Hydrometallurgy 150 (2014) 83–91

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Study on recognition and separation of rare earth ions at picometre scale

by using efficient ion-surface imprinted polymer materials
Baojiao Gao a,⁎, Yongqi Zhang b, Yang Xu b
a
Department of Chemical Engineering, North University of China, Taiyuan 030051, People's Republic of China
b
General Research Institute for Nonferrous Metals, Beijing 100088, People's Republic of China

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

Article history: The graft-polymerization of hydroxyethyl methylacrylate (HEMA) on micro-sized silica gel particles was first
Received 27 February 2014 conducted by initiating of a surface-initiating system, which was constituted by the bonded amino groups on
Received in revised form 10 September 2014 the modified silica gel particles and persulfate in the solution, obtaining the grafted particles PHEMA/SiO2 with
Accepted 15 September 2014
a high grafting degree of 40 g/100 g. Subsequently, 8-hydroxyquinoline as a ligand with strong chelating ability
Available online 5 October 2014
for metal ions was bonded on the side chains of the grafted macromolecule PHEMA through the substitution re-
Keywords:
action between 5-chloromethyl-8-hydroxyquinoline (CHQ) and the hydroxyl group of the grafted macromole-
Ion surface imprinting technique cule PHEMA, preparing the functional grafted particles HQ-PHEMA/SiO2. On the basis of examining the
Rare earth ion chelating adsorption property of HQ-PHEMA/SiO2 particles for Pr3+ ion, the Pr3+ ion surface-imprinting was car-
Ion recognition ried out by using the effective surface-imprinting technique of “pre-grafting and post-crosslinking/imprinting”
Separation established by our group. During the surface-imprinting process, Pr3+ ion was used as a template ion, and
2,