ion rejection (around 85%) for
20 mg/l Cu(NO3)2 aqueous solution. The prepared membrane
was also able to remove 75%of Cu(II) ions from almost low
concentration feed solution (5 mg/l). Showing the minimum
agglomeration and high NPs dispersion in FESEM and AFM
images, the FA0.1 membrane composition was selected as the
optimum composition for mixed matrix membrane. The results
demonstrated that the adsorption mechanism was dominating
ion rejection of the membranes. By the isotherm conrmation
results, the most probable adsorption isotherm was
Redlich-Peterson isotherm expressing relatively complex adsorption
mechanism. The regeneration results conrmed that the prepared
nanocomposite membrane can offer excellent reusability as well as
durability in ltration process.
List of symbols
b
y
l
rf
a
AFM
APS
B
b
C0
Ce
Cf
Cp
D
DMAc
DW
EDTA
FA0.01
FA0.1
FA1
FESEM
FTIR
K
k
m
Mm
NPs
PANI
PES
PVP
Q
Qe
R
RMSE
R-P
Sa
Sq
SSE
Sz
TEM
TM
V
Vm
Wd
Ww
XRD
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