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Journal of the Taiwan Institute of Chemical Engineers

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Characterization of reduced graphene oxide supported mesoporous

Fe2 O3 /TiO2 nanoparticles and adsorption of As(III) and As(V) from
potable water
Cadiam Mohan Babu a,b, Rajangam Vinodh a,b, Balachandran Sundaravel d, Aziz Abidov a,b,
Mei Mei Peng a,b, Wang Seog Cha b,c, Hyun-Tae Jang a,b,∗
a
Department of Chemical Engineering, Hanseo University, Seosan 360-706, South Korea
b
Korea Carbon Capture and Sequestration R and D Centre, 360 Daegok-ri, Haemi-myun, Seosan-si 356 706, Chungcheongnam-do, South Korea
c
School of Civil and Environmental Engineering, Kunsan National University, Kunsan, 573-701, South Korea
d
Department of Chemistry, Anna University, Chennai 600 025, India

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

Article history: The removal of hazardous anions is essential to supply safe drinking water. In this study mesoporous
Received 23 September 2015 Fe2 O3 /TiO2 was synthesized by sol–gel route using Pluronic P123 as the structure directing agent. The
Revised 23 December 2015
synthesized mesoporous Fe2 O3 /TiO2 nanoparticles dispersed over the reduced graphene oxide, to sup-
Accepted 2 February 2016
press the aggregation of the nanoparticles and to expose more number of active sites present in the
Available online xxx
nanoparticles. The mesoporous nature of the nanoparticles was confirmed from low angle X-ray diffrac-
Keywords: tion. The reduced graphene oxide supported Fe2 O3 /TiO2 nanoparticles was characterized by FT-IR, Raman,
Reduced graphene oxide XPS, N2 sorption, HR-TEM and SEM. The reduced graphene oxide supported Fe2 O3 /TiO2 nanoparticles was
Mesoporous tested for the sorption of both arsenate (AsV) and arsenite (AsIII) in water. The equilibrium adsorption
Nanocomposites was attained within 15 mins for both As(III) and As(V). The maximum adsorption capacity for As(V) and
Adsorption As(III) was found to be 99.5 and 77.7 mg/g at pH 6 and 7 respectively. The sorption was found to be high
Arsenic
in the pH range of 6–7. The low adsorption at lower and higher pHs other than 6 and 7 was due to zero
point charge of nanocomposite which is equal to 6. The IR spectrum showed characteristic vibrations for
arsenate in the nanocomposite. The recyclability study of nanocomposite not only confirmed the stabil-
ity but also exhibited same sorption capacity for four cycles. This nanocomposite could be used for the
removal of other hazardous inorganic ions.
© 2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
The presence of arsenic in drinking water causes severe dam-
age to human health [1]. Arsenic is predominantly present in wa-
ter as As(V) and As(III) states [2]. Arsenite exists in neutral form
in drinking water and hence it is difficult to remove from aqueous
solution [3]. The health organisations like US environmental pro-
tection agency and WHO set a maximum upper limit of 10 ppb for
arsenic in drinking water [4,5].
Various treatment methods like adsorption, ion-exchange and
reverse osmosis have been applied for the removal of arsenic
in drinking water [6–8]. Among them, ion-exchange and reverse
osmosis are efficient and not cost effective compared to other
techniques. Now a days nanomaterials exhibit vital contribution in
adsorption studies [9–12]. Fe2 O3 nanowire deposited on diatomite
∗
Corresponding author. Tel.: +82 041 660 1423; fax: +82 041 688 4143.
E-mail address: htjang@hanseo.ac.kr (H.-T. Jang).
(siliceous rock) showed high adsorption capacity for arsenic [13].
Titanate nanofibres showed high affinity for the removal of arsenic
from drinking water [14]. Binary metal oxide possesses high
adsorption capacity compared to mono metal oxide [15]. Zhang et
al [16] reported high adsorption of arsenic on Fe–Ce bimetal oxide
due to the presence of many M–OH groups. Materials with ordered
mesopores were used as efficient adsorbents in water treatment
[17]. Mesoporous alumina showed enhanced adsorption for arsenic
due to their mesopores [18]. The ordered mesoporous MnO2 was
used as synergistic adsorbent for the removal of arsenite [19].
Wei-Hong et al. [20] reported superparamagnetic mesoporous
MnFe2 O4 for high and rapid adsorption of arsenite. Mesoporous
Ti–Zi oxide nanofibres with high surface area showed enhanced
adsorption of heavy metals [21]. Iron oxide loaded on mesoporous
silica exhibited as an efficient support for arsenic removal [22].
Jie Ma et al. [23] reported that uniform dispersion of iron oxide
on carbon nanotubes as excellent adsorbents for removal of both
arsenate and arsenite from aqueous solution. Bo chen et al. [24]

