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Ekoloji 22, 89, 89-96 (2013)

doi: 10.5053/ekoloji.2013.8911

RESEARCH NOTE

Synthesis, Characterization and, the Heavy Metal


Removal Efficiency of MFe2O4 (M=Ni, Cu)
Nanoparticles
Naim SEZGIN1*, Musa SAHIN2, Arzu YALCIN1, Yuksel KOSEOGLU3,4
1 Istanbul

University, Faculty of Engineering, Department of Environmental Engineering,


34320, Avcilar, Istanbul-TURKEY
2 Istanbul

University, Faculty of Engineering, Department of Chemistry, 34320, Avcilar,


Istanbul-TURKEY
3 Fatih

University, Department of Physics, Buyukcekmece 34500 Istanbul- TURKEY

4 Suleyman Demirel University, Faculty of Engineering and Natural Sciences, AlmatyKAZAKHSTAN


*Corresponding

author: nsezgin@istanbul.edu.tr

Abstract
The purpose of the study described in this paper was to compare the removal of the heavy metals zinc,
nickel, and copper from synthetic wastewater by using nanoparticles of CuFe2O4 and NiFe2O4. The
nanoparticles of nickel and copper ferrite (CuFe2O4 and NiFe2O4) were produced by the PEG assisted
hydrothermal method. The structural and morphological characterizations were determined using XRD,
FT-IR, and SEM. These nanoparticles were dispersed into synthetic wastewater contaminated with zinc,
nickel, and copper. Once they had bound to the heavy metals, they were removed from the water solution
using a strong magnet. The metal concentrations of the filtered samples were determined by using atomic
absorption spectrophotometry (AAS). Then the heavy metal removal efficiencies and adsorption capacities
of the nanoparticles (CuFe2O4 and NiFe2O4) were calculated. The removal efficiencies of Cu(II), Ni(II)
and Zn(II) by using CuFe2O4 nanoparticles was calculated as 83.50%, 98.85%, and 99.80%, respectively.
The removal efficiencies of Cu(II), Ni(II), and Zn(II) by using NiFe2O4 nanoparticles were calculated as
92.55%, 36.56 %, and 99.91%, respectively. The measurements were repeated several times with the same
sample and almost the same results were obtained each time.
Keywords: Adsorption, adsorption capacity, copper ferrite, heavy metal, nanoparticles, nickel ferrite.
MFe2O4 (M=Ni, Cu) Nanopartikllerinin Sentezi, Karakterizasyonu ve Ar Metal Giderim
Verimlilii
zet
Bu makalede anlatlan almann amac sentetik atksulardan inko, nikel ve bakr gibi ar metallerin
giderimini CuFe2O4 ve NiFe2O4 nanopartiklleri kullanarak incelemektir. Nikel ve bakr ferrit
nanopartikller (CuFe2O4 ve NiFe2O4) PEG-destekli hidrotermal metod kullanlarak sentezlenmitir.
Nanopartikllerin yapsal ve morfolojik karakterizasyonu iin XRD, FT-IR ve SEM kullanlmtr.
Karakterize edilen nanopartikller inko, nikel ve bakr ieren sentetik atksuyun ierisine braklmtr. Ar
metallerin nanopartikllerle adsorpsiyonunun ardndan gl bir mknats ile nanopartikller atksudan
ayrlmtr. Szlen atksu ierisindeki ar metal konsantrasyonlar atomik absorpsiyon spektrofotometresi
(AAS) ile belirlenmitir. Daha sonra kullanlan nanopartikllerin (CuFe2O4 ve NiFe2O4) ar metal
giderim verimleri ile adsorpsiyon kapasiteleri hesaplanmtr. CuFe2O4 nanopartiklnn Cu(II), Ni(II) ve
Zn(II) giderim verimleri srasyla %83,50, %98,85 ve %99,80 olarak belirlenmitir. NiFe2O4
nanopartiklnn Cu(II), Ni(II) ve Zn(II) giderim verimleri ise srasyla %92.55, %36.56 ve %99.91 olarak
hesaplanmtr. Deneyler ayn rnekle birok kez tekrar edilmi ve benzer sonular elde edilmitir.
Anahtar Kelimeler: ar metaller, adsorpsiyon, adsorpsiyon kapasitesi, bakr ferrit, nanopartikller, nikel
ferrit.
Sezgin N, Sahin M, Yalcin A, Koseoglu Y (2013) Synthesis, Characterization and, the Heavy Metal Removal
Efficiency of MFe2O4 (M=Ni, Cu) Nanoparticles. Ekoloji 22(89): 89-96.

