Chemical Engineering Journal 327 (2017) 286–296

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Chemical Engineering Journal

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

Selective separation of rare earth ions from aqueous solution using

functionalized magnetite nanoparticles: kinetic and thermodynamic
studies
Radwa M. Ashour a,b, Ramy El-sayed c, Ahmed F. Abdel-Magied b, Ahmed A. Abdel-khalek d, M.M. Ali b,
Kerstin Forsberg e, A. Uheida a, Mamoun Muhammed f, Joydeep Dutta a,⇑
a
Functional Materials, Applied Physics Department, SCI School, Isafjordsgatan 22, SE-164 40 Kista Stockholm, Sweden
b
Nuclear Materials Authority, P.O. Box 530, El Maadi, Cairo, Egypt
c
Experimental Cancer Medicine, KFC, Novum, Department of Laboratory Medicine, Karolinska Institute, 141 86 Stockholm, Sweden
d
Department of Chemistry, Faculty of Science, Beni-Suef University, Beni-Suef, Egypt
e
Department of Chemical Engineering, KTH Royal Institute of Technology, 100 44 Stockholm, Sweden
f
Institute of Graduate Studies and Research, Alexandria University, Alexandria, Egypt

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Functionalized Fe3O4 NPs with citric

acid and L-cysteine were prepared.
3+ 3+

Selective separation of La , Nd ,
Gd3+ and Y3+ by the functionalized
Fe3O4 NPs.
3+

Cys@Fe3O4 NPs showed high La ,
Nd3+, Gd3+ and Y3+ adsorption
capacity.

The adsorption process followed a
pseudo-second order rate law.

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

Article history: Separation of rare earth ions (RE3+) from aqueous solution is a tricky problem due to their physico-
Received 11 May 2017 chemical similarities of properties. In this study, we investigate the influence of the functionalized
Received in revised form 18 June 2017 ligands on the adsorption efficiency and selective adsorption of La3+, Nd3+, Gd3+ and Y3+ from aqueous
Accepted 19 June 2017
solution using Magnetite (Fe3O4) nanoparticles (NPs) functionalized with citric acid (CA@Fe3O4 NPs) or
Available online 20 June 2017
L-cysteine (Cys@Fe3O4 NPs). The microstructure, thermal behavior and surface functionalization of the
synthesized nanoparticles were studied. The general adsorption capacity of Cys@Fe3O4 NPs was found
Keywords:
to be high (98 mg g1) in comparison to CA@Fe3O4 NPs (52 mg g1) at neutral pH 7.0. The adsorption
Magnetic nanoparticles
Rare earths
kinetic studies revealed that the adsorption of RE3+ ions follows a pseudo second-order model and the
Functionalization adsorption equilibrium data fits well to the Langmuir isotherm. Thermodynamic studies imply that the
Citric acid adsorption process was endothermic and spontaneous in nature. Controlled desorption within 30 min
L-cysteine of the adsorbed RE3+ ions from both Cys@Fe3O4 NPs and CA@Fe3O4 NPs was achieved with 0.5 M
Adsorption HNO3. Furthermore, Cys@Fe3O4 NPs exhibited a higher separation factor (SF) in the separation of Gd3+/
La3+, Gd3+/Nd3+, Gd3+/Y3+ ions compared to CA@Fe3O4 NPs.
Ó 2017 Elsevier B.V. All rights reserved.

⇑ Corresponding author.
E-mail address: joydeep@kth.se (J. Dutta).