http://dx.doi.org/10.1016/j.jtice.2016.02.005
1876-1070/© 2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: C.M. Babu et al., Characterization of reduced graphene oxide supported mesoporous Fe2 O3 /TiO2 nanopar-
ticles and adsorption of As(III) and As(V) from potable water, Journal of the Taiwan Institute of Chemical Engineers (2016),
http://dx.doi.org/10.1016/j.jtice.2016.02.005
JID: JTICE
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2 C.M. Babu et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2016) 1–10
reported surfactant assisted binary Ce–Fe oxide dispersed on
multiwalled carbon nanotubes as adsorbent for the removal of
arsenic. Zirconium immobilized on nano carbon with high active
sites showed good adsorption of arsenic [25].
Graphene, a carbon based two dimensional material, is found to
exhibit enormous applications in fields such as sensor, lithium ion
batteries, catalyst and adsorption [26–29]. Graphene metal oxide
composites were used as adsorbent and as photocatalyst in wa-
ter treatment [30]. Seung et al [31] reported macroporous reduced
graphene oxide as an efficient adsorbent for oils and organic sol-
vents. Magnetic graphene oxide was used for the removal of heavy
metals and As(V) from aqueous solution [32,33].
Compared to other supports for metal oxides, graphene is found
to be better, and hence it was chosen as the support. Many re-
searchers used Fe2 O3 solely as an adsorbent for arsenic removal.
Our motivation is to increase the number of active sites for the
adsorption. When synthesized mixed metal oxides with excess of
–OH groups to create defective sites and thus ultimately enhances
the adsorption of As. So in this work we synthesized various
weight ratios of Fe2 O3 /TiO2 (10:90, 30:70, 50:50 70:30 and 90:10),
in that 50:50 wt% showed maximum adsorption compared to oth-
ers. So, we had chosen 50:50 wt% Fe2 O3 /TiO2 nanoparticles for
the adsorption. Mesoporous Fe2 O3 /TiO2 nanoparticles were syn-
thesized by sol–gel method using Pluronic P123 as the template,
and characterized using different techniques. Graphene oxide was
prepared by Hummers method [34]. This graphene oxide was re-
duced by hydrazine hydrochloride to obtain reduced graphene ox-
ide. Then, mesoporous nano Fe2 O3 /TiO2 was dispersed on reduced
graphene oxide to obtain reduced graphene oxide supported meso-
porous Fe2 O3 /TiO2 (RGO-MFT) nanocomposites. The nanocompos-
ites were characterized using XRD, HRTEM, SEM, XPS, FT-IR, Raman
and BET techniques. The amount of arsenic present in water be-
fore and after adsorption on nanocomposites was determined us-
ing ICP-OES.
2. Experimental details
2.1. Reagents and materials
Graphite flakes (Alfa essar) were used for the synthesis of
graphene oxide. All the reagents and chemicals were of analyti-
cal grade and used without further purification. Titanium (IV) iso-
propoxide (Merck) and iron (III) nitrate nanohydrate (Fisher) were
used as the sources for Ti and Fe respectively. Triblock copoly-
mer [poly (ethylene glycol)-block-poly(propylene glycol)-block-
poly(ethylene glycol)] (Pluronic P123, molecular weight = 5800,
EO20PO70EO20, Aldrich) was used as the structure directing tem-
plate. Sodium arsenate (Na2 HAsO4 .7H2 O) and sodium arsenite
(NaAsO2 ) were used as the sources for As(V) and As(III) respec-
tively.
2.2. Synthesis of reduced graphene oxide (RGO)
Graphene oxide was synthesized by modified Hummers method
[34]. Graphite (1 g) and NaNO3 (1 g) were added to 40 ml H2 SO4
kept in a 500 ml round bottomed flask and stirred at low temper-
ature (0–5 °C). KMnO4 (6 g) was slowly added to the mixture and
the reaction temperature was maintained below 10 °C. The temper-
ature was then increased to 35 °C and stirred another 1 h. It was
then slowly diluted with 60 ml water and the solution stirred for
additional 30 mins at 90 °C. Finally water (120 ml) and H2 O2 (30%)
(6 ml) were added to obtain a yellow precipitate. The precipitate
was filtered and washed with 10% HCl and water, and the residue
was dried under vacuum to obtain graphene oxide.
Graphene oxide (100 mg) was dispersed in distilled water
(50 ml) and the pH of the mixture was adjusted to 10 using KOH
Please cite this article as: C.M. Babu et al., Characterization of reduced graphene oxide supported mesoporous Fe2 O3 /TiO2 nanopar-
ticles and adsorption of As(III) and As(V) from potable water, Journal of the Taiwan Institute of Chemical Engineers (2016),
http://dx.doi.org/10.1016/j.jtice.2016.02.005
[m5G;February 23, 2016;15:23]
solution. Hydrazine monohydrate (1 ml) was added to it and stirred
for 24 h at 90 °C. The black precipitate was filtered and washed
several times with distilled water to remove the excess hydrazine.
The black powder was dried at 80 °C under vacuum to obtain re-
duced graphene oxide.
2.3. Synthesis of mesoporous Fe2 O3 /TiO2 nanoparticles
Mesoporous Fe2 O3 /TiO2 nanoparticles were synthesized by sol–
gel method using Pluronic P123 as the structure directing agent
[36]. The synthesis procedure of meso-50:50 wt% Fe2 O3 /TiO2
(meso- Fe2 O3 /TiO2 ) was as follows: 1 g Pluronic P123 was added
to 30 ml ethanol kept in a polypropylene bottle and stirred for 4 h
at room temperature. Titanium isopropoxide (3.71 ml) and iron (III)
nitrate nonahydrate (2.53 g) were added to it and stirred for ad-
ditional 2 h. Ammonia (10 ml) was added drop by drop to main-
tain the pH around 10. Then distilled water (10 ml) was added, and
stirred for additional 24 h. The reaction mixture was kept in dark
(12 h) for nucleation. It was then centrifuged, and the residue dried
at 100 °C and ground to fine powder. The powder was calcined at
500 °C for 5 h in nitrogen atmosphere to remove the template com-
pletely. Mesoporous TiO2 and Fe2 O3 were synthesized separately
using the same procedure with the respective metal salt.
2.4. Synthesis of reduced graphene oxide supported nanocomposites
(RGO-MFT)
Meso- Fe2 O3 /TiO2 (95 mg) and RGO (5 mg) were added to a
250 ml beaker containing 100 ml distilled water, and sonicated for
2 h. It was then stirred for 24 h, filtered and dried at 70 °C under
vacuum.
2.5. Characterization
The X-ray diffraction (XRD) patterns were recorded on a PAN-
alytical X’Pert Pro X-ray diffractometer using CuKα radiation as
the X-ray source. The attenuated total reflectance-infrared (ATR-IR)
spectra were recorded on an ATR-IR spectrometer (Perkin Elmer,
Spectrum Two) in the scan range of 40 0 0–40 0 cm−1 . Raman spec-
tra for the samples were recorded on a LABRAM HR 800 spectrom-
eter (HORIBA JOBIN YVON) using a 633 nm He–Ne laser source.
Brunauer–Emmett–Teller (BET) surface area, pore volume and pore
size were obtained from Micromeritics ASAP 2020 volumetric ad-
sorption analyser. Prior to each adsorption experiment, the sam-
ples were degassed for 3 h at 100 °C. The morphology of the ma-
terial was examined by scanning electron microscope (SEM) (JEOL,
JSM-5600) at an accelerating voltage of 20 kV, and high resolution
transmission electron microscope (HR-TEM) (JEOL- 2100) at an ac-
celerating voltage of 200 kV. Thermogravimetric analysis (TGA) was
carried out from 40 to 900 °C at a heating rate of 15 °C min−1
under nitrogen atmosphere on a Perkin Elmer SII (Diamond se-
ries). The X-ray photoelectron spectra (XPS) of the materials were
recorded on an MS Omicron XM-10 0 0 with AlKα as the radia-
tion source operated at 200 W and a hemispherical electron en-
ergy analyser. The pH of point of zero charge (pHpzc) for the
nanocomposite was determined using the literature reported pro-
cedure [35]. The procedure was carried out twice and the average
value was taken. The concentration of adsorbate (As(III) and As(V))
in the aqueous solution before and after adsorption was deter-
mined using a inductively coupled plasma-optical emission spec-
trometer (ICP-OES) (Perkin Elmer (OPTIMA 70 0 0 DV)).
2.6. Batch sorption experiments
2.6.1. Adsorption isotherm and kinetics
The adsorption experiments were carried out in a closed
polypropylene flask and kept on a mechanical shaker revolving
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(d)

Intensity (a.u.)
(c)
Intensity (a.u.)

