Journal of Hazardous Materials 299 (2015) 316324

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Fluoride adsorption by doped and un-doped magnetic ferrites

CuCex Fe2-x O4 : Preparation, characterization, optimization and
modeling for effectual remediation technologies
Muhammad Abdur Rehman a,b, , Ismail Yusoff a , Yatimah Alias b
a
b

Department of Geology, Faculty of Science, University of Malaya, Kuala Lumpur 50603, Malaysia
Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia

h i g h l i g h t s

A series of doped and un-doped magnetic ferrites adsorbents has been prepared by W/O micro-emulsion.
The adsorption, electrochemical and magnetic properties of the adsorbents was compared.
A uoride adsorption model was developed based on central composite design of experiments.
Effect of concomitants HCO3 1 , SO4 2 , NO3 1 , Cl1 and Arsenic on uoride adsorption.
Response surface method for adsorption of uoride.

a r t i c l e

i n f o

Article history:
Received 24 April 2015
Received in revised form 5 June 2015
Accepted 19 June 2015
Available online 23 June 2015
Keywords:
Fluorides
Micro-emulsion
CuFe2 O4
Adsorption
Ion chromatography
Ferrites

a b s t r a c t
A series of doped and un-doped magnetic adsorbents CuCex Fe2-x O4 (x = 0.00.5) for uoride were prepared with the micro-emulsion method. Fluoride adsorption was optimized for solution pH, temperature,
contact time, and initial concentration and was monitored via normal phase ion chromatography (IC). The
effect of concomitant anions was also explored to perform and simulate competitive uoride adsorption
in real water samples. Optimal adsorption was discovered by a simple quadratic model based on central
composite design (CCD) and the response surface method (RSM). The adsorption, electrochemical and
magnetic properties were compared between doped and un-doped ferrites. Doped ferrites (x = 0.10.5)
were found to be superior to un-doped ferrites (x = 0) regarding the active sites, functional groups and uoride adsorption. The characterization, optimization and application results of the doped ferrites indicated
enhanced uoride adsorption and easy separation with a simple magnet.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Fluoride is a necessary nutrient for dental health because it
increases dental resistance to the attacks of acids formed by bacterial plaque and prevents the formation of cavities. However, when
uoride is present in public water supplies beyond certain limits, it
is injurious to health [13]. The maximum allowable uoride concentration level (MCL) of 1.5 mg/L has been set for drinking water by
World Health Organization (WHO). The consumption of excess uoride can cause impaired physical growth and intelligence, skeletal

Corresponding author at: Department of Geology, Faculty of Science, University

of Malaya, Kuala Lumpur 50603, Malaysia.
E-mail address: drmarehman83@gmail.com (M.A. Rehman).
http://dx.doi.org/10.1016/j.jhazmat.2015.06.030
0304-3894/ 2015 Elsevier B.V. All rights reserved.

uorosis, osteoporosis, arthritis, and even cancer in extreme cases

[48]. Adsorption is considered the most efcient method due to its
reduced cost, environmental friendliness and ease of operation. A
number of adsorbents have been developed for uoride adsorption
[911]. The criteria for selecting a suitable adsorbent is based on the
desirable properties, large specic surface area, larger number of
active functional sites, pore size and volume, stability, and magnetic
separation capability [12,13]. However, some obstacles remain in
the development of adsorbents for uoride adsorption, such as
instability, matrix effects, mechanical strength and poor adsorption capacity. Therefore, more efforts should be devoted toward
new classes of adsorbents with high de-uoridation capacity.
Recently, magnetic adsorbents with high adsorption capacity and environmental friendliness have been developed and