http://dx.doi.org/10.1016/j.cej.2017.06.101
1385-8947/Ó 2017 Elsevier B.V. All rights reserved.
 R.M. Ashour et al. / Chemical Engineering Journal 327 (2017) 286–296
1. Introduction
Rare earth elements (REEs) have received attention due to their
use in different applications such as in superconductors, telecom-
munications, nuclear and solar energy conversion, photocatalysis,
and biosciences [1,2]. In recent years, RREs separation chemistry
has gained a great attention not only for their industrial applica-
tions, but also their environmental mitigation. Gadolinium (Gd)
is useful in ceramic industries, metallurgy, nuclear techniques in
fuel element fabrications and heavy water reactors as neutron poi-
son. Aqueous Gd3+ ion, even at trace level, considered as hazardous
material [3,4]. In view of all the above-mentioned uses and its high
toxicity, selective separation of Gd3+ from aqueous solutions is of
extreme importance. Due to the similar chemical and physical
properties of REEs, separating them from a mixture is still a chal-
lenging task [5,6]. The most commonly used techniques for the
separation and recovery of REEs are precipitation [7], liquid-
liquid extraction [8], ion exchange [9] and adsorption [10].
Amongst these, solid-phase extraction (SPE) is proven to be an
effective and convenient method for REEs recovery. SPE has been
proven to be an easy operation offering high adsorption capacities,
rapid phase separation and economical cost effectiveness [11]. Var-
ious types of adsorbents (organic, inorganic, carbon based material
and bio-sorbents) have been developed for SPE recovery of REEs
[12–17]. Magnetic nanoparticles have been found increased atten-
tion as nanoadsorbents for environmental decontamination due to
the possibilities of using external magnetic field to guide the pro-
cess of separation [18]. Furthermore, upon desorption of the
adsorbed ions, the magnetic nanoparticles can be reused, making
them promising sustainable adsorbents. Functionalized magnetic
nanoparticles using inorganic materials have been demonstrated
to be excellent candidates for selective adsorption of RE3+ ions
and metal traces from aqueous solution [19–23]. Dupont et al.
reported the functionalization of magnetite (Fe3O4) and nonmag-
netic (silica and titanium dioxide) nanoparticles with N-[(3-trime
thoxysilyl)propyl]ethylenediamine triacetic acid (TMS-EDTA) and
their behavior towards the adsorption and separation of RE3+ ions
in aqueous media [24]. Selective extraction of heavy samarium-
holmium (Sm–Ho) and Light lanthanum-niobium (La–Nd) lan-
thanides from aqueous solutions using diethylenetriamine-
pentaacetic acid (DTPA) functionalized Fe3O4 NPs, achieving high
SF between heavy-lanthanides and light-lanthanides reaching the
maximal value of 11.5 at low pH (2.0) in 30 min was reported by
Qiang et al. recently [25].
The choice of appropriate functional chelating groups is a criti-
cal factor to obtain maximum adsorption efficiency and selectivity.
Citric acid and L-cysteine are two major classes of chelating agents
that have been studied as chelators for adsorption of metal ions
[26]. Citric acid contains three carboxyl groups and a hydroxyl
group, while L-cysteine is constituted of three different functional
groups, amine, thiol and carboxylic acid (Fig. 1). Both citric acid
and L-cysteine ligands lead to the availability of functional groups
on Fe3O4 NPs for controlled adsorption but also affects the size,
morphology and colloidal stability of the nanoparticles [21].
Fig. 1. Chemical structure of the functionalization ligands used in this study: (a)
Citric acid and (b) L-cysteine.
287
Herein, we report the synthesis and characterization of mag-
netic nanoparticles functionalized with citric acid (CA@Fe3O4
NPs) and L-cysteine (Cys@Fe3O4 NPs) ligands, respectively. We
investigate the influence of CA@Fe3O4 NPs and Cys@Fe3O4 NPs on
the selective adsorption of RE3+ (= La3+, Nd3+, Gd3+ and Y3+) and
the adsorption mechanism from aqueous solution. The dependence
of adsorption parameters such as contact time, pH, temperature
and initial concentration of metal ions on the adsorption efficiency
were studied. In addition, we report the desorption characteristics
of REEs from the loaded CA@Fe3O4 NPs and Cys@Fe3O4 NPs using
different eluents such as NaOH and HNO3. Adsorption kinetics
and adsorption isotherms were analyzed using a non-linear
method and the thermodynamic parameters (DG°, DH° and DS°)
were derived from the obtained experimental results.
2. Materials and methods
2.1. Chemicals
Ferric chloride hexahydrate (FeCl36H2O,  99%), ferrous chlo-
ride tetrahydrate (FeCl24H2O,  98%), ammonium hydroxide
(25%), citric acid monohydrate (98%), L-cysteine, nitric acid (65%),
sodium hydroxide (98%), lanthanum(III) nitrate hexahydrate
(99.9%) [La(NO3)36H2O], neodymium(III) nitrate hexahydrate
(99.9%) [Nd(NO3)36H2O], gadolinium(III) nitrate hexahydrate
(99.9%) [Gd(NO3)36H2O], yttrium(III) nitrate hexahydrate (99.9%)
[Y(NO3)36H2O] and standard solutions (1000 mg/L) of Mg(NO3)2,
Ca(NO3)2and Ni(NO3)2 were purchased from Sigma Aldrich. All
chemicals were of analytical grade reagents and used as received
without further purification. Deionized water with a resistivity of
18 MX cm was used in all the experiments.
2.2. Characterization
High resolution transmission electron microscopy (HRTEM)
(HR-FEG-TEM, JEOL JEM-2100, Tokyo, Japan) was used for the char-
acterization of the morphology and size distribution of the synthe-
sized nanoparticles. For structural evaluation X-Ray Powder
Diffraction analysis (XRPD, PANalytical Empyrean) was carried
out. Fourier transform infra–red (FT–IR) spectrometer (Nicolet
Instruments model Avatar-100 equipped with diamond ATR, Madi-
son, WI, USA) was used to study characteristic functional groups on
the nanoparticle surfaces in the range of 500–4000 cm1. Specific
surface area calculations were determined by the Brunauer-
Emmett-Teller (BET) method with N2 gas using Micromeritics ASAP
2000 surface area and porosity system (Quantachrome, USA) by
first degassing the samples at 150 °C for 1 hour. Zeta potential of
synthesized nanoparticles and surface charge of nanoparticles
were determined by (Delsa Nano C, Beckman Coulter, CA, USA).
The percentage weight loss of CA@Fe3O4 NPs and Cys@Fe3O4 NPs
were studied in the temperature range of 30–600 °C at a heating
rate of 10 °C min in nitrogen atmosphere, using Thermogravimetric
analysis (TGA) (Q5000, TA instruments, DE, USA). The concentra-
tions of metal ions were determined by Inductively Coupled
Plasma-Optical Emission Spectroscopy (ICP-OES) iCAP 6500 ICP
from Thermo Scientific (MA, USA). Adjustments of solutions pH
were measured by a pH-meter (ORION 410).