(b)

(a)

20 30 40 50 60 70 10 20 30 40 50 60 70
2 theta (degree)
2 theta (degree)
Fig. 1. XRD patterns of (a) meso-TiO2 , (b) meso-Fe2 O3 , (c) meso- Fe2 O3 /TiO2 and
Fig. 2. XRD pattern of RGO. Inset figure shows low angle XRD pattern of meso-
(d) RGO-MFT.
Fe2 O3 /TiO2 .

at 175 rpm. Different concentrations of arsenic (3–80 mg/L) were

prepared from the stock solution of sodium arsenate heptahydrate
and sodium arsenite with deionized water. RGO-MFT (0.2 g/L) was
added to 100 ml each of As(III) and As(V) solution and shaken for
Transmittance (a.u)
3 h. After adsorption, the concentration of arsenic in the aqueous (a)
solution was analysed by ICP-OES (Optima 70 0 0 DV). Adsorption
kinetics was also carried out for different time interval from 1 to (b)
120 min.
(c)
2.6.2. Effect of pH
RGO-MFT (0.2 g/L) was dispersed in a polypropylene flask con-
taining 100 ml of adsorbate (20 mg/L) solution of different pH (3–
10). The pH was adjusted using 0.1 N HCl and 0.1 N NaOH. The so-
lution was kept on a mechanical shaker revolving around 175 rpm
for 3 h at 35 °C. The equilibrium adsorption capacity (qe ) was cal- (d)
culated using Eq. (1) [37].
V (C0 − Ce ) 4000 3500 3000 2500 2000 1500 1000 500
qe = (1)
M Wavenumber (cm )
-1

where C0 and Ce are the initial and equilibrium concentration

(mg/L) of adsorbate in the solution, V is the volume of adsorbate Fig. 3. FT-IR spectra of (a) GO, (b) RGO, (c) meso- Fe2 O3 /TiO2 and (d) RGO-MFT.
solution and M is the weight of adsorbent in g.

2.7. Regeneration of the adsorbent
RGO-MFT (0.2 g/L) was added to a flask containing 100 ml of
adsorbate (20 mg/L) maintained at pH 7 and kept on a shaker for
24 h. After adsorption, the nanocomposite was filtered and regen-
erated using 0.3 M NaOH. The regenerated nanocomposite was fur-
ther used for second and third runs. The regeneration efficiency
was calculated using Eq. (2)
qe in the second run
Regeneration efficiency (% ) = × 100
qe in the first run
where qe is the equilibrium adsorption capacity.
3. Results and discussion
3.1. Characterization of RGO-MFT nanocomposites
The XRD pattern of TiO2 , Fe2 O3 , meso- Fe2 O3 /TiO2 and RGO-
MFT are shown in Fig. 1. The XRD pattern of TiO2 matched well
with anatase phase reported in the literature [38]. The patterns of
Fe2 O3 revealed formation of α -phase of Fe2 O3 [39]. Both TiO2 and
Fe2 O3 are free from amorphous phase. The XRD patterns of meso-
Fe2 O3 /TiO2 showed the characteristic patterns of TiO2 and Fe2 O3 .
In addition, there were new peaks assigned to rutile phase of tita-
nia [38]. Based on the broadening of the peaks it was established
the low crystallinity of the material. The RGO (Fig. 2) showed a
broad peak at 24.2° (2θ ) which is the characteristic peak for re-
duced graphene oxide [35].The patterns of RGO-MFT showed all
the peaks corresponding to meso- Fe2 O3 /TiO2 . As the pattern of
RGO was not observed in the XRD, the entire RGO might be com-
(2) pletely covered with Fe2 O3 and TiO2 . Since the composite con-
tained only 5% of reduced graphene oxide, it could be presumed
that it was completely covered with Fe2 O3 and TiO2 . The average
grain size of Fe2 O3 /TiO2 and Fe2 O3 /TiO2 in composites was calcu-
lated using Scherrer equation and it was found to be in the range
of 20–45 nm. The inset figure showed the low angle XRD patterns
of meso-Fe2 O3 /TiO2 (Fig. 2). The intense peak at 0.5° (2θ ) evidently
proved the formation of orderly arranged mesopores.
The FT-IR spectra of GO, RGO, meso-Fe2 O3 /TiO2 and RGO-MFT
are shown in Fig. 3. The spectrum of GO showed an intense broad
peak in the high energy region due to –OH stretching of alcoholic,
water and –COOH groups. The broadening was due to hydrogen

Please cite this article as: C.M. Babu et al., Characterization of reduced graphene oxide supported mesoporous Fe2 O3 /TiO2 nanopar-
ticles and adsorption of As(III) and As(V) from potable water, Journal of the Taiwan Institute of Chemical Engineers (2016),
http://dx.doi.org/10.1016/j.jtice.2016.02.005
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disorders present in the carbonaceous materials. All the three spec-

(D band)
(G band) tra showed peaks at 1350 and 1590 cm−1 which correspond to D
and G bands of graphene. The D band represented the structural
(c)
defects of sp3 carbon and breathing mode κ -point phonons of A1g
symmetry. The G band represented the first-order scattering of E2g
mode for sp2 carbon [38]. The intensity ratio of D and G bands was
Intensity (a.u.)

used to measure the defects and disorder present in the graphene

1000 1200 1400 1600
-1
Wavenumber (cm )
Fig. 4. Raman spectra of (a) GO, (b) RGO and (c) RGO-MFT.
bonding of such groups. The C = C and carbonyl stretching vibra-
tions were observed from the peaks at 1575 and 1725 cm−1 respec-
tively. The peaks at 1026 and 1175 cm−1 are assigned to alkoxy C–O
and epoxy C–O stretching vibrations respectively. The FT-IR spec-
trum of RGO showed a drastic reduction in the intensity of all the
peaks. The –OH stretching vibration was almost lost. The peaks
due to epoxy C–O, alkoxy C–O and C = O showed significant re-
duction in intensity, thus confirmed the reduction of GO. The FT-IR
spectrum of meso- Fe2 O3 /TiO2 showed peaks below 750 cm−1 due
to M–O vibrations [16]. The FT-IR spectrum of RGO-MFT showed
the characteristic peaks of M–O vibrations below 700 cm−1 . The
FT-IR spectrum of adsorbate and adsorbent are shown in Fig. S1.
The peak around 834 cm−1 was assigned to (As–O) arsenate vibra-
tion [16]. This peak was absent in the FT-IR spectrum of RGO-MFT.
Hence IR spectrum also supported adsorption of arsenate on the
adsorbent.
The Raman spectra of GO, RGO and RGO-MFT are shown in
Fig. 4. The Raman spectra established the structural defects and
oxide and reduced graphene oxide. The intensity ratio of GO (0.73)
(b) was less than RGO (1.1), which clearly revealed the sp3 defects in
RGO due to reduction of graphene oxide. The intensity ratio (ID/IG)
of RGO-MFT (1.23) is higher than RGO. This is attributed to the in-
teraction between nanoparticles and reduced graphene oxide.
(a) The SEM image of meso-Fe2 O3 /TiO2 is shown in Fig. 5a. The im-
age did not exhibit any distinct morphology. The particles were of
different sizes. The SEM image of GO (Fig. 5b) showed the stack-
ing of many sheets into layer like structure. The SEM image of
1800 2000
RGO (Fig. 5c) also showed the pealing of graphene oxide layer
into wrinkled and crumpled sheets. The RGO-MFT (Fig. 5d) showed
complete covering of RGO-MFT with meso- Fe2 O3 /TiO2 .
The TEM image of meso-Fe2 O3 /TiO2 is shown in Fig. 6a. There
were tiny particles of nearly uniform size. The black particles
were due to Fe2 O3 and others due to TiO2 . The particles were
well separated without much agglomeration. The TEM image of
reduced graphene oxide sheets is shown in Fig. 6b. The sheets
were folded as seen in the image. The TEM image of RGO sup-
ported meso- Fe2 O3 /TiO2 showed tiny particles of metal oxide as
shown in Fig. 6c. The particles were well pulverized by sonication
and subsequently supported on reduced graphene oxide. The TEM
image of RGO-MFT at high magnification is shown in Fig. 6d.
The size of the Fe2 O3 /TiO2 and Fe2 O3 /TiO2 in composites was
found to be 20–50 nm. The appearance indicated intercalation of
Fe2 O3 /TiO2 in between the reduced graphene oxide sheets. The
diffraction pattern of SAED analysis showed the amorphous nature
of reduced graphene and crystalline nature of RGO-MFT due to the
presence of Fe2 O3 /TiO2 (Fig. 6e and f).
The N2 adsorption isotherms of RGO, meso-Fe2 O3 /TiO2 and
RGO-MFT are shown in Fig. 7. The surface area, pore volume
and pore diameter are presented in Table 1. The isotherm of
Fe2 O3 /TiO2 showed hysteresis loop in the relative pressure