M.A. Rehman et al. / Journal of Hazardous Materials 299 (2015) 316324

applied for the treatment of anionic contaminants, such as uoride,

nitrate, sulfate, arsenate and phosphate. These magnetic adsorbents include magnetic materials, such as iron, copper, cobalt and
nickel oxides [14]. The exible geometric structures of transition
metal oxides enables the production of adsorbents with unique
properties [15]. The cubic close packed geometry of CuFe2 O4 offer
two types of sites, i.e., tetrahedral sites (A) and octahedral sites (B)
[16]. The electrical and magnetic properties depend on the position
of each metal on each site. These sites play a very critical role in
the electromagnetic properties [17]. Ferrites exhibit the exchange
of electrons during FeFe interaction, causing polarizations and
electrical conductivity [17]. However, doping rare earth cations
changes the electrical, magnetic and physical properties [18,19].
Cerium (Ce) is a unique single electron system; it facilitates particle dispersion, which is a desirable and expected properties for an
adsorbent. Cerium also promotes a larger number of active functional sites, surface area, and a larger pore size and pore volume.
These improvements facilitate the adsorbateadsorbent interactions because the adsorbate can easily diffuse and reach the active
sites for adsorption.
The design of experiments (DOE) strategy is an advantageous
method compared with the use of the OVAT strategy, which incorporates one variable at a time [20,21]. DOE provides better insights
into interactions among selected variables with a minimum number of experiments, thereby reducing the cost of research of new
adsorbents [10,16,21]. Normally, multiple interactions of variables
and non-linear behavior of adsorption processes result in a complex
overall mechanism [11,14,17,20,22]. To understand such complex
mechanisms, the response surface methodology (RSM) is a competitive modeling tool that can be used to analyze and present
complex nonlinear relationships among variables either alone or in
combination and their synergistic or opposed effects on adsorption
[10,2325]. The principle of RSM is to discover optimum system
response with the help of polynomial equations [16,22]. From feasibility studies, signicant experimental variables are co-varied over
a pre-selected range to determine their interactive effects, nally
combining all of the interactions to build a mathematical model
[26]. The model is implemented in an adsorption system to achieve
optimum performance through the use of a minimum number of
experiments and by eradicating insignicant variables [27].
The ion chromatographic (IC) separation and detection method
for quantifying anions provides multiple advantages. First, only a
small amount of sample (20 L) is required, which allows for the
separation of concomitant ions, depending on their retention times
(tR ). Second, inline ion suppressor controls the conductivity by suppressing the concomitant ions, thereby causing high conductivity.
Third, a number of anions can be simultaneously detected and
quantied in a single run due to the specic interaction and partition between the stationary phase and the mobile phase. Moreover,
IC separation is a highly specic, selective, reproducible, robust and
cost-effective method.
In the study, magnetic CuCex Fe2-x O4 ferrites were prepared
either with or without Ce doping to compare their capacity for
uoride adsorption. The characteristics were determined using
the following techniques: X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, eld emission scanning electron
microscopy (FESEM), BrunauerEmmettTeller (BET) surface area,
electrochemical impedance spectroscopy (EIS), Linear scan cyclic
voltammetry (LSV) and vibrating sample magnetometer (VSM). A
series of interactive experiments were conducted to study the effect
of pH, temperature, adsorbent dose and uoride initial concentration. The concomitant effects of HCO3 1 , SO4 2 , NO3 1 , Cl1
and As were also studied to determined uoride adsorption at
different concentrations. Through this study, the model and mechanism of uoride removal by magnetic ferrites were explained in
detail.