INTRODUCTION
The removal of heavy metals as a pollutant in
water has been under intense research due to their

potential toxicity which causes heavier exposure for


some organism and the ecology even at very low
concentration. The presence of heavy metals like
Received: 17.01.2013 / Accepted: 14.06.2013

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zinc, nickel, and copper may exhibit toxicity and
carcinogenicity for the human body. Although zinc
and copper are essential in small quantities, the
excess of them is hazardous to the human body
(Mishra and Patel 2009). Copper in even a low
amount causes toxic effects in living cells due to the
fact that copper produces oxygen species which can
damage lipids, nucleic acids, and proteins (Halliwell
and Gutteridge 1992). The excess of nickel may
cause some health problems such as paralysis,
diarrhea, low blood pressure, lung irritation, and
bone defects (Kudesia 1990). The maximum
concentration limits (MCL) for some hazardous
heavy metals, were constituted by the USEPA and
are given in Table 1 (Babel and Kurniawan 2003).
What is needed is materials capable of effective
adsorption. Therefore, it is also very important to
develop some processes to remove heavy metals
from discharged waters as a result of their release by
industry, chemical plants, mining, electroplating,
paints, pesticides, agriculture, combustion of fossil
fuels, and traffic (Ylmaz et al. 2006, Osma et al.
2012). Various techniques currently used for heavy
metal removal from discharged water are physicochemical precipitation (Meunier et al. 2006, Djedidi
et al. 2009), ion exchange (Lacour et al. 2001),
solvent extraction (Li and Chen et al. 2008),
adsorbents (Cokadar et al. 2003, Li and Tang et al.
2008, Shahwan et al. 2010, Goren et al. 2010),
reverse osmosis (Bakalar et al. 2009, Aljendeel
2011), ultrafiltration (Juang and Shiau 2000),
biosorption (leri and Cakir 2006, Senturk and
Buyukgungor 2013), and
electrodialysis
(Dermentzis 2010) along with polymeric structures
like hydrogels (Essawy and Ibrahim 2004, Sezgin
2012). While there are ways to remove heavy metals,
they are expensive and require extensive hardware
and high-pressure pumps that run on electricity.
Nonmaterials recently have been studied for water
and wastewater treatment (Kseolu 2010, Ozmen
et al. 2010, Mahdavi et al. 2013, Mueller et al. 2013).
Nanoparticulate metal oxides are among the most
used nanoparticles (Nowack et al. 2007). The
ferrospinels are interesting sorbents for the removal
of heavy metals contaminants (Dixit and Hering
2003). Ferrospinels have the general formula of
AFe2O4 (where A: Fe, Co, Ni, Zn, etc.) and the unit
cell contains 32 O-atoms in cubic close packing with
8 Td (tetra-hedral) and 16 Oh (octahedral) occupied
sites. When magnetic ferrospinels are made as
90

Sezgin et al.
Table 1. The MCL standards for the most hazardous heavy
metals.