2.3. Synthesis of precursor Fe3O4 NPs
The detailed synthetic process of Fe3O4 NPs (10 nm) have been
described elsewhere [27]. Briefly, 1.988 g (0.125 mol) of FeCl24H2-
O and 5.406 g (0.25 mol) of FeCl36H2O (1:2 molar ratio) were dis-
solved in 80 mL of water in a round bottomed flask at room
temperature. Then the temperature was slowly increased to
288 R.M. Ashour et al. / Chemical Engineering Journal 327 (2017) 286–296
70 °C in nitrogen atmosphere with continuous mechanical stirring
at 370 rpm for 30 min, then 20 mL of ammonium hydroxide solu-
tion (25%) was added to the reaction mixture and the mixture
was then kept at 70 °C for another 30 min. The obtained black pre-
cipitate was then washed three times with deionized water and
separated from the supernatant using a permanent magnet to
obtain the Fe3O4 NPs (about 1.30 g was obtained typically).
2.4. Synthesis of CA@Fe3O4 NPs and Cys@Fe3O4 NPs
In order to functionalize the synthesized Fe3O4 NPs with
citrates, 4 mL of an aqueous solution of citric acid (0.3 g mL1)
was added to the Fe3O4 NPs in deionized water and the tempera-
ture then raised slowly to 90 °C under refluxing conditions with
continuous mechanical stirring for 1 h. The obtained precipitate
was rinsed with water and separated by an external permanent
magnet to obtain CA@Fe3O4 NPs.
Surface functionalization of Fe3O4 NPs with L-cysteine was car-
ried out by mixing a known quantity of Fe3O4 NPs with 50 mL
(0.1 M) L-cysteine and the reaction mixture was kept under vigor-
ous shaking overnight. The product was separated from the solu-
tion using magnetic decantation and was washed three times
using deionized water to obtain Cys@Fe3O4 NPs.
2.5. Adsorption studies
Stock solutions of lanthanum(III) nitrate, neodymium(III)
nitrate, gadolinium(III) nitrate and yttrium(III) nitrate were pre-
pared by dissolving an appropriate amount of the required salt in
deionized water. Adsorption experiments were conducted by mix-
ing 10 mL of RE3+ mixture solution containing lanthanum La3+,
neodymium Nd3+, gadolinium Gd3+ and yttrium Y3+ with 2.5 mg
of magnetic nanoadsorbents (CA@Fe3O4 NPs or Cys@Fe3O4 NPs)
and the mixture was subjected to continuous shaking. Batch
adsorption experiments were carried out to investigate RE3+ ions
adsorption as a function of pH. The pH was adjusted in the range
3–8 by using nitric acid and sodium hydroxide, respectively. Initial
RE3+ concentration was varied from 5 to 50 mg L1 to study the
adsorption isotherms of RE3+ on surface functionalized Fe3O4
NPs. Contact time was changed from 1 to 120 min to study the
adsorption kinetic efficiency. Temperature was varied from 278
to 318 K to study thermodynamic parameters. The magnetic
nanoadsorbents CA@Fe3O4 NPs or Cys@Fe3O4 NPs were separated
from the aqueous phase with an external magnet. The adsorption
experiments were performed in duplicate and the average values
of total adsorption are reported. The adsorption capacity qe
(mg g1) of the adsorbents were determined by Eq. (1).
ðCi  Ce ÞV
Adsorption capacityðqe Þ ¼
m NPs and Cys@Fe3O4 NPs are 12 ± 3 nm and 10 ± 5 nm, respectively
where, Ci is the initial RE3+ concentration (mg L1), Ce is the equilib-
rium RE3+ concentration (mg L1) in aqueous solution, V is the total
volume of water (mL) and m is the mass of CA@Fe3O4 NPs or
Cys@Fe3O4 NPs (mg).
The adsorption isotherms were analyzed with the nonlinear
equations of Langmuir and Freundlich models using Eqs. (2) and
(3).
qmax kCe
qe ¼
1 þ kCe
qe ¼ K f C e1=n
1
where, qmax (mg g ) is the maximum adsorption capacity, k
(L mg1) is the Langmuir equilibrium constant, Kf (mg1n Ln g1)
is Freundlich constant and 1/n is the heterogeneity factor.
The adsorption kinetic experimental data were fitted to a non-
linear form of pseudo-first order and pseudo-second order models
using Eqs. (4) and (5), respectively.
qt ¼ qe ð1  ek 1t Þ ð4Þ
k2 q2e t
qt ¼ ð5Þ
1 þ k 2 qe t
where, k1 (min1) is the pseudo-first order rate constant of
adsorption, k2 (g mg1 min) is the pseudo-second order rate con-
stant of adsorption, qe (mg g1) is the adsorption capacity at equi-
librium and qt (mg g1) is the adsorption capacity at a given time t.
2.6. Selective adsorption studies
Experiments were performed to study the selectivity of
CA@Fe3O4 NPs and Cys@Fe3O4 NPs towards RE3+ adsorption. The
selective adsorption experiments were carried out by mixing a
known amount of CA@Fe3O4 NPs or Cys@Fe3O4 NPs with La3+,
Nd3+, Gd3+ and Y3+ solutions containing Ni2+, Ca2+ and Mg2+ at
1:1 molar ratio using a shaker at room temperature. The aqueous
phase was separated from the solid phase by using an external
magnet followed by ultra-centrifuging of the supernatant at
10,000 rpm and the concentration of metal ions in the supernatant
was determined by ICP-OES.
2.7. Desorption studies
To examine the feasibility of recycling the coated nanoparticles,
desorption studies were performed using 0.1–1 mol L1 of eluting
solution of NaOH or HNO3 for 30 min. The desorption efficiency
of La3+, Nd3+, Gd3+ and Y3+ from the loaded CA@Fe3O4 NPs or
Cys@Fe3O4 NPs was calculated using Eq. (6).
Cdes
Desorption% ¼ x100 ð6Þ
Cads
where, Cdes is the amount of La3+, Nd3+, Gd3+ and Y3+ released
into aqueous solution (mg L1) and Cads is the amount of La3+,
Nd3+, Gd3+ and Y3+ adsorbed on the coated Fe3O4 NPs (mg L1).
3. Results and discussion
3.1. Characterization of CA@Fe3O4 NPs and Cys@Fe3O4 NPs
The TEM images of CA@Fe3O4 NPs and Cys@Fe3O4 NPs
(Fig. 2a and b, respectively), revealed that Fe3O4 NPs are well sep-
arated spherical particles. The particle size distribution determined
from TEM micrographs, showed that the particles size of CA@Fe3O4
ð1Þ
(Fig. 2a (inset) and b (inset)).
The XRD patterns of the synthesized CA@Fe3O4 NPs and
Cys@Fe3O4 NPs are presented in Fig. 2c and d, respectively. Five
characteristic peaks for Fe3O4 NPs corresponding to (2 Theta)
= 30.136, 35.554, 43.2, 53.529, 57.012 and 62.961 for (2 2 0),
(3 1 1), (4 0 0), (4 2 2), (5 1 1) and (4 4 0) planes were observed. These
peaks are well matched with the magnetite characteristic peaks
confirming the functionalization process did not result in phase
alteration of Fe3O4 NPs [28].
ð2Þ The TGA thermograms of pristine Fe3O4 NPs, CA@Fe3O4 NPs and
Cys@Fe3O4 NPs are shown in Fig. 2e and f, respectively. About 1%
weight loss for all NPs are observed at 50–200 °C due to the dehy-
ð3Þ
dration of NP surface. Above 200 °C, 8.8% weight loss of CA@Fe3O4
NPs and 2.8% for Cys@Fe3O4 NPs were observed due to the removal
of the ligands. Weight losses above 450 °C is related to transforma-
tion of Fe3O4–Fe2O3 [28]. The obtained TGA results confirm that the
 R.M. Ashour et al. / Chemical Engineering Journal 327 (2017) 286–296 289