317

2. Materials and method

2.1. Materials
The analytical grade chemicals ferric nitrate heptahydrate
Fe(NO3 )3. 9H2 O, copper nitrate Cu(NO3 )2 , cerium ammonium
nitrate (NH4 )2 Ce (NO3 )6 , ammonium hydroxide NH4 OH, cyclohexane, 1-propanol, sodium carbonate Na2 CO3 , and sodium
bicarbonate NaHCO3 were purchased and used in the form in which
they were received from SigmaAldrich. A stock 1000 mg/L uoride solution was prepared in deionized water with resistivity
of 18 M cm1 (Millipore, USA). Fluoride working solutions were
prepared via the dilution method. Standard solutions of anions
(chloride, nitrate, sulfate and bicarbonate) were prepared by dissolving sodium salts purchased from SigmaAldrich, Malaysia.
Sulfuric acid (Merck, Malaysia) was used as a scavenger for the ion
suppressor.
2.2. Instruments
The IC system (Metrohm-850 Professional IC) equipped with a
pump, column oven, sample injector, self-regenerating suppressor,
Metrohm suppressor module (MSM), degasser and conductivity
detector was used for the separation and detection of the anions. All
separations using the IC system were performed on a column (Metrosep A supp 4 250/4.0 mm). The mobile phase containing 3.2 mM
sodium carbonate, 1.7 mM sodium bicarbonate and 2% acetone was
passed through the column at a ow rate of 0.70 mL/min. A sample
volume of 20 L was injected through a hexa-port valve sample
injector, and the column temperature was maintained at 26 C.
The ion suppressor was continuously regenerated with a constant
ow of 0.5 mL/min of 50-mM sulfuric acid. Each analysis was performed within a period of 30 min, and the data were processed and
analyzed using MagICNetTM 1.1.
2.3. Preparation of ferrite adsorbents
A transparent micro-emulsion (1.0 dm3 ) was prepared through
the sonication of a surfactant hexadecyl-trimethyl-ammonium
bromide (CTAB) in cyclohexane, 1-propanol and water. Preweighed quantities of the respective aforementioned salts were
separately dissolved and magnetically stirred at 60 C. Ammonium
hydroxide was poured drop wise with continuous stirring to pH 8.0.
Aging of the precipitates was completed by keeping the solution for
24 h at room temperature. Cleaning and removal of impurities was
accomplished by successive washing with 80% methanol solution.
Each ferrite was kept in an air electric furnace at 650 C for 3.0 h
after heating at a rate of 5 C min1 . Finally, the dried particles were
ground into ne powder for the sequence experiments.
2.4. Characterization of the adsorbents
The electric, magnetic and dielectric behavior of ferrites is a
function of structural properties [2830]. As a result, XRD, FTIR and
FESEM were used for adsorbent characterization. The high penetrating power of X-rays provides important information regarding
the structural properties of matter. The angle of diffraction and the
intensity of the diffracted beam are both characteristics of a particular crystal structure. Every material is unique because of the sizes of
its atoms, the arrangement of its atoms and the ability of each atom
to scatter X-rays. Because no two atoms have exactly the same size
and X-ray scattering ability, the intensities of the diffracted beam
are unique for every material. This uniqueness helps identify the
structure and determine the structural parameters of the material
under study [16]. Multiphase structure, crystallite sizes and crystal
strains of CuCex Fe2-x O4 were observed using an XRD instrument

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M.A. Rehman et al. / Journal of Hazardous Materials 299 (2015) 316324

Table 1
Retention times of the selected anions during ion chromatography.
Anions

Cl

NO3

SO4 2

tR

4.047

5.535

8.87

16.601

(PANanalyticals Emprean) that was equipped with a monochromatic Cu-K radiation source. The surface morphology and particle
size distribution of the ferrites were studied using FESEM. FTIR
analysis was performed on a PerkinElmer System 2000 series spectrophotometer (USA) over the spectral range of 4000400 cm1 .
Magnetic hysteresis loops were recorded on a VSM. BET specic
surface area analysis of the samples was performed on the basis of
nitrogen adsorption desorption isotherms measured at 77 K using
a BELSORP-max nitrogen adsorption apparatus (Japan Inc.). CV
and EIS experiments were performed on an Autolab PGSTAT 302N
instrument, and NOVA 1.10 software was used to analyze the experimental data.
2.5. Design of experiments
Central composite design (CCD) was selected for the design of
the uoride adsorption experiments. Adsorption experiments were
performed as suggested by the results of the software. The equilibrium uoride adsorption capacity (qe mg g1 ) was calculated using
the following equation (Eq. (1)) [31].
qe =

(Co Ce ) V
m

(1)

where Co and Ce denote the initial and equilibrium adsorbate concentration (mg L1 ), respectively, V is the total volume of solution
in liters, and m is the mass of the adsorbent (g). Adsorption experiments were repeated to check for systematic variations to conrm
the reproducibility of the results.
The statistical models give a better insight into the complex,
mutually inuencing system of variables, the structure of the interactions, and the level of inuence on the system overall response
[20,21]. Moreover, statistical models also identify the most and
least inuential variables [27]. In this work, Eq. (2) presents the
selected quadratic model [21,32].
k

i=1

i=1

qe = o +  i xi +  + i xi2 +   ij xi xj + i =
/ j

(2)