Fig. 5. SEM images of (a) meso- Fe2 O3 /TiO2 , (b) GO, (c) RGO and (d) RGO-MFT.

Please cite this article as: C.M. Babu et al., Characterization of reduced graphene oxide supported mesoporous Fe2 O3 /TiO2 nanopar-
ticles and adsorption of As(III) and As(V) from potable water, Journal of the Taiwan Institute of Chemical Engineers (2016),
http://dx.doi.org/10.1016/j.jtice.2016.02.005
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Fig. 6. TEM images of (a) meso-Fe2 O3 /TiO2 , (b) RGO, (c and d) RGO-MFT, (e) SAED of RGO and (f) SAED of RGO-MFT.

Table 1
Textural parameters of Fe2 O3 /TiO2 , RGO and RGO-MFT.

Adsorbent Specific surface area (m2 /g) Pore volume (cm3 /g) Pore diameter (nm)

Fe2 O3 /TiO2 155.35 0.2866 16.876

RGO 315.24 0.6123 4.657
RGO-MFT 275.23 0.5231 12.235

100 (c)

90 (b)
Volume of N2 adsorbed (cm /g)

(a)
3

80
Weight loss (%)

(d)
70

60
(b)
50

40 (a)

30

20

10
(c)
100 200 300 400 500 600 700
O
0.0 0.2 0.4 0.6 0.8 1.0 Temperature ( C)
Relative pressure (p/p0) Fig. 8. TGA curves of (a) GO, (b) RGO, (c) meso- Fe2 O3 /TiO2 and (d) RGO-MFT.

Fig. 7. N2 sorption isotherms of (a) RGO, (b) meso- Fe2 O3 /TiO2 and (c) RGO-MFT.
between 0.8 and 1, due to condensation of nitrogen inside the
mesopores. The pore diameter of meso-Fe2 O3 /TiO2 confirmed
the presence of mesopores, which was also evident in the XRD
pattern. The surface area of meso-Fe2 O3 /TiO2 was lower than RGO
and nanocomposites. The pore diameter of meso-Fe2 O3 /TiO2 was
higher than that of nanocomposites. The pore diameter of RGO
was found to be 4.6 nm. The origin of pores in reduced graphene
oxide might be due to folding of graphene sheets. RGO supported
meso-Fe2 O3 /TiO2 also showed pore diameter of 12.23 nm. Hence,
the pores of Fe2 O3 /TiO2 might contribute more to pore diameter
rather than RGO itself. Though the pore diameter of supported
metal oxide was higher than RGO, pore volume of RGO and RGO-
MFT was almost similar. Hence number of pores per cm2 in RGO
might be higher than RGO-MFT. The surface area of RGO-MFT was

Please cite this article as: C.M. Babu et al., Characterization of reduced graphene oxide supported mesoporous Fe2 O3 /TiO2 nanopar-
ticles and adsorption of As(III) and As(V) from potable water, Journal of the Taiwan Institute of Chemical Engineers (2016),
http://dx.doi.org/10.1016/j.jtice.2016.02.005
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a O 1s b C 1s
Fe 2p O KLL

C 1s C-C, C=C

Intensity (a.u.)
Intensity (a.u.)

Ti 2s
Ti 2p

C-O-C, C-OH
Ti 3s
Ti 3p
O 2s

C=O

0 200 400 600 800 1000 282 284 286 288 290
Binding Energy (eV) Binding Energy (eV)

c Fe 2p 3/2 Fe 2p 1/2 d

Ti 2p 3/2
Intensity (a.u.)

Intensity (a.u.)
Ti 2p 1/2

710 715 720 725 730 735 740 455 460 465 470
Binding Energy (eV) Binding Energy (eV)

e
Intensity (a.u.)

-
O2

-OH
C-O

526 528 530 532 534 536

Binding Energy (eV)

Fig. 9. XPS spectrum of RGO-MFT (a) survey spectrum, (b) C 1s spectrum, (c) Fe 2p spectrum, (d) Ti 2p spectrum and (e) O 1s spectrum.

lower than that of RGO due to substitution of light graphene by RGO-MFT showed a gradual decrease in weight from 150 to 750 °C.
heavy metal oxide. As there was no weight loss below 150 °C, there might not be any
The results of thermogravimetric analysis of GO, RGO, meso- free water on the surface of the material. However, the metal oxide
Fe2 O3 /TiO2 and RGO-MFT are shown in Fig. 8. The thermogram chemisorbed water yielded weight loss above 200 °C due to dehy-
of GO showed a major weight loss from 50 to 300 °C. It is as- dration. The presence of –OH groups (3400 cm−1 ) was also evident
signed to loss of water between 50 and 150 °C, and decompo- in the FT-IR spectrum of RGO supported metal oxide (Fig. 2)
sition of functional groups between 150 and 300 °C. The weight The XPS survey spectrum of RGO-MFT is shown in Fig. 9a. The
loss was not significant above 300 °C and hence the final material characteristic peaks for C, Ti, Fe and O at their respective binding
might contain only very few functional groups. The thermogram energy were observed in the spectrum. The XPS spectrum of O 1 s
of meso-Fe2 O3 /TiO2 showed very slight change in weight with in- of RGO-MFT is shown in Fig. 9e. Deconvolution of the broad peak
crease in temperature, which may be attributed to dehydration of showed three overlapping peaks corresponding to O2− , –OH and
OH groups. The thermogram of RGO showed a slight decrease in C–O at 530.1, 530.9 and 532.3 eV respectively. The peak due to –
weight from 200 to 500 °C and hence there might be some resid- OH was broadened due to entry of Fe3+ in to the lattice of TiO2 .
ual –OH groups in it. The weight loss was also high above 500 °C The content of defective OH groups might be high on the external
due to decomposition of distinct OH groups. The thermogram of surface, as Fe3+ could be better inserted on the external surface