Fig. 2. Characterization of the functionalized CA@Fe3O4 NPs and Cys@Fe3O4 NPs: TEM image of (a) CA@Fe3O4 NPs and (b) Cys@Fe3O4 NPs with particle size distribution
(inset); XRD pattern of (c) CA@Fe3O4 NPs and (d) Cys@Fe3O4 NPs; TGA curves of (e) CA@Fe3O4 NPs, (f) Cys@Fe3O4 NPs and pristine Fe3O4 NPs; FT-IR analysis of (g) CA, Fe3O4
NPs and CA@Fe3O4 NPs and (h) Cys, Fe3O4 NPs and Cys@Fe3O4 NPs.

surface of Fe3O4 NPs was successfully functionalized with CA and
Cys.
FT-IR spectrum of CA@Fe3O4 NPs (Fig. 2g) showed that car-
boxylic functional group at 1680 cm1 assigned to C@O vibration
of CA was shifted to lower wave number due to the covalent bond-
ing on the surface of Fe3O4 nanoparticles as confirmed by the
appearance at 1582 cm1. The symmetric stretching of the COO
group of CA at 1401 cm1 is also slightly shifted to lower frequen-
cies with a strong but broad band appearing at 1389 cm1, con-
firming the successful functionalization of Fe3O4 nanoparticles
with CA [29]. Similarly, the infrared spectrum of Cys@Fe3O4 NPs
(Fig. 2h), reveal a strong broad peak at 3055 cm1, attributed to
290 R.M. Ashour et al. / Chemical Engineering Journal 327 (2017) 286–296
the ANH2 stretches, at 1586 cm1 due to the symmetric stretching
of the C@O, at 1375 cm-1 due to the symmetric stretching of the
COO The band at 2555 cm1 attributed to the –SH group of Cys,
disappear in Cys@Fe3O4 NPs implying that the Cys molecules
attaches to the surface of the Fe3O4 NPs via the formation of FeAS
covalent bond [26,28].
The BET analysis for Fe3O4 NPs, CA@Fe3O4 NPs and Cys@Fe3O4
NPs are shown in Fig. S1a, b and c (ESIy), respectively. The specific
surface area of Fe3O4 NPs, CA@Fe3O4 NPs and Cys@Fe3O4 NPs were
87.95, 94.65 and 53.95 m2 g1, respectively. The magnetic proper-
ties of the magnetic nanoparticles have been reported elsewhere
[30].
The zeta potential of CA@Fe3O4 NPs and Cys@Fe3O4 NPs in the
pH range of 2–10 are shown in Fig. 3. In case of CA@Fe3O4 NPs, high
negative charges on the surface is observed and the isoelectric
point (IEP) could not be found in the entire pH range studied, as
also observed by others [29]. The amount of the negative charges
increased with increasing pH due to the deprotonation of car-
boxylic groups in the case of functionalisation with citrates. The
obtained results thus confirm that grafting of carboxylic groups
to the surface of Fe3O4 NPs has occurred [31], as the IEP of Fe3O4
NPs is expected to be at pH 6.5 [32]. The zeta potential measure-
ments of Cys@Fe3O4 NPs showed that the zeta potential values of
Cys varies with pH, similar to other amino acids.[33] The IEP of
Cys has been reported to be at pH 5.1 [34]. Below the IEP, a positive
charge of Cys due to the protonation of amino and carboxylic
groups on the surface of the Fe3O4 NPs, render the overall charge
positive. Above IEP, the surface is negatively charged due to depro-
tonation of carboxylic and amino groups at higher pH values which
causes the surface potential to cross from zero to the negatively
charged region [35].
3.2. Adsorption kinetics
The kinetic data for the adsorption of La3+, Nd3+, Gd3+ and Y3+
ions on CA@Fe3O4 NPs and Cys@Fe3O4 NPs are shown in
Fig. 4a and b, respectively. It is clear that the adsorption of La3+,
Nd3+, Gd3+ and Y3+ ions increase rapidly in the first 5 and 15 min
for both the Cys@Fe3O4 NPs and CA@Fe3O4 NPs. and adsorption
equilibrium was achieved within 15 and 30 min. The rapid adsorp-
tion of La3+, Nd3+, Gd3+ and Y3+ ions is attributed to the abundance
of surface sites on the Fe3O4 surface-functionalized with Cys and
CA [36].
The adsorption kinetics is an important aspect that can provide
useful information of the adsorption mechanisms. Experimentally
Fig. 3. Zeta potential of CA@Fe3O4 NPs and Cys@Fe3O4 NPs at different pH.
determined kinetic data were analyzed using nonlinear pseudo
first-order and pseudo second-order models. The obtained fit of
the kinetic parameters of CA@Fe3O4 NPs and Cys@Fe3O4 NPs are
shown in Table 1. The pseudo-second-order model fitted well with
all experimental data (La3+: R2 = 0.999, Nd3+: R2 = 0.996, Gd3+:
R2 = 0.995 and Y3+: R2 = 0.991 for CA@Fe3O4 NPs and La3+:
R2 = 0.993, Nd3+: R2 = 0.995, Gd3+: R2 = 0.987 and Y3+: R2 = 0.998
for Cys@Fe3O4 NPs), and also the obtained qe,cal values from the
pseudo-second-order model were found to agree well to the exper-
imentally obtained qe,exp. The fitting results thus indicate that the
adsorption rate was mainly determined by the chemical adsorp-
tion process through sharing or exchange of electrons between
La3+, Nd3+, Gd3+ and Y3+ ions on the CA@Fe3O4 NPs and Cys@Fe3O4
NPs [37].
3.3. Effect of pH
pH factor plays an important role in the adsorption of RE3+ ions
on the surface of the NPs. To investigate the effect of pH on the
adsorption of La3+, Nd3+, Gd3+ and Y3+ ions on CA@Fe3O4 NPs and
Cys@Fe3O4 NPs, we prepared a series of mixed sample solutions
containing 5 mg L1 of La3+, Nd3+, Gd3+ and Y3+ ions
(Fig. 4c and d). The pH values of the solutions were adjusted by
HNO3 or NaOH solution. This study is restricted up to a maximum
pH 8.0 since beyond this pH, precipitation of RE3+ ions occur as
observed from the speciation of REEs [38]. At pH > 8, REEs could
be precipitated as insoluble hydroxides i.e. RE(OH)3(s) [38,39].
The obtained results revealed that the adsorption capacity of
CA@Fe3O4 NPs and Cys@Fe3O4 NPs for La3+, Nd3+, Gd3+ and Y3+ ions
increased with increasing the pH, so, pH = 7.0 was selected for sub-
sequent studies.
3.4. Temperature dependence
The temperature dependence of La3+, Nd3+, Gd3+ and Y3+ adsorp-
tion on the surface of CA@Fe3O4 NPs and Cys@Fe3O4 NPs were
studied at 278–318 K. From the data represented in Fig. S2 (ESIy),
the adsorption capacity of CA@Fe3O4 NPs and Cys@Fe3O4 NPs for
the adsorption of La3+, Nd3+, Gd3+ and Y3+ ions increased upon
increasing the temperature due to the higher energy of the system
facilitating the adsorption process, as well as due to the higher
affinity of active binding sites on the surface of the coated Fe3O4
NPs [40].
3.5. Thermodynamics parameters
The standard enthalpy change (DH°), entropy change (DS°), and
Gibb‘s energy change (DG°) were evaluated by applying Eqs. (7)
and (8) [41].
DH  DS
lnKd ¼  þ ð7Þ
RT R
DG ¼ DH  T DS ð8Þ
1 1
where, R is the gas constant (8.314 J mol K ), T is the absolute
temperature (Kelvin) and the distribution coefficients (Kd, mL g1)
were defined by using Eq. (9) [42].
ðCi  Cf Þ
Kd ðRE3þ Þ ¼  V=m ð9Þ
Cf
where, Kd (RE3+) is the distribution coefficient, Ci = initial concentra-
tion, Cf = final concentration, V = volume of solution, and m = mass
of CA@Fe3O4 NPs or Cys@Fe3O4 NPs, which is defined as the ratio
of the concentration of rare earth ions in the solid phase to that
in liquid phase.
 R.M. Ashour et al. / Chemical Engineering Journal 327 (2017) 286–296 291