i=1j=2

where o is a constant coefcient,  represents the error, xi and xj

are independent variables, and i , ii , and ij represent coefcients
of linear, quadratic, and interaction effects, respectively. Adsorption results against each experiment were analyzed and tted into
the quadratic models. The model was veried by statistical tests,
e.g., analysis of variance (ANOVA), residuals analysis (RA), scaling
residuals (SR) and prediction error sum of squares (PRESS) [21,23].
The veried and validated model was applied to optimize the four
input variables and to maximize the output, i.e., uoride adsorption
capacity.
2.6. Determination of the anions
The anions were identied and quantied based on their
retention time (tR ) when performing ion chromatography (IC), as
presented in Table 1.
Anion calibration standards of 1, 5 and 10 mgL1 were run
to develop a calibration method. The tR values of standards and
samples were compared and quantied with MagICNetTM 1.0. In
suppressed ion chromatographic separation, an ion suppressor
was inserted between the separating column and the detector to
reduce the inherent conductivity of the eluent for improved anion

Fig. 1. XRD spectra [A] un-doped CuFe2 O4 , [B] doped CuCe0.1 Fe1.9 O4 , [C] CuCe0.2 Fe1.8
O4 , [D] CuCe0.3 Fe1.7 O4 , [E] CuCe0.4 Fe1.6 O4 , and [F] CuCe0.5 Fe1.5 O4 adsorbents for
uoride, annealed at 650 C for 3 h.

detection. The reactions involved with the chemical suppressor are

represented by the following equation [33].

+
+
+
R SO
3 H + Na HCO3 R SO3 Na + H2 O + CO2
+
R SO
3H

+ Na + F

+
R SO
3 Na

+H +F

(3)

(4)

Na+

H+

ions coming in mobile phase are replaced with

ions,
quenching the conductivity of the background electrolyte, as represented by Eq. (3). The anion in sample, e.g., F remains unaffected
by the suppressor, detected and quantied by IC system, as represented by Eq. (4).
3. Results and discussion
3.1. XRD phase analysis
Stacked XRD patterns of CuCex Fe2-x O4 (x = 0.00.5) are shown
in Fig. 1. In the absence of cerium (x = 0.0), all of the identied
peaks matched with copper ferrite (CuFe2 O4 , Reference code # 96901-2842), which indicated the formation of spinel-type CuFe2 O4
[34]. After the addition of Ce (x = 0.1), some additional peaks of
low intensity appeared in the XRD spectra corresponding to CeO2
(CeO2 , Reference code # 96-900-9009) [35]. A systematic increase
in dopant concentration (x) resulted in a gradual increase in the
intensity of the CeO2 peaks. Moreover, we observed a decrease in
the (3 1 1) peak. The addition of cerium into the pristine copper
ferrite exhibited a distinct change in the percentages of the respective phases. The average crystallite size (nm) was calculated using
Scherers formula (Table 2).
A comparison among the crystallite sizes reveals a systematic
decrease of crystallite size with a gradual increase in dopant (Ce).
Table 2
Crystal sizes and the micro-strain and BET properties of a series of copper ferrites
CuCex Fe2-x O4 (x = 00.5).
Property
2

BET Surface area (m /g)

Crystallite sizes D (nm)
Average pore size (nm)
Pore volume (cm3 /g)
Lattice strain  (%)

x = 0.0

x = 0.1

x = 0.2

x = 0.3

x = 0.4

x = 0.5

70
72
38
0.44
0.17

75
50
34
0.4
0.25

79
34
30
0.38
0.38

83
30
25
0.34
0.42

88
20
20
0.29
0.64

92
18
17
0.26
0.69

M.A. Rehman et al. / Journal of Hazardous Materials 299 (2015) 316324

319

Fig. 2. (A) Effect of the applied potential on the current response and (B) Nyquist diagrams of (x = 0) un-doped CuFe2 O4 (x = 0.1), doped CuCe0.1 Fe1.9 O4 (x = 0.2), CuCe0.2 Fe1.8
O4 (x = 0.3), CuCe0.3 Fe1.7 O4 (x = 0.4), and CuCe0.4 Fe1.6 O4 (x = 0.4) CuCe0.5 Fe1.5 O4 in 0.1 M KCl solution containing 1.0 mM Fe(CN)6 3/4 (1:1).