Please cite this article as: C.M. Babu et al., Characterization of reduced graphene oxide supported mesoporous Fe2 O3 /TiO2 nanopar-
ticles and adsorption of As(III) and As(V) from potable water, Journal of the Taiwan Institute of Chemical Engineers (2016),
http://dx.doi.org/10.1016/j.jtice.2016.02.005
JID: JTICE
ARTICLE IN PRESS [m5G;February 23, 2016;15:23]

C.M. Babu et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2016) 1–10 7

Table 2

E q u ilib riu m ad so rp tio n cap acity (m g /g )

Langmuir and Freundlich adsorption
isotherm constants for As(III) and As(V) 100
on RGO-MFT. As(V)
As(III)
RGO-MFT
80
As(III) As(V)

Langmuir
qmax (mg/g) 77.76 99.5
60
b (L/mg) 0.4727 0.4866
R2 0.98605 0.9913
Freundlich
Kf 30.20 32.8722 40
n 4.5 3.6337
R2 0.9649 0.9662

20
rather than in the bulk of TiO2 lattices. The –OH groups might also
be present even on free TiO2 but their content was very minimum 0 10 20 30 40 50 60 70
as the peak due to –OH was not split in the spectrum.
The C1s spectrum of RGO-MFT is shown in Fig. 9b. The peaks Equilibrium concentration (mg/L)
due to C–C and C = C were very much intense, but the peaks Fig. 10. Equilibrium adsorption isotherms of As(III) and As(V) on RGO-MFT at 30 °C.
due to C–O–C, C = O and COOH were very minimal, thus support- Adsorbate concentration (3–80 mg/L), adsorbent dose 0.2 g/L, contact time 3 h, pH 7
ing the reduction of GO into RGO [38]. The peaks due to TiO2 are for As(III) and pH 6 for As(V).
shown in Fig. 9d. The peaks due to Ti 2p3/2 were more intense than
Ti 2p1/2 due to higher j value of the former than the later.
The XPS spectrum of iron below 710 and 740 eV are shown in Freundlich isotherm model suggested that the adsorption ca-
Fig. 9c. The presence of free Fe2 O3 was established based on the pacity occurred on different adsorption sites on the adsorbent, and
major peaks of Fe 2p3/2 and Fe 2p1/2 . Broadening of both peaks did not depend on the formation of monolayer. The linear expres-
could be attributed to bonding of some of the iron sites with tita- sion of Freundlich isotherm is as follows
nium via oxygen. In addition, the defective Fe sites carrying –OH 1
groups might also contribute to the broadening. log qe = log K f + log Ce (2)
n

3.2. Adsorption isotherms
Equilibrium adsorption studies of As(III) and As(V) on RGO-MFT
were performed to obtain adsorption capacity of RGO-MFT and
the results are depicted in Fig. 10. The experimental adsorption
data were fitted with Langmuir and Freundlich isotherms [40]. The
Langmuir isotherm suggested monolayer coverage of adsorbate on
heterogeneous adsorbent surface. The linear expression of Lang-
muir isotherm is
Ce 1 Ce
= +
qe qmax b qmax
From the Eq. (1), qmax and b can be determined experimentally by
plotting Ce versus Ce /qe (Fig. S2), where qe is the equilibrium ad-
sorption capacity, Ce is the equilibrium concentration of metal ion
(mg/L) in solution, qmax is the maximum adsorption capacity and
b the Langmuir constant.
From Eq. (2), Kf and 1/n were determined experimentally by plot-
ting log qe versus log Ce (Fig. S3), where qe is the equilibrium ad-
sorption capacity, Ce is the equilibrium concentration of metal ion
(mg/L) in solution, and n and Kf are Freundlich constants. The pa-
rameters of Langmuir and Freundlich isotherm models are given in
Table 2. The comparison of the linear correlation coefficients (r2 ) of
both isotherms, Langmuir isotherm found to fit well compared to
Freundlich isotherm for both As(III) and As(V). The maximum ad-
sorption capacity of RGO-MFT was 99.05 and 77.76 mg/g for As(V)
and As(III) respectively. Bare mesoporous Fe2 O3 /TiO2 showed max-
(1) imum adsorption capacity of 83.45 and 69.83 mg/g, after load-
ing over reduced graphene oxide the adsorption capacity was in-
creased. The adsorption behaviour of RGO-MFT for As(III) and As(V)
depended on monolayer adsorption.
The adsorption capacity of RGO-MFT with other adsorbent is
presented in Table 3. Some of the metal oxides loaded over cel-
lulose, CNT, reduced graphene oxide and polycaprolactone showed

Table 3
Comparison of the As(III) and As(V) adsorption characteristics with respect to the pH, Langmiur adsorption capacity and pseudo-second order rate constant of
reported adsorbents and RGO-MFT.

Adsorbents pH qmax (mg/g)Langmiur Pseudo-second order Rate Constant (k2 )(g/mg min) Reference

As(III) As(V) As(III) As(V) As(III) As(V)

Cellulose @ Fe2 O3 7 7 23.16 32.11 – – [1]

Ce–Fe Oxide- CNTs 7.5 4 28.74 30.96 0.0 0 05 0.0017 [24]
α -Fe2 O3 nanowire/Diatomite 3.5 3.5 60.6 81.2 – – [41]
CeO2 –Fe3 O4 polycaprolactone (MC2) 7 7 32 28 0.008 0.003 [42]
Mesoporous γ -Fe2 O3 – 7 – 73.2 – – [43]
Mesoporous Al2 O3 – 6.6 36.6 – 0.0034 [18]
Mesoporous MnFe2 O4 7 – 17.8 – 0.002 – [20]
Copper oxide incorporated mesoporous Al2 O3 6.5-7.2 6.5-7.2 2.161 2.017 0.011 0.404 [44]
Hydrous cerium oxide–graphene composites – 4 – 62.33 – 1.019 [45]
Fe3 O4 –GO (MGO) – 6.5 – 59.6 – 0.05 [33]
FeMnOx /RGO 7 7 22.42 22.22 0.007 0.015 [46]
Meso-Fe2 O3 / TiO2 -RGO (RGO-MFT) 7 6 77.76 99.5 0.005 0.006 This study