Fig. 4. Typical pseudo-second order fitting of the adsorption of La3+, Nd3+, Gd3+ and Y3+ ions using (a) CA@Fe3O4 NPs and (b) Cys@Fe3O4 NPs. Experimental conditions: Ci
3+
(RE) = 5 mg L1, pH = 7.0, m of adsorbents = 2.5 mg and v = 10 mL at room temperature. Effect of pH on adsorption of La3+, Nd3+, Gd3+ and Y3+ ions using (c) CA@Fe3O4 NPs,
1
time = 30 min and (d) Cys@Fe3O4 NPs, time = 15 min. Experimental conditions: C3+)i(RE = 5 mg L , m of adsorbents = 2.5 mg and v = 10 mL at room temperature.

Table 1
Kinetic parameters of La3+, Nd3+, Gd3+ and Y3+ adsorption on CA@Fe3O4 NPs and Cys@Fe3O4 NPs.

Model La3+ Nd3+ Gd3+ Y3+

CA@Fe3O4 NPs
Pseudo-first order qe,cal. (mg g1) 9.1 ± 0.01 12 ± 0.02 16.9 ± 0.02 11.1 ± 0.01
qe,exp. (mg g1) 10 13.3 18 12
k1 (min1) 0.15 ± 0.005 0.09 ± 0.005 0.064 ± 0.003 0.1 ± 0.001
R2 0.961 0.982 0.982 0.984
Pseudo-second order qe,cal (mg g1) 10.1 ± 0.30 14 ± 0.24 19.6 ± 0.41 12.4 ± 0.13
qe,exp. (mg g1) 10 13.3 18 12
k2 (g mg1 min1) 0.02 ± 0.001 0.007 ± 0.005 0.003 ± 0.003 0.01 ± 0.001
R2 0.999 0.996 0.995 0.991
Cys@Fe3O4 NPs
Pseudo-first order qe,cal (mg g1) 18.4 ± 0.08 20.1 ± 0.08 21.3 ± 0.02 20 ± 0.04
qe,exp.(mg g1) 18.5 20.3 21.5 20.1
k1 (min1) 2.5 ± 0.15 3.2 ± 0.13 3.8 ± 0.16 2.3 ± 0.14
R2 0.891 0.863 0.833 0.892
Pseudo-second order qe,cal. (mg g1) 18.5 ± 0.04 20.32 ± 0.01 21.45 ± 0.015 20.1 ± 0.006
qe,exp.(mg g1) 18.5 20.3 21.5 20.1
k2 (g mg1 min1) 0.52 ± 0.03 1.03 ± 0.002 1.8 ± 0.15 0.44 ± 0.008
R2 0.993 0.995 0.987 0.998