Doping copper ferrites with Ce reduced the crystallite sizes of

pristine ferrite. This decrease was attributed to the formation of secondary phases [36]. This decrease was also supported by a relative
increase in the lattice parameters. Annealing at elevated temperature forced Ce3+ ions to migrate into the crystal structure, the
interstitial regions, or the grain boundary sites. A large ionic radius
of Ce3+ (1.020 ) compared with that of Fe3+ (0.645 ) offered a relative space hindrance to the competitive vacant crystal or interstitial
sites in copper ferrites [37]. Consequently, the Ce3+ ions were oxidized to Ce4+ at this temperature and appeared as a distinct phase
in the XRD spectrum (Fig. 1).
The surface properties, surface area, and pore size and volume of
the adsorbents were analyzed via BET. Table 2 indicates that a gradual increase in dopant concentration (x) corresponds to an increase
in the BET surface area. Cerium oxide likely inhibits the growth of
larger particles because of its high dispersion [18]. The BET results
indicate that during adsorption, more uoride can interact with the
available active sites that are created by doping in these magnetic
ferrites.

3.2. Electrochemical properties

The electrochemical properties of ferrite modied electrodes
were studied using electrochemical impedance spectroscopy (EIS).
EIS measures the charge transfer resistance (Rct ) and separation
efciency between the holes and electrons. Rct is a critical factor in
the charge separation efciency. Fig. 2 shows a typical Nyquist plot
of the ferrite. The arc radius of the Nyquist plot reects the interface layer resistance at the surface of the electrode. A smaller arc
radius indicates a higher charge transfer efciency. The bare electrode response of a semicircle of larger radius compared with that
of the ferrites modied electrodes due to the large value of Rct at
the electrodeelectrolyte interface. The arc radius decreases from
x = 0 to x = 0.2, which indicates higher charge resistance with higher
Ce content. According to the hopping mechanism, changes in the
mobility of the charge carriers lead to the conduction of current
by hopping from one iron atom to the next [38]. When cerium is
doped in the place of iron, the resistivity of the sample is found to
increases. This behavior can be explained by the greater resistivity
of cerium (74.4 108  m) compared with iron (8.57 108  m)
[39]. Further increase in the Ce dopant in the range of x = 0.30.5
again reveals that larger semicircles are associated with the higher
amounts of Rct .

Fig. 3. FTIR overlay spectra of (A) un-doped CuFe2 O4 , (B) doped CuCe0.1 Fe1.9 O4 , (C)
CuCe0.2 Fe1.8 O4 , (D) CuCe0.3 Fe1.7 O4 , (E) CuCe0.4 Fe1.6 O4 , and (F) CuCe0.5 Fe1.5 O4 .

LSV analysis was used to study the electrochemical properties of the adsorbents. Ferrite with x = 0.2 exhibited the maximum
photocurrent response, followed by x = 0.1 (Fig. 2). The photoelectrochemical activity is well known to be determined by the
light harvesting capacity and the separation of electron-hole pairs
[40]. Generally, a high value of the photocurrent indicates that the
sample has a strong ability to generate and transfer the photoexcited charger carrier under irradiation. The EIS and LSV results
conrm that the ferrite adsorbents can be used as photo-catalysts
and photo-electrode materials in addition to their excellent adsorbent properties.
3.3. FTIR spectroscopy of spinel structures
The inter-metallic ionic mode of vibration in FTIR spectroscopy
analysis provides information regarding the ions involved in the
formation of the crystal lattice [40,41]. The characteristic peaks
of the spinel structure observed in the range of 560580 cm1
are attributed to Fe O stretching vibration at the tetrahedral site

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M.A. Rehman et al. / Journal of Hazardous Materials 299 (2015) 316324

Fig. 4. FESEM images of (A) un-doped CuFe2 O4 , (B) doped CuCe0.1 Fe1.9 O4 , (C) CuCe0.2 Fe1.8 O4 , (D) CuCe0.3 Fe1.7 O4 , (E) CuCe0.4 Fe1.6 O4 , and (F) CuCe0.5 Fe1.5 O4 prepared in
micro-emulsion (w = 15).