Please cite this article as: C.M. Babu et al., Characterization of reduced graphene oxide supported mesoporous Fe2 O3 /TiO2 nanopar-
ticles and adsorption of As(III) and As(V) from potable water, Journal of the Taiwan Institute of Chemical Engineers (2016),
http://dx.doi.org/10.1016/j.jtice.2016.02.005
JID: JTICE
8 C.M. Babu et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2016) 1–10
70
E q u ilib riu m ad so p tio n cap acity (m g /g )
60
50
40
30
20
10
0 20
Fig. 11. Adsorption kinetics of As(III) and As(V) on RGO-MFT at 30 °C. Adsorbate
concentration (20 mg/L), adsorbent dose 0.2 g/L, contact time 2 h, pH 7 for As(III)
and pH 6 for As(V).
Table 4
Pseudo-second order kinetic parameters for As(III) and As(V) on
RGO-MFT.
Oxidation state Pseudo-second order model
k2
As(III) 0.005
As(V) 0.006
lower adsorption capacity for both As(III) and As(V). Cerium
oxide–graphene nanocomposites and iron oxide–graphene oxide
nanocomposites showed maximum adsorption capacity of 62.33
and 59.6 mg/g for As(V) only. Mesoporous metal oxides such as
Al2 O3 , MnFe2 O4 and copper oxide incorporated Al2 O3 showed
lower adsorption, but γ -Fe2 O3 showed high adsorption for As(V)
only and not for As(III). α - Fe2 O3 supported over diatomite have
high adsorption capacity for both As(III) and As(V), but the adsorp-
tion was high in pH 3.5. In the present study RGO-MFT showed
high adsorption for As(III) at neutral pH and for As(V) at pH 6.
Hence RGO-MFT can be a competitive adsorbent for both As(III)
and As(V) from potable water.
3.3. Adsorption kinetics
The adsorption kinetics of As(III) and As(V) on RGO-MFT are
shown in Fig. 11. The adsorption equilibrium established within
15 min for both As(III) and As(V). The results obtained from the
experiments were well fitted with pseudo-second order kinetic
model with a correlation coefficient of 0.99 (Table 4). The linear
form [40] of the model is given in Eq. (3).
t 1 1 As(III). The adsorbent was found to be better for adsorption of
= + t (3)
qt k2 qe 2 qe
From Eq. (3), qe and k2 were determined experimentally by plot-
ting t versus t/qt (Fig. S4), where qe and qt are the equilibrium
adsorption capacity (mg/g) and equilibrium adsorption capacity
(mg/g) at time t respectively, and k2 is the rate constant for pseudo
second order adsorption (g/mg min). The equilibrium concentra-
tion for As(III) and As(V) calculated from pseudo-second order ki-
netic model was found to be nearly equal to equilibrium concen-
tration (qe ) obtained from the experimental data.
Please cite this article as: C.M. Babu et al., Characterization of reduced graphene oxide supported mesoporous Fe2 O3 /TiO2 nanopar-
ticles and adsorption of As(III) and As(V) from potable water, Journal of the Taiwan Institute of Chemical Engineers (2016),
http://dx.doi.org/10.1016/j.jtice.2016.02.005
ARTICLE IN PRESS [m5G;February 23, 2016;15:23]
80
Equilibrium adsorption capacity (mg/g)
As(V)
70 As(III)
As(V)
60
50
As(III)
40
30
20
10
0
40 60 80 100 120 2 3 4 5 6 7 8 9 10
Time (min) pH
Fig. 12. Effect of pH on the removal of As(III) and As(V) using RGO-MFT: concen-
tration 20 mg/L, temperature 30 °C, adsorbent 0.2 g/L and contact time 3 h.
3.4. Effect of pH
The results of the influence of pH on the adsorption capacity
of RGO-MFT for the sorption of As(III) and As(V) are illustrated in
Fig. 12. In the sorption of As(III) the adsorption capacity increased
qeq (mg/g) (calculated) R2 with increase of pH until 7 and above which it decreased. Since
50.25 0.999
pKa1 of As(III) is equal to 9.23, the arsenious acid remained undis-
66.53 0.999 sociated below pH 9.23. Since the point of zero charge of RGO-MFT
is 5.8, the surface was positive at low pHs and above pH 6 the
surface was negative. Irrespective of the charge on the surface of
RGO-MFT, it was expected to increase adsorption with increase of
pH. In line with our view the adsorption capacity increased from
pH 3 to 7 and above 7 it decreased. Since the surface of RGO-MFT
nanocomposites was negative and As(III) was also partially disso-
ciated above pH 7, the adsorption capacity decreased beyond pH 7.
Since both RGO-MFT and As(III) are negative, adsorption decreased
with the increase in pH above 7. As expected, the adsorption was
very low around pH 9.23. So, the point of zero charge and dis-
sociation constant of As(III) were found to control the adsorption
capacity of the adsorbent.
The adsorption capacity towards As(V) showed an increase in
adsorption from pH 3 to 4, followed by a decrease at pH 10. The
increased adsorption capacity at lower pH was due to the effect
of point of zero charge of RGO-MFT (5.8). Since the point of zero
charge RGO-MFT is 6, at lower pHs the surface was positively
charged and As(V) present in the state of first dissociation, the
columbic interaction between them enhanced the adsorption. Close
to pH 6 and above, the adsorption decreased as the surface of ti-
tania and As(V) were negatively charged and repelled each other.
Adsorption of As(V) was also influenced by point of zero charge
of RGO-MFT and dissociation constant of As(V). The comparison of
adsorption of As(V) and As(III) over RGO-MFT showed higher de-
crease of adsorption capacity at above (pH 6) As(V) and (pH 7)
As(V) than As(III) at pHs below the point of zero charge of RGO-
MFT.
3.5. Effect of interfering anions
The effect of interfering anions such as sulphate, phosphate,
nitrate, chloride and fluoride on the adsorption of arsenate and
arsenite over RGO-MFT was examined at pH 6. The results are
depicted in Fig. S5. The results revealed that the presence of
phosphate showed strong interference for the adsorption of As(V)
JID: JTICE
ARTICLE IN PRESS
C.M. Babu et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2016) 1–10
100 As(V)
As(III)
Regeneration efficiency (%)
80
60
40
20
0 Korean Government.
1 2 3 4
Number of Cycles
Fig. 13. Regeneration efficiency for the removal of As(III) and As(V) on RGO-MFT at
pH 7: concentration 20 mg/l, temperature 30 °C, adsorbent 0.2 g/L and contact time
24 h.
and As(III) at a concentration of 20 ppm. Since the pKa of As(V)
(pka1 = 2.3, pka2 = 6.97 and pka3 = 11.53) was close to that of phos-
phate (pka1 = 2.15, pka2 = 7.20 and pka3 = 12.37), the interference
of phosphate was significant. Since As(V) and phosphate possess
uninegative charge, the adsorption capacity for As(V) and phos-