The standard enthalpy change (DH°) and the entropy change for
CA@Fe3O4 NPs and Cys@Fe3O4 NPs can be calculated from the slope
and intercept of the plot of ln Kd vs. 1/T using the van’t Hoff plot as
shown in Fig. 5a and b, respectively. The obtained values of DG°
(kJ mol1), DH° (kJ mol1) and DS° (J mol1) are summarized in
Table 2. The values of enthalpy change (DH°) are positive,
indicating that the adsorption of La3+, Nd3+, Gd3+ and Y3+ ions are
endo-thermally driven and thus increasing the temperature is
advantageous for higher adsorption. The positive values of entropy
change (DS°) obtained in this study indicates an increase in the
degree of freedom at the solid-liquid interface [27]. It favors
complexation and stability of the adsorption of RE3+ ions in both
the systems studied in this work. In addition, the negative charge
of Gibb’s free energy (DG°) values in the temperature range stud-
ied, suggest that the adsorption process is spontaneous and more
favorable at higher temperatures indicating that the adsorption
reactions are primarily driven towards the products.
3.6. Adsorption isotherms
The effect of the concentration of RE3+ (La3+, Nd3+, Gd3+ and Y3+
ions) on the adsorption efficiency were investigated under the
292 R.M. Ashour et al. / Chemical Engineering Journal 327 (2017) 286–296
Fig. 5. Linear plot of ln Kd versus 1/T for adsorption capacity of La3+, Nd3+, Gd3+ and Y3+ on (a) CA@Fe3O4 NPs, time = 30 min and (b) Cys@Fe3O4 NPs, time = 15 min.
1
Experimental condition: C3+)i(RE = 5.0 mg L , pH = 7.0, m of adsorbents = 2.5 mg and v = 10 mL.
Table 2
Thermodynamic parameters for the adsorption of La3+, Nd3+, Gd3+ and Y3+ by CA@Fe3O4 NPs and Cys@Fe3O4 NPs at 278–318 K.
Parameters La3+
CA@Fe3O4 NPs
DH° (kJ mol1) 41.85
DS° (J mol1) 165
DG°(kJ mol1) (–46 to –52)
R2 0. 995
Cys@Fe3O4 NPs
DH° (kJ mol1) 16.7
DS° (J mol1) 87
DG°(kJ mol1) (–24 to –28)
R2 0.996
optimized conditions. The results demonstrate that the adsorbed
amount of RE3+ ions (qe) on CA@Fe3O4 NPs and Cys@Fe3O4 NPs
increased with increasing initial concentration of RE3+ and reached
a plateau at higher concentrations due to saturation of the number
of binding sites in a fixed amount of CA@Fe3O4 NPs and Cys@Fe3O4
NPs. The experimental data was interpreted by non-linear Lang-
muir and Freundlich sorption isotherms (Fig. 6a and b) and the cor-
responding parameters related to Langmuir and Freundlich models
are summarized in Table 3. It was found that the equilibrium
adsorption capacity was better described by the Langmuir iso-
therm model, indicating that the monolayer adsorption process
can explain the metal adsorption. The obtained qmax values
(Table 3) suggest that the adsorption affinity of both systems
decreased in the order Gd3+ > Nd3+ > Y3+ > La3+ due to the compet-
itive adsorption between La3+, Nd3+, Gd3+ and Y3+ ions on the same
adsorption site on the surface of the NPs. The relative order is con-
sistent with the chemical properties of RE3+ such as the sequence
of the electronegativity and the size of the metal ions. The maxi-
mum adsorption capacity values of RE3+ ions for Cys@Fe3O4 NPs
is almost double the values of CA@Fe3O4 NPs, which is attributed
to the two different functional groups (amine and carboxylic
groups in Cys) that leads to increased active sites on the Fe3O4
NPs surfaces.
A comparison of the adsorption capacity with different func-
tionalized nanoparticles are represented in Table 4.
3.7. Adsorption mechanism
Based on the results obtained from zeta potential measure-
ments (Fig. 3), FT-IR spectrum (Fig. S3, ESIy) and the trend of
RE3+ ions adsorption at different pH values (Fig. 4c and d), we pro-
pose a schematic representation of the adsorption mechanisms as
shown in scheme 1. Generally, The RE3+ ions can be estimated from
the stability constants; it is clear that RE3+ ions in solution is
Nd3+ Gd3+ Y3+
53 35 44
201 135 168
(–56 to –64) (–38 to–43) (–47 to –53)
0. 993 0. 995 0. 999
14 15.5 11
89 92 65
(–25 to –28) (–25 to –29) (–18 to –20)
0. 991 0.997 0. 994
predominated by positively charged species such as RE3+ ions that
are present in the form of RE3+, RE(OH)+, RE(OH)2 and RE(OH)3 at
various pH values. At pH < 8, the main species of RE3+ ions are
RE3+ and RE(OH)+ and the removal of RE3+ is mainly accomplished
by surface complexation. For CA@Fe3O4 NPs, the negatively
charged COO groups have strong coordinative affinity towards
La3+, Nd3+, Gd3+ and Y3+ ions. These carboxylate ions capture the
RE3+ ions by forming complexes and the ability of surface complex-
ation increases with increasing pH of the solution. At higher pH,
the chelating complexes of carboxylate and La3+, Nd3+, Gd3+ and
Y3+ ions are expected more than at lower pH because the chelation
sites occupied by H+ are released at higher pH leading to the
desired chelation [47].
In case of Cys@Fe3O4 NPs, there are two different surface func-
tional groups, carboxylate (COO) and amine (ANH2) At low pH,
the Cys@Fe3O4 NPs surface has a net positive charge due to the pro-
tonation of amine (ANH+3). RE3+ ions adsorption occurred at pH < 5
in the range 5–10 mg g1. This could be attributed to the electro-
static repulsion between RE3+ and the surface of Fe3O4 NPs, which
increase the conversion of ANH2 groups to ANH+3 and there were
few of ANH2OH sites available on the Cys@Fe3O4 NPs surface
for the adsorption of ions through surface complexation [48]. At
higher pH the concentration of H+ increases as observed from the
zeta potential measurements. The increase in the negative charge
on the surface of Fe3O4 NPs are possibly due to the carboxylate
sites on Fe3O4 NPs and the formation of NH2OH sites. Also, the
increased adsorption capacity of metal ions through the electro-
static attraction mechanism between (NH2OH and RE3+) and sur-
face complexation mechanism between (COO and RE3+) seems to
be the major routes for the adsorption of RE3+ ions on the surface of
Cys@Fe3O4 NPs [27].
FT-IR spectra of the RE3+ loaded (CA@Fe3O4 NPs-RE3+) is shown
in Fig. S1a (ESIy). The stretching vibrational of C@O peak was
longer, broad and shifted from 1582 to 1605 cm1. Additionally,
 R.M. Ashour et al. / Chemical Engineering Journal 327 (2017) 286–296 293