(Fig. 3). FTIR functional groups were compared in pristine and

Ce-doped ferrites. All Ce-doped ferrites have distinct peaks near
850 cm1 and 1440 cm1 . The additional functionality is thought
to be responsible for the electrostatic interaction with the adsorbate to enhance the overall uoride adsorption. The hydroxyl and
sulfate groups are clearly involved in the uoride adsorption. The
abundance of these groups in the Ce-doped ferrite may be the main
reason for the high uoride uptake.
3.4. FESEM results
Fig. 4 shows FESEM images of the respective ferrites (x = 0.00.5).
When x = 0.0, we observe normally sized CuFe2 O4 nano-crystals
(74 nm) with uniform morphology along with some agglomerations of larger size (180 nm). This behavior was due to the large
specic surface of the ne particles for van der Waals interactions.
From a nanochemistry perspective, adjacent nanoparticles that
share a common crystallographic orientation may collide with each
other, which leads to coalescence [42] because adjacent primary
particles attach to each other and form aggregates. In addition,
due to the nanometer-scale sizes, these particles continue to collide and coalesce to form even larger particles. This phenomenon
may eventually cause agglomeration in the fabricated ferrites. The
agglomeration is affected by various processing parameters, such
as speed, intensity and mixing time. Relatively smaller sizes were
observed with further addition of ceria (x = 0.10.5). Moreover, the
addition of ceria particles was found to increase the surface area by
allowing for maximum dispersion and retarding large grain growth.
These results complement the XRD results and provide evidence
of an increased surface area, which can facilitate better uoride
adsorption. These results also agree with those of other studies,
indicating that doping lanthanides hinders particle grain growth
[36,43]. The observed incremental decrease in grain morphology
via the systematic doping of ceria promotes uoride adsorption.
3.5. Magnetic properties
The magnetic hysteresis loops of CuCex Fe2-x O4 (x = 0.00.5) are
shown in Fig. 5. The value of the squareness ratio (SQ) was calculated by dividing the value of the magnetic remanence (Mr) by

Fig. 5. Magnetic properties of (A) un-doped CuFe2 O4 , (B) doped CuCe0.1 Fe1.9 O4 , (C)
CuCe0.2 Fe1.8 O4 , (D) CuCe0.3 Fe1.7 O4 , (E) CuCe0.4 Fe1.6 O4 , and (F) CuCe0.5 Fe1.5 O4 .

the magnetic saturation (Ms). The SQ value reects the magnetocrystalline anisotropy and the super-exchange interactions of the
ferrite series [44]. CuFe2 O4 exhibits a SQ value of 0.13 (x = 0.0), but
after Ce doping, this value increases in the cases of x = 0.1 and x = 0.2.
Note that the incorporation of Ce reduced the magneto-static interactions [45]. However, the further addition of Ce exhibits a regular
declining trend from x = 0.3 to x = 0.5. This phenomenon indicates
that the local canting effect is taking control over the surface canting effects associated with crystallite size and coercivity [46]. The
relative change in Mr and Ms with Ce content has exactly the same
trend, as expected from the SQ values for each member of the series
Table 3.
From Table 3, the Hc value is clearly increasing with the amount
of dopant (x from x = 0.0 to x = 0.2), and further doping results in a
regular decline (from x = 0.3; the maximum decrease occurs when
x = 0.5), which is attributed to extrinsic and intrinsic factors. The
extrinsic factors depend on the density, morphology and grain size
[47]. The intrinsic factors, such as relative occupation of sub-lattice
sites, contributed to the magnetism in the nano-ferrites [48]. The
shape and width of the hysteresis loops depend on the method of
preparation, composition, and distribution of the metal cations at

M.A. Rehman et al. / Journal of Hazardous Materials 299 (2015) 316324

321

Table 3
Magnetic properties of the CuCex Fe2-x O4 adsorbents by VSM.
Magnetic parameters

x = 0.0

x = 0.1

x = 0.2

x = 0.3

x = 0.4

x = 0.5

Coercivity (Hc)/T
Saturation magnetization (Ms) (emu/g)
Retentivity (Mr) (emu/g)
Squareness (SQ)