nanoparticles, the smaller particle size and high


surface area enhances its capacity for As removal
(Yavuz et al. 2006). By using NiFe2O4, it obtained a
90 % removal efficiency of arsenic from wastewater
(Koseoglu 2010). In a study by Ozmen at al. (2010),
copper(II) was removed from water by using a
modified Fe3O4. The experimental results showed
that the removal efficiency of copper(II) in the
presences of co-existing ions (Pb(II), Zn(II), Ni(II),
Co(II), Cr(III) etc.) were in the range of 31.6-39.6
%, as a result of the competition with copper(II) for
adsorption. Thus, they found that it was lower than
that (75.3 %) with only the presence of copper(II) in
the solution.
Generally, it is known that heavy metals can be
separated from nanoparticles by desorption in an
inorganic acid or alkaline medium (Afkhami and
Moosavi 2010, Hao et al. 2010, Tang and Lo 2013).
Thus, the heavy metals are recovered and the
nanoparticles can be reused many times for
desorption. It should also be remembered that
desorption of heavy metals from nanoparticles in
strong acid or an alkaline medium may lead to
nanoparticle dissolution (Yantase et al. 2007).
Therefore, a weak acid medium must be used for
desorption.
Nanophase materials with an average grain size
in the range of 1 to 50 nm have attracted research
interest for more than a decade since their physical
properties are quite different from that of their bulk
micron-sized counterparts because of the large
volume fraction of atoms that occupies the grain
boundary area (Gleiter 1989, Koseoglu and Kavas
2008). The surface area of the nanostructured
materials is large as the grain sizes are small. The
increase in the interfacial energy due to defects,
dislocations, and lattice imperfections leads to
changes in various physical properties and hence
one can tailor the materials with specific properties.
Almost 50 % of the atoms reside in the grain
boundary area when the grain size is reduced to less
than 10 nm, whereas, it is only 1-3 % when the grain
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Synthesis, Characterization and, the Heavy Metal Removal...

size is 100 nm (Gleiter 1989, Mutschele and


Kircheim 1987).
In this paper we report the synthesis of copper
and nickel ferrite nanoparticles (CuFe2O4 and
NiFe2O4) by using the polyethylene glycol (PEG)
assisted hydrothermal method and the removal
studies for zinc, copper, and nickel ions from
synthetic wastewater with these spinel ferrite
nanoparticles.
The
experiments
involved
suspending pure samples of uniform-sized nickel
and copper ferrite nanoparticles in water.
MATERIAL AND METHODS
Synthesis of Nanoparticles
The synthesis of the nanoparticles was done by
using the PEG assisted hydrothermal method used
for the synthesis of different ferrite nanoparticles
(Gozuak et al. 2009, Koseoglu et al. 2011, Koseoglu
et al. 2012). All the reagents used in the experiments
were analytically pure and were purchased from
Merck Chemicals Company, and were used without
further purication. To form a clear solution 0.725g
Ni(NO3)26H2O and 2.02g of Fe(NO3)39H2O
were each dissolved in 10 mL of distilled water and
mixed with a magnetic stirrer. These mixtures of
Ni(NO3)26H2O and Fe(NO3)39H2O were
successively dissolved. The reaction molar ratio of
Ni and Fe has to be 1:2. After reaching the proper
ratio, 20 mL of polyethylene glycol (PEG) was
added to the solution and then the solution was
stirred again with a magnetic stirrer until the
reactants were dissolved completely, approximately
30 min. The aim of the PEG addition is to prevent
an increase in the size of the nanoparticles. The pH
of the solution was adjusted to 11.0 by adding 0.2 M
NaOH dropwise during stirring. After continuous
stirring at 400 rpm for half an hour, a homogeneous
solution was obtained. Then the solution was
poured in to a Teflon lined stainless autoclave. The
autoclave was kept at 180C in an oven for 24h and
then cooled to room temperature naturally. The
products were centrifuged and washed several times
with de-ionized water, acetone, and absolute
ethanol. Then the samples were put again in an oven
at 70C to dry. After drying the solid phase samples
were ground in a mortar to make them powder. The
obtained powders were used for all of the
measurements. The same procedure was followed
for the synthesis of CuFe2O4 nanoparticles by
changing nickel nitrate with copper nitrate.