Fig. 6. The non-linear Langmuir and Freundlich fitting of adsorption capacity of La3+, Nd3+, Gd3+ and Y3+ on (a) CA@Fe3O4 NPs, time = 30 min and (b) Cys@Fe3O4 NPs,
time = 15 min. Experimental condition: pH = 7.0, m of adsorbents = 2.5 mg and v = 10 mL at room temperature.

Table 3
Parameters of Langmuir and Freundlich adsorption isotherm models.

Model La3+ Nd3+ Gd3+ Y3+

CA@Fe3O4 NPs
Langmuir qe, (mg g1) 32.5 ± 0.71 41 ± 0.11 52 ± 0.20 35.8 ± 0.72
kL (L mg1) 0.7 ± 0.08 0.3 ± 0.09 0.3 ± 0.03 0.67 ± 0.02
R2 0.995 0.999 0.993 0.991
Freundlich n 16 13.8 18 17.3
kF (mg g1)(L g1)n 4.526 3.2 3.35 4.53
R2 0.973 0.978 0.978 0.955
Cys@Fe3O4 NPs
Langmuir qe,(mg g1) 57.2 ± 0.31 85.5 ± 0.39 98 ± 0.50 73 ± 0.34
kL(L mg1) 1.73 ± 0.46 1.812 ± 0.4 0.81 ± 0.11 0.47 ± 0.08
R2 0.988 0. 987 0. 998 0.997
Freundlich n 32.75 46.73 18 13.8
kF (mg g1)(L g1)n 5.32 4.0 3.3 2.98
R2 0.921 0.979 0.978 0.946

Table 4
Reported literature review of La3+, Nd3+, Gd3+ and Y3+ ions adsorption capacity by different adsorbents.

Adsorbents Ions Adsorption

capacity (mg g1)
Magnetic nano-hydroxyapatite [40] Nd and Sm 323 and 370
Magnetic silica nanocomposite (P507) [43] La 55.9
Magnetic alginate (P507) microcapsules [44] Nd 149.3
Fe3O4 (humic acid) [45] Eu 10.6
Dibenzo- 18-crown-6 ether onto Cs 50.32
mesoporous silica monoliths [46]
CA@Fe3O4 NPs (this work) La, Nd, Gd, Y 32.5, 41, 52 and 35.8
Cys@Fe3O4 NPs (this work) La, Nd, Gd, Y 57.2, 85.5, 98 and 73

the symmetric stretching of COO group shifted to 1361 cm1, that the v(C@O) band at 1586 cm1 shifted to 1628 cm1. The
indicating that the oxygen in COO and C@O are involved in chelat- broad and strong bands of tertiary amine at 3055 cm1 were
ing adsorption of RE3+. The FTIR spectrum for Cys@Fe3O4 NPs after shifted to 3378 cm1 due to the interaction between carboxylate
adsorption of RE3+ ions are presented in Fig. S1b (ESIy). It is clear and amine groups in Cys and RE3+ ions [49].
294 R.M. Ashour et al. / Chemical Engineering Journal 327 (2017) 286–296

Scheme 1. Schematic representations of proposed mechanisms for adsorption of RE3+ ions by (a) CA@Fe3O4 NPs and (b) Cys@Fe3O4 NPs.