0.0069
30.137
4.336
0.144

0.0091
25.307
3.889
0.154

0.0104
15.531
3.093
0.199

0.01
13
2.5
0.192

0.0087
11.646
2.106
0.181

0.0037
8.885
0.823
0.093

the tetrahedral and octahedral sites, the spin canting and the crystallite size [41]. The values of Mr and Ms exhibit a regular decline.
This behavior could be explained by the reduction of D from 73 nm
to 18 nm (Table 1) and the respective increase in the Ce content
at the B-sites. Because the magnetic moment of Ce is less than
that of Fe, theoretically, increasing the Ce content will reduce the
Ms monotonically [46,49]. Generally, rare-earth elements have a
strong anisotropic subsystem with a sufciently high anisotropic
exchange constant for iron [50]. Thermal excitation breaks the
Kondo state, which causes a gradual recovery of magnetic moments
[51].
Ce3+ magnetic moments are governed by direct or indirect
exchange interaction, namely RKKY interaction mediated by conduction electrons [52]. Sufciently strong exchange interaction
produces a magnetically ordered ground state. In the present state,
ferrite with x = 0.4 and x = 0.5 have such an interaction, as shown
in Fig. 5. However, in the case of x = 0.3, a dominance of the Kondo
interaction occurs, which results in a nonmagnetic ground state.
A variation in the coercive eld (Hc ) directly depends on the surface spin disorder [53]. The decrease in Hc of the present series
afrmed the reduced surface spin disorder. The magnetic properties of the ferrites are controlled by FeFe interaction via the spin

coupling of 3d valance electrons [54]. The present decrease in coercivity is attributed to morphology-increased magnetic moments
and domain wall migration [55]. The lower values of Mr and Ms are
due to the oxidation of cerium into diamagnetic states [56]. However, the present decrease in magnetic character has little effect
on the uoride adsorption capacity, but it affects the magnetic
separation capability due to the change in its morphology, crystal
structure and related electromagnetic properties.
3.6. Fluoride adsorption model
The uoride adsorption model is given by Eq. (5). The ANOVA
test was applied to obtain the coefcients for each variable. A positive value of a coefcient symbolizes a synergistic effect, whereas
a negative value indicates an opposite effect [57].
qe = +1039.71 + 74.29 X1 + 25.31 X2 + 36.99 X3
+ 8.31 X4 0.32 X1 X2 0.261 X1 X3 0.21X1 X4
0.23X2 X3 0.10 X2 X4 0.13X3 X4 4.49 X12
0.93 X22 0.44 X32 0.03 X42

(5)

Fig. 6. Response surfaces showing the effects of two variables on uoride adsorption (A) pH and F1 (mg L1 ), (B) pH and Ads. Dose (mg), (C) F1 (mg L1 ) and Ads. Dose (mg),
and (D) Temp. ( C) and Ads. Dose (mg).

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M.A. Rehman et al. / Journal of Hazardous Materials 299 (2015) 316324

Fig. 7. Effect of some concomitant anions on uoride adsorption, m = 0.1 gL1 , [F]0 = 10 mgL1 , pH 7.0: (A) un-doped CuFe2 O4 , (B) doped CuCe0.2 Fe1.8 O4 , (C) CuCe0.3 Fe1.7 O4 ,
and (D) CuCe0.5 Fe1.5 O4 .

where X1 X4 are the coded variables for pH, F1 (mgL1 ), Temp.

( C) and ferrite dose (mg), respectively.
The adequacy of the model was ensured and tested by Fischer
variation (F-value), probability values (p-value) and the correlation coefcient (R2 ). The lack of t value of the model of 0.74 was
insignicant relative to the pure error. The predicted R2 value of
0.9988 was in reasonable agreement with an adjusted R2 of 0.9994.
The adequate precision of the model is a measure of the signal-tonoise ratio. A ratio greater than 4 is desirable. In the present case, a
ratio of 194.521 indicates an adequate signal. The effect of variables
was analyzed by comparing the values of the linear, quadratic and
interaction terms.
The pH linear term (X1 ) with an F-value of 2112.63 indicates
the signicant role of pH in uoride adsorption. However, the pH
quadratic term (X1 2 ) has an F-value of 2239.4, which is greater
than that of the linear term and indicates a positive role of pH
increase in the selected range on uoride adsorption. An optimum
uoride adsorption was achieved at neutral pH, as shown in Fig. 6
(RSM AC). According to the speciation of uoride, it exists as a
HF species instead of ionic (F1 ), which may be the reason for the
reduced adsorption under acidic conditions [58]. According to the
electrostatic interaction mechanism, a relatively stronger attraction is obtained at a pH below 6.12. However, pH is not the only
factor that controls the uoride adsorption. Similarly, the linear and
quadratic terms of the uoride initial concentration are signicant
during uoride adsorption. An increase in the uoride initial concentration improved the rate of adsorption. However, increasing
the uoride concentration beyond the optimum reduces the uo-