phate did not differ for both. As a result the adsorption capac-
ity of the sorbent for As(V) in the presence of phosphate was re-
duced slightly. The adsorption of As(III) with pKa (pka1 = 2.15 and
pka2 = 7.20) was strongly reduced by phosphate. Since its second
dissociation was partially completed, it could not compete with
phosphate. So the adsorption was very much interfered by the
presence of phosphate. Since sulphate, nitrate and chloride ions
of Fe3+ are soluble, their interference for adsorption of As(V) and
As(III) was not significant. Similarly the interference of fluoride ion
was also not significant on the adsorption of As(III) and As(V). The
order of interfering anions for As(III) and As(V) follows phosphate
> sulphate > nitrate > chloride > fluoride.
3.6. Regeneration and stability of adsorbent
The regeneration efficiency of adsorbent was examined in order
to confirm its recyclability. The used RGO-MFT adsorbent (0.2 g)
was stirred with 10 ml 0.3 M NaOH solution in a 100 ml beaker and
then it was filtered through a Whatman filter paper. The residue
was washed thrice with NaOH solution, distilled water and dried
in an oven at 50 °C for 12 h for regeneration. The dried residue was
again tested for adsorption of As(V) and As(III). The same proce-
dure was repeated for 4 cycles. The plot of regeneration efficiency
as a function of cycles is shown in Fig. 13. The adsorption capac-
ity decreased by 7–8 % in the first regeneration efficiency, and in
further three cycles showed less than 3% decrease in adsorption ca-
pacity. Hence the same adsorbent can be recycled for the sorption
of As(III) and As(V) without loss. Though NaOH solution could neu-
tralize surface defective –OH groups on metallic oxide, they were
regenerated when they were finally washed with water. Hence the
same adsorption characteristics were retained in all the cycles.
4. Conclusion
The RGO was found to be a good support for meso-Fe2 O3 /TiO2 .
RGO showed a finely divided dispersion of metal oxides on the
surface. Such dispersion is important to enhance active adsorption
Please cite this article as: C.M. Babu et al., Characterization of reduced graphene oxide supported mesoporous Fe2 O3 /TiO2 nanopar-
ticles and adsorption of As(III) and As(V) from potable water, Journal of the Taiwan Institute of Chemical Engineers (2016),
http://dx.doi.org/10.1016/j.jtice.2016.02.005
[m5G;February 23, 2016;15:23]
9
sites on the surface of the metal oxides. The pH of the solution
influenced the adsorption capacity of RGO-MFT. The influence of
point of zero charge of RGO-MFT on the adsorption of As(III) and
As(V) revealed that adsorption at pH 6 was found to be better than
at higher pHs. Among the ions such as phosphate, sulphate, nitrate,
chloride and fluoride, phosphate significantly interfered in the ad-
sorption of arsenite rather than arsenate. So it is concluded that if
the pH was brought close to 7, As(III) existed as negative, and the
interference of phosphate will be less. Hence the effect of phos-
phate interference could be minimal, if pH 6 is kept for adsorption
of arsenate and pH 7 for arsenite.
Acknowledgement
This work was supported by grants from Korea CCS R&D Centre,
funded by the Ministry of Education, Science and Technology of the
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.jtice.2016.02.005.
References
[1] Yu X, Tong S, Ge M, Zuo J, Cao C, Song W. One-step synthesis of magnetic
composites of cellulose@iron oxide nanoparticles for arsenic removal. J Mater
Chem A 2013;1:959–65.
[2] Caporale AG, Pigna M, Azam SMGG, Sommella A, Rao MA, Violante A. Effect
of competing ligands on the sorption/desorption of arsenite on/from Mg–Fe
layered double hydroxides (Mg–Fe-LDH). Chem Eng J 2013;225:704–9.
[3] Tang W, Su Y, Li Q, Gao S, Shang J. Mg-doping: a facile approach to impart
enhanced arsenic adsorption performance and easy magnetic separation capa-
bility to a-Fe2 O3 nanoadsorbents. J Mater Chem A 2013;1:830–6.
[4] Basu T, Nandi D, Sen P, Ghosh UC. Equilibrium modeling of As(III,V) sorp-
tion in the absence/presence of some groundwater occurring ions by iron(III)–
cerium(IV) oxide nanoparticle agglomerates: a mechanistic approach of surface
interaction. Chem Eng J 2013;228:665–78.
[5] Glocheux Y, Pasarin MM, Albadarin AB, Allen SJ, Walker GM. Removal of ar-
senic from groundwater by adsorption onto an acidified laterite by-product.
Chem Eng J 2013;228:565–74.
[6] Rengaraj S, Moon SH, Sivabalan R, Arabindoo B, Murugesan V. Removal of phe-
nol from aqueous solution and resin manufacturing industry wastewater using
an agricultural waste: rubber seed coat. J Hazard Mater 2002;B89:185–96.
[7] Zhao Y, Huang M, Wu W, Jin W. Synthesis of the cotton cellulose based Fe(III)-
loaded adsorbent for arsenic(V) removal from drinking water. Desalination
20 09;249:10 06–11.
[8] Akin I, Arslan G, Tor A, Cengeloglu Y, Ersoz M. Removal of arsenate [As(V)] and
arsenite [As(III)] from water by SWHR and BW-30 reverse osmosis. Desalina-
tion 2011;281:88–92.
[9] Luo X, Wang C, Wanga L, Deng F, Luo S, Tu X, et al. Nanocomposites of
graphene oxide-hydrated zirconium oxide for simultaneous removal of As(III)
and As(V) from water. Chem Eng J 2013;220:98–106.
[10] Pillay K, Cukrowska EM, Coville NJ. Multi-walled carbon nanotubes as adsor-
bents for the removal of parts per billion levels of hexavalent chromium from
aqueous solution. J Hazard Mater 2009;166:1067–75.
[11] Maliyekkal SM, Anshup AKR, Pradeep T. High yield combustion synthesis
of nanomagnesia and its application for fluoride removal. Sci Total Environ
2010;408:2273–82.
[12] Parsons JG, Lopez ML, Peralta-Videa JR, Gardea-Torresdey JL. Determination
of arsenic(III) and arsenic(V) binding to microwave assisted hydrothermal
synthetically prepared Fe3 O4 , Mn3 O4 , MnFe2 O4 nanoadsorbents. Microchem J
20 09;91:10 0–6.
[13] Du Y, Fan H, Wang L, Wang J, Wu J, Dai H. α -Fe2 O3 nanowires deposited di-
atomite: highly efficient absorbents for the removal of arsenic.. J Mater Chem
A 2013;1:7729–37.
[14] Hristovski K, Westerhoff P, Crittenden J. An approach for evaluating nanomate-
rials for use as packed bed adsorber media: a case study of arsenate removal
by titanate nanofibers. J Hazard Mater 2008;156:604–11.
[15] Xu W, Wang J, Wang L, Sheng G, Liu J, Yu H, et al. Enhanced arsenic removal
from water by hierarchically porous CeO2 -ZrO2 nanospheres: role of surface-