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Characterization of Nanoparticles
The X-ray powder diffraction analysis was
conducted with a Huber JSO-DEBYEFLEX 1001
Diffractometer (XRD) using Cu K (operated at 40
kV and 35 mA). The FT-IR transmission spectra
were taken with a Mattson Satellite Infrared
Spectrometer from 4000 to 400 cm-1. The structural
and morphological characterizations of the samples
were accomplished using a field emission scanning
electron microscopy (FE-SEM JEOL 7001 FE).
The samples were coated with carbon prior to SEM
measurements.
Heavy Metal Removal Experiments
Here we report the synthesis of copper and
nickel ferrite (CuFe2O4 and NiFe2O4) nanoparticles
and the potential uses of these nanocomposites for
Cu(II), Ni(II), and Zn(II) removal from the
synthetic wastewater. For this purpose, we prepared
the synthetic waste water by dissolving salts of
Ni(NO3)26H2O, Cu(NO3)23H2O, and N2O6Zn
6H2O in distilled water by using measured
amounts. An 0.1 g of nanoparticles were used and
mixed with the wastewater which is a composite
metal mix consisting of Cu(II), Ni(II), and Zn(II)
metal ions. The concentrations of Cu(II), Ni(II),
and Zn(II) in the synthetic wastewater were 18.94,
42.42, and 42.73 mg/L, respectively. The samples of
25 ml of wastewater in 100 ml schliff-erlenmeyers
were prepared in two groups; 0.1 g of CuFe2O4 was
added to the first group and 0.1 g of NiFe2O4 was
added to the second group. The samples were mixed
in a shaker (Gallenkamp orbital incubator, 25C) at
120 rpm for 24 hours and then filtered with an 0.5
micron paper filter. The samples were then
acidulated with 0.2% nitric acid. The amounts of
Cu(II), Ni(II), and Zn(II) were determined by
atomic absorption spectrometry (AAS) with a Varian
Spectra instrument model 220 spectrometer. A
standard solution containing the same matrix as the
samples was made up at the appropriate
concentrations for each element and used to draw a
calibration curve in AAS.
The removal efficiencies and adsorption
capacities of nanoparticles (CuFe2O4 and NiFe2O4)
were calculated using equations 1 and 2.
(1)

(2)

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where E (%) is the removal efficiency, q (mg/g) is
adsorption capacity, C0 (mg/L) and Ce (mg/L) are
the initial and equilibrated metal concentrations,
respectively, V(L) is the volume of added solution,
and m (g) is the mass of the adsorbent (dry).
The Apparatus Used
The following materials and equipment were
used during the proposed validation study.
Materials: Cu standard stock solution (1000 g
Cu/L), Ni standard stock solution (1000 g Ni/L),
Zn standard stock solution (1000 g Zn/mL), Nitric
acid solution(65%), and distillated water.
Equipment: Varian Spectra instrument model
220 Atomic absorption spectrometer, and a Gallenkamp orbital incubator.
RESULTS
Structural Characterization of Nanoparticles
The phase identification, of the as-prepared
NiFe2O4 and CuFe2O4 samples, was determined by
X-ray diffraction (XRD). Figures 1 and 2 show the
XRD patterns of the as prepared samples of
NiFe2O4 and CuFe2O4 and they indicate that both
samples have a single spinel phase with a good
crystallinity. By comparing XRD patterns of present
investigations with the standard data (JCPDS: 00010-0325 for NiFe2O4 and JCPDS: 77-10 for
CuFe2O4), it has been concluded that both samples
can be perfectly indexed to the cubic spinel
structure indicated in the reflecting planes (111),
(220), (311), (222), (400), (422), (511), and (440) in
the patterns. Using Scherrer's equation: D=0.9 /
cos where D is the average crystalline size, is the
wavelength of Cu K, is the full width at half
maximum (FWHM) of most intense diffraction
peak (311), and is the Bragg's angle, the average
particle sizes are estimated to be around 25.6 nm for
NiFe2O4 and 11.3 nm for CuFe2O4.
FT-IR Spectroscopy
Figure 3 shows the representative IR spectra of
the as prepared ferrites of CuFe2O4 and NiFe2O4.
The two main broad metal-oxygen bands are
important in the IR spectra of all spinels, especially
in ferrites. The highest IR band, V1, is generally
observed in the higher frequency range of 600-550
cm-1, corresponding to the intrinsic stretching
vibrations of the metal-oxygen bond at the
tetrahedral site, Mtetra-O. The lowest IR band, V2, is
usually observed in the frequency range of 450-385
cm-1, assigned to stretching vibrations of the metal92

