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doi: 10.5053/ekoloji.2013.8911
RESEARCH NOTE
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
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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
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Sezgin et al.
Table 1. The MCL standards for the most hazardous heavy
metals.
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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.
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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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