and structure-dependent properties. J Hazard Mater 2013;260:498–507.
[16] Zhang Y, Yang M, Dou XM, He H, Wang DS. Arsenate adsorption on an Fe-
Ce bimetal oxide adsorbent: role of surface properties. Environ Sci Technol
2005;39:7246–53.
[17] Wu Z, Zhao D. Ordered mesoporous materials as adsorbents. Chem Commun
2011;47:3332–8.
[18] Han C, Li H, Pu H, Yu H, Deng L, Huang S, et al. Synthesis and characterization
of mesoporous alumina and their performances for removing arsenic(V). Chem
Eng J 2013;217:1–9.
JID: JTICE
ARTICLE IN PRESS
10 C.M. Babu et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2016) 1–10
[19] Zhi B, Ding H, Wang D, Cao Y, Zhang Y, Wang X, et al. Ordered mesoporous
MnO2 as synergetic adsorbent for effective arsenic(III) removal. J Mater Chem
A 2014;2:2374–82.
[20] Xu WH, Wang L, Wang J, Sheng GP, Liu JH, Yu HQ, et al. Superparamagnetic
mesoporous ferrite nanocrystal clusters for efficient removal of arsenite from
water. Cryst Eng Commun 2013;15:7895–903.
[21] Choi J, Ide A, Truong YB, Kyratzis IL, Caruso RA. High surface area mesoporous
titanium–zirconium oxide nanofibrous web: a heavy metal ion adsorbent. J
Mater Chem A 2013;1:5847–53.
[22] Li F. Layer-by-layer loading iron onto mesoporous silica surfaces: synthesis,
characterization and application for As(V) removal. Micropor Mesopor Mat
2013;171:139–46.
[23] Ma J, Zhu Z, Chen B, Yang M, Zhou H, Li C, et al. One-pot, large-scale synthe-
sis of magnetic activated carbon nanotubes and their applications for arsenic
removal. J Mater Chem. A 2013;1:4662–6.
[24] Chen B, Zhu Z, Ma J, Qiu Y, Chen J. Surfactant assisted Ce–Fe mixed oxide deco-
rated multiwalled carbon nanotubes and their arsenic adsorption performance.
J. Mater. Chem A 2013;1:11355–67.
[25] Mahanta N, Chen JP. A novel route to the engineering of zirconium immo-
bilized nano-scale carbon for arsenate removal from water. J Mater Chem A
2013;1:8636–44.
[26] Gan T, Sun J, Huang K, Song L, Li Y. A graphene oxide–mesoporous MnO2
nanocomposite modified glassy carbon electrode as a novel and efficient
voltammetric sensor for simultaneous determination of hydroquinone and cat-
echol. Sensor Actuat B 2013;177:412–18.
[27] Zhuo L, Wu Y, Wang L, Ming J, Yu Y, Zhang X, et al. CO2 –expanded ethanol
chemical synthesis of aFe3 O4 @graphene composite and its good electro-
chemical properties as anode material for Li-ion batteries. J Mater Chem A
2013;1:3954–60.
[28] Guo S, Zhang G, Guo Y, Yu JC. Graphene oxide-Fe2 O3 hybrid material as highly
efficient heterogeneous catalyst for degradation of organic contaminants. Car-
bon 2013;60:437–44.
[29] Farghali AA, Bahgat M, El Rouby WMA, Khedr MH. Preparation, decoration
and characterization of graphene sheets for methyl green adsorption. J Alloy
Compd 2013;555:193–200.
[30] Upadhyay RK, Soin N, Roy SS. Role of graphene/metal oxide composites as pho-
tocatalysts, adsorbents and disinfectants in water treatment: a review. RSC Adv
2014;4:3823–51.
[31] Yang SJ, Kang JH, Jung H, Kim T, Park CR. Preparation of a freestanding, macro-
porous reduced graphene oxide film as an efficient and recyclable sorbent for
oils and organic solvents. J Mater Chem A 2013;1:9427–32.
[32] Zhang W, Shi X, Zhang Y, Gu W, Li B, Xian Y. Synthesis of water-soluble mag-
netic graphene nanocomposites for recyclable removal of heavy metal ions. J
Mater Chem A 2013;1:1745–53.
Please cite this article as: C.M. Babu et al., Characterization of reduced graphene oxide supported mesoporous Fe2 O3 /TiO2 nanopar-
ticles and adsorption of As(III) and As(V) from potable water, Journal of the Taiwan Institute of Chemical Engineers (2016),
http://dx.doi.org/10.1016/j.jtice.2016.02.005
[m5G;February 23, 2016;15:23]
[33] Sheng G, Li Y, Yang X, Ren X, Yang S, Hu J, et al. Efficient removal of arsenate
by versatile magnetic graphene oxide Composites. RSC Adv 2012;2:12400–7.
[34] Chandra V, Park J, Chun Y, Lee JW, Hwang IC, Kim KS. Water-dispersible
magnetite-reduced graphene oxide composites for arsenic removal. ACS Nano
2010;4:3979–86.
[35] Mahmood T, Din SU, Naeem A, Mustafa S, Waseem M, Hamayun M. Adsorption
of arsenate from aqueous solution on binary mixed oxide of iron and silicon.
Chem Eng J 2012;192:90–8.
[36] Palanisamy B, Babu CM, Sundaravel B, Anandan S, Murugesan V. Sol–gel syn-
thesis of mesoporous mixed Fe2 O3 /TiO2 photocatalyst: application for degra-
dation of 4-chlorophenol. J Hazard Mater 2013;252-253:233–42.
[37] Wu Y, Zhou M, Zhang B, Wu B, Li J, Qiao J, et al. Amino acid assisted tem-
plating synthesis of hierarchical zeolitic imidazolate framework-8 for efficient
arsenate removal. Nanoscale 2014;6:1105–12.
[38] Wang P, Wang J, Wang X, Yua H, Yu J, Lei M, et al. One-step synthesis of
easy-recycling TiO2 -rGO nanocomposite photocatalysts with enhanced photo-
catalytic activity. Appl Catal B-Environ 2013;132-133:452–9.
[39] Islama MS, Kurawaki J, Kusumoto Y, Abdulla-Al-Mamun M, Bin Mukhlish MZ.
Hydrothermal novel synthesis of neck-structured hyperthermia-suitable mag-
netic (Fe3 O4 , γ -Fe2 O3 and α -Fe2 O3 ) nanoparticles. J Sci Res 2012;4:99–107.
[40] Yu Y, Murthy BN, Shapter JG, Constantopoulos KT, Voelcker NH, Ellis AV. Ben-
zene carboxylic acid derivatized graphene oxide nanosheets on natural zeolites
as effective adsorbents for cationic dye removal. J Hazard Mater 2013;260:330–
8.
[41] Du Y, Fan H, Wang L, Wang J, Wu J, Dai H. α -Fe2 O3 nanowires deposited di-
atomite: highly efficient absorbents for the removal of arsenic. J Mater Chem
A 2013;1:7729–37.
[42] Setyono D, Valiyaveettil S. Multi-metal oxide incorporated microcapsules for
efficient As(III) and As(V) removal from water. RSC Adv 2014;4:53365–73.
[43] Lin YF, Chen JL. Synthesis of mesoporous maghemite (γ -Fe2 O3 ) nanostructures
with enhanced arsenic removal efficiency. RSC Adv 2013;3:15344–9.
[44] Pillewan P, Mukherjee S, Roychowdhury T, Das S, Bansiwal A, Rayalu S. Re-
moval of As(III) and As(V) from water by copper oxide incorporated meso-
porous alumina. J Hazard Mater 2011;186:367–75.
[45] Yu L, Ma Y, Ong CN, Xie J, Liu Y. Rapid adsorption removal of arsenate by
hydrous cerium oxide-graphene composite. RSC Adv 2015;5:64983–90.
[46] Zhu J, Lou Z, Liu Y, Fu R, Baig SA, Xu X. Adsorption behavior and re-
moval mechanism of arsenic on graphene modified by iron–manganese bi-
nary oxide (FeMnOx /RGO) from aqueous solutions. RSC Adv 2015;5:67951–
67961.