Sezgin et al.

Fig 1. The XRD pattern for NiFe2O4 nanoparticles


synthesized by the PEG assisted hydrothermal
method.

Fig 2. The XRD pattern for CuFe2O4 nanoparticles


synthesized by the PEG assisted hydrothermal
method.

oxygen bond at the octahedral site, Mocta-O. As seen


in the Figure 3, both the V1 and V2 stretching
vibrations were observed with the normal mode of
vibration of the tetrahedral cluster and is higher than
that of the octahedral cluster. This can be attributed
to the shortness of the tetrahedral bond and the
length of the octahedral bond. Since both Cu2+ and
Ni2+ ions preferentially occupy the octahedral sites
and Fe3+ ions can occupy both octahedral and
tetrahedral sites, both of the V1 and V2 bands
observed are the characteristics of the prepared Cu
and Ni ferrites (Koseoglu et al. 2011, Marinca et al.
2012). In the FT-IR spectra, V1 (540 cm-1) ) and V2
(427 cm-1) for CuFe2O4 shifted slightly to higher
frequencies as V1 (550 cm-1)) and V2 (460 cm-1)
values by replacing the Cu2+ ion with an Ni2+ ion.
Slight shifts of the V1 and V2 peak positions indicate
that changes due to the Ni2+ substitution has
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Synthesis, Characterization and, the Heavy Metal Removal...

Fig 3. The FT-IR spectra of both adsorbents.

Fig 4. SEM pictures taken from (a) CuFe2O4 and (b)


NiFe2O4 nanoparticles synthesized by PEG assisted
hydrothermal method.

slightly affected the metal-oxygen force constants in


the tetrahedral and octahedral sites. This can be
explained by the very small difference in both the
atomic mass and ionic radii of the Cu and Ni ions
(Faraz et al. 2012).
SEM Measurements
Figure 4 shows the field emission scanning
electron micro-graphs (FE-SEM) of the CuFe2O4
and NiFe2O4 nanoparticles. The SEM images show
that the samples consist of spherical shaped
nanoparticles with small agglomeration. As seen in
the SEM pictures the nanoparticles have sizes of
more than 100 nm and they are dense and
distributed regularly with-in the whole area (see Fig.
4(a b)). In addition to this, although these smaller
crystallites are so closely arranged together, a clear
boundary between neighboring particles can also be
observed. The larger particle sizes of the
nanoparticles can be attributed to the PEG coating
which doesnt count in crystallite sizes obtained
from XRD since PEG is amorphous.
Removal of Heavy Metals
The graphs of the removal efficiencies of Cu(II),
Ni(II), and Zn(II) from synthetic wastewater are