3.8. Desorption studies
The recovery of adsorbed RE3+ ions from the loaded CA@Fe3O4
NPs and Cys@Fe3O4 NPs was tested using different eluting solu-
tions. The desorption experiments were carried out in an aqueous
solution of sodium hydroxide (0–0.72%), whereby it was found that
the recovered amounts of La3+, Nd3+, Gd3+ and Y3+ were negligible.
The low recovery of all metals may be attributed to the strong
binding between CA@Fe3O4 NPs/Cys@Fe3O4 NPs with the RE3+ ions
in alkaline conditions which is in conformation to the observations
made from pH studies and zeta potential measurements as well as
the observations from the FT-IR measurements. Different concen-
trations of nitric acid were tested for the recovery of RE3+ species
from the loaded coated Fe3O4 NPs. as shown in Fig. 7a and b. It is
clear that recovery of all metals can be accomplished with 0.5 M
HNO3 in which 85% and 97% recovery can be achieved for
CA@Fe3O4 NPs and Cys@Fe3O4 NPs, respectively.
3.9. Selective separation
The selective separation performance of La3+, Nd3+, Gd3+ and Y3+
ions from a mixture of a base metal solution containing RE3+ and
Mg2+, Ca2+ and Ni2+ ions with initial concentration of
0.01 mmol L1 and 0.05 mmol L1 at pH 7.0 was investigated. From
the obtained results (Fig. 8), CA@Fe3O4 NPs and Cys@Fe3O4 NPs
adsorbed much more RE3+ ions than other base metal ions. This
can be explained in terms of strong binding of La3+, Nd3+, Gd3+
and Y3+ with O and N donor atoms than with the common interfer-
ing ions. The RE3+ ions are hard Lewis acid cations and have high
tendency to complex with hard Lewis base atoms [50]. Here, the
CA@Fe3O4 NPs and Cys@Fe3O4 NPs containing O and N donor
atoms strongly bind to La3+, Nd3+, Gd3+ and Y3+ than the other com-
peting cations according to Pearson’s hard and soft acid and base
theory [51]. The results indicate that the CA@Fe3O4 NPs and
Cys@Fe3O4 NPs have higher adsorption affinity of heavy rare earth
ions such as (Gd3+, Y3+) ions than light rare earth ions such as
(Nd3+, La3+). Ionic strength does not significantly seem to affect
adsorption process.
The selectivity was reported using separation factor (SF),
which compares the molar ratio of two element ions. The
separation of Gd3+ ions was chosen because of the difference
in the ionic radius. SF was defined as the ratio of distribution
coefficients; SF(Gd/La) = Kd(Gd)/Kd(La), SF(Gd/Nd) = Kd(Gd)/Kd(Nd)
and SF(Gd/Y) = Kd(Gd)/Kd(Y) (see Eq. (9) for more details).

Fig. 7. Recovery efficiency% of La3+, Nd3+, Gd3+ and Y3+ from the loaded (a) CA@Fe3O4 NPs and (b) Cys@Fe3O4 NPs using different concentration of HNO3 as an eluting solution.
 R.M. Ashour et al. / Chemical Engineering Journal 327 (2017) 286–296
Fig. 8. Separation of La3+, Nd3+, Gd3+ and Y3+ from a mixture of (RE3+ ions and Mg2+, Ca2+ and Ni2+) of 0.01 and 0.05 mmol L1 concentrations by (a) CA@Fe3O4 NPs,
time = 30 min and (b) Cys@Fe3O4 NPs time = 15 min and pH = 7.0 at room temperature.
Table 5
Selective SF of Gd3+ from the mixed Gd3+/La3+, Gd3+/Nd3+ and Gd3+/Y3+ solution using CA@Fe3O4 NPs and Cys@Fe3O4 NPs.
CA@Fe3O4 NPs 0.01 M 0.05 M
SF(Gd3+/La3+) 3.7 1.98
SF(Gd3+/Nd3+) 1.4 1.04
SF(Gd3+/Y3+) 1.8 1.66
One can notice that SF increases rapidly at the beginning of the
Gd3+/La3+, Gd3+/Nd3+and Gd3+/Y3+ separation series and stagnates
for the heaviest lanthanides. The obtained results in Table 5,
demonstrate that the separation of Gd3+ from mixed Gd3+/La3+,
Gd3+/Nd3+ and Gd3+/Y3+ solution was achieved by using CA@Fe3O4
NPs and Cys@Fe3O4 NPs. The Cys@Fe3O4 NPs have a higher selectiv-
ity separation toward heavier rare earth ions than CA@Fe3O4 NPs,
which can be explained by the fact that it has amine and carboxylic
functional groups on the surface.
4. Conclusions
In this work, different chelating functional groups with mag-
netic nanoparticles (CA@Fe3O4 NPs and Cys@Fe3O4 NPs) were suc-
cessfully synthesized and characterized. The role of the functional
groups on the adsorption of rare earth ion and selective separation
of Gd3+ from aqueous solutions was investigated. The adsorption
behaviour was found to be highly dependent on the surface func-
tionality of Fe3O4 NPs. The time needed to reach maximum adsorp-
tion was attained in less than 30 min and high loading capacity
was obtained (98 mg g1 and 52 mg g1 for Cys@Fe3O4 NPs and
CA@Fe3O4 NPs, respectively). Maximum adsorption capacity qmax
of the RE3+ was better descried by Langmuir isotherm model, and
the relative order of qmax values Gd3+ > Nd3+ > Y3+ > La3+ was con-
sistent with the sequence of electronegativity and ionic radial sizes
of REEs. The adsorption process is of endothermic nature in both
the systems are more favourable at higher temperatures. Adsorp-
tion kinetic studies follow a pseudo-second order model suggest-
ing that the rate-limiting step is chemisorption. The adsorption
of La3+, Nd3+, Gd3+ and Y3+ was not affected by commonly coexist-
ing ions such as Ca2+, Mg2+ and Ni2+, which illustrates the selective
adsorption of La3+, Nd3+, Gd3+ and Y3+ from diluted aqueous solu-
tions. High desorption efficiency was obtained in which more than
90% RE3+ ions recovery was achieved in both systems under acidic
conditions. The Cys@Fe3O4 NPs exhibits highly selective separation
factor for pairs of Gd3+ /La3+, Gd3+/Nd3+, Gd3+/Y3+ ions more than
CA@Fe3O4 NPs. These results therefore demonstrate that Cys@Fe3-
O4 NPs possesses high specificity for the separation of RE3+ ions
from aqueous solution and could be applied in the field of recovery
and separation of REEs from mineral sources.
295
Cys@Fe3O4 NPs 0.01 M 0.05 M
SF(Gd3+/La3+) 4.8 2.3
SF(Gd3+/Nd3+) 2.3 1.5
SF(Gd3+/Y3+) 2.23 1.8
Acknowledgments
Radwa M. Ashour is grateful to Erasmus Mundus program (EM-
WELCOME) for financial support and KTH for hosting and giving
the opportunity to work in Functional Materials Laboratory.
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.cej.2017.06.101.
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