ride adsorption, as shown in Fig. 6 (RSM A and D). The linear and
quadratic terms of temperature (X3 and X3 2 ) indicate a decrease in
uoride adsorption at elevated temperatures. The most prominent
variable was adsorbent dose (X4 ), which has a signicant inuence on uoride adsorption. This inuence can be explained by the
adsorbent dose being directly related with the number of active
sites for uoride adsorption.
3.7. Effect of competing anions
Concomitant anions, such as chlorides, bicarbonate, nitrate, sulfate and arsenate, commonly exist in surface and ground water.
Because these anions compete with uorides for adsorbent active
sites, their inuence on uoride adsorption was experimentally
studied under different concentrations (0.1, 1.0 and 10 mM), as
shown in Fig. 7. In addition, arsenate (As), which is a concomitant anion of widespread concern, was studied at four different
concentrations (2, 5, 10 and 30 mgL1 ). According to Fig. 7 (AD),
uoride adsorption was affected by the presence of competitive
anions. The red, orange, yellow, green and blue areas highlight the
degree of adverse effect, with red indicating the greatest effect and
blue indicating the least effect on uoride adsorption.
Fig. 7(A) shows the effect of concomitant anions on the uoride
adsorption capacity for pristine CuFe2 O4 (x=0.0). The presence of
bicarbonate in solution exhibits the most negative effect on uoride removal. Note that uoride adsorption decreased by 12% in
the presence of 0.1 mM HCO3 1 at pH 7.0. Bicarbonate appears to
have the most negative effect, followed by nitrates and arsenate.

M.A. Rehman et al. / Journal of Hazardous Materials 299 (2015) 316324

These anions may strongly compete for ferrites active sites during
adsorption. Fig. 7(B) shows the effect of HCO3 1 , SO4 2 , NO3 1 , Cl1
and As on Ce-doped ferrite (x = 0.2). The adsorption of uoride was
unaffected by the lower concentration of the anions. However, the
higher concentration, as usually encountered in industrial waste
water, adversely affected the uoride removal process. Fig. 7(C),
demonstrates the effect of HCO3 1 , SO4 2 , NO3 1 , Cl1 and As on
ferrite (x = 0.3) at pH 7.0. For this particular adsorbent, the 10 mM
NO3 1 exhibited a 45% decrease in uoride adsorption, as indicated
by the orange color. The presence of chlorides has a mild effect, even
at a concentration of 10 mM. An arsenic concentration of 30 mgL1
in the solution also exhibited a 39% decrease in uoride adsorption.
Fig. 7(D) shows the effect of HCO3 1 , SO4 2 , NO3 1 , Cl1 and As on
the last member of the ferrite series (x = 0.5). The elevated levels
of HCO3 1 , NO3 1 and As were mapped in the danger zone of the
graphs. In some regions with higher concentration of competing
anions, careful pretreatment is mandatory before adsorption. However, lower concentration levels may not cause any concern during
the uoride removal process. Hence, this adsorbent is suitable for
the de-uoridation of the surface and ground water because the
chloride, bicarbonate, nitrate, sulfate and arsenic levels are lower
than those given above.
4. Conclusion
In summary, by using a straightforward doping of cerium into
magnetic ferrite, we successfully fabricated a series of novel magnetic adsorbents for uoride adsorption and water remediation
technology. Compared with un-doped parent material, superior
results were obtained, and the present enhancement in adsorption behavior contributed to the active functional groups created
after doping, the increased surface area with suitable porosity and
the electro-magnetic properties. However, the presence of some
concomitant species that are usually found in high concentration
in industrial efuents reduced the efciency of the present series
of adsorbents due to competition for adsorbent active sites, which
led to a decline in uoride removal. These ferrite-based adsorbents
for uoride open new vistas for a broad range of applications and
may lead to better insights into energy efcient magnetic adsorbents, electrochemical sensors and photo catalysts for environment
remediation.
Acknowledgments
We gratefully thank Bright Spark (BSP), University
of Malaya, and High Impact Research MoE Grant UM
.C/625/1/HIR/MoE/SC/04/01 from the Ministry of Education
Malaysia, University Malaya Center for Ionic liquids (UMCiL) and
IPPP grant # PG215-2014B for funding the cost of chemicals and
analysis.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jhazmat.2015.06.
030
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