No: 89, 2013

Ekoloji
shown in Fig. 5 for 0.1 g CuFe2O4 and Fig. 6 for 0.1
g NiFe2O4.
The removal efficiencies of Cu(II), Ni(II), and
Zn(II) by using CuFe2O4 nanoparticles are
calculated as 83.50%, 98.85%,
and 99.80%,
respectively. It was found that the higher efficiency
was obtained for the removal of Zn(II) and the
lower efficiency was obtained for the removal of
Cu(II) as shown in Figure 5. The removal
efficiencies of Cu(II), Ni(II), and Zn(II) by using
NiFe2O4 nanoparticles are calculated as 92.55%,
36.56%, and 99.91%, respectively. It was found that
the higher efficiency is again in the removal of
Zn(II) and the lower efficiency is in the removal of
Ni(II) as shown in Figure 6. As compared with the
literature, Ozmen et al. (2010) found 75.3% value
for Cu(II) removal efficiency from an aqueous
media with the modified Fe3O4 nanoparticles (pH
of the solution 4, contact time 1 h, and the amount
of adsorbent 1.25 g/L) and Mahdavi et al. (2012)
found the removal efficiencies of Cd, Cu, Ni, and
Pb, in which Fe3O4, ZnO, and CuO nanoparticles
were used, between 9.2% and 81.5%.
It is also calculated as the adsorption capacities
(q) of CuFe2O4 and NiFe2O4 nanoparticles for
Cu(II), Ni(II), and Zn(II). The adsorption
capacities (q) are shown in Figures. 7 and 8 for
CuFe2O4 and NiFe2O4, respectively. The amounts
adsorbed by CuFe2O4 nanoparticles were calculated
as 3.95, 10.48, and 10.66 mg/g for Cu(II), Ni(II),
and Zn(II), respectively. By using NiFe2O4
nanoparticles, the adsorption amounts were found
as 4.38, 3.88, and 10.67 mg/g for Cu(II), Ni(II), and
Zn(II), respectively. Zn(II) has the highest value
when examining the metal adsorption capacities of
CuFe2O4 and NiFe2O4 nanoparticles.
DISCUSSION
The synthesis of copper and nickel ferrite
(CuFe2O4 and NiFe2O4) nanoparticles using the
PEG assisted hydrothermal method and the
potential uses of these nanocomposites as adsorbent
for the removal of heavy metals from synthetic
wastewater was investigated. The FT-IR and XRD
spectra indicated that the samples have single phase
spinel structure with sizes 25.6 nm for NiFe2O4 and
11.3 nm for CuFe2O4. The SEM pictures show that
the nanoparticles have spherical shapes with small
agglomeration.
It was seen that these spinel ferrites are very
efficient for the removal of heavy metals (zinc,
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Fig 5. The removal Efficiencies (%) of Cu(II), Ni(II), and


Zn(II) by using 0.1 g CuFe2O4 nanoparticles.

Sezgin et al.

Fig 7. The adsorption capacities (q) of 0.1 g CuFe2O4


nanoparticles for Cu(II), Ni(II), and Zn(II)

Fig 8. The adsorption capacities (q) of 0.1 g NiFe2O4


nanoparticles for Cu(II), Ni(II), and Zn(II)
Fig 6. The removal Efficiencies (%) of Cu(II), Ni(II), and
Zn(II) by using NiFe2O4 nanoparticles.

copper, and nickel) from synthetic wastewater by


adsorption by magnetic nanoparticles and a
subsequent simple magnetic separation process.
In this paper, the removal efficiencies of Cu(II),
Ni(II), and Zn(II) by using CuFe2O4 nanoparticles
was calculated as 83.50 %, 98.85%, and 99.80%,
respectively. It was found that the higher efficiency
is for the removal of Zn(II) and the lower efficiency
is for the removal of Cu(II). The removal
efficiencies of Cu(II), Ni(II), and Zn(II) by using
NiFe2O4 nanoparticles were calculated as 92.55%,

36.56%, and 99.91%, respectively. It was found that


the higher efficiency is again for the removal of
Zn(II) and the lower efficiency is for the removal of
Ni(II).
The results indicate that CuFe2O4 and NiFe2O4
nanoferrites synthesized by the PEG assisted
hydrothermal method are useful for heavy metal
removal from wastewater and they have high heavy
metal removal efficiencies.
ACKNOWLEDGEMENTS
This work was supported ny Scientific Research
Projects Coordination Unit of Istanbul University.
Project number 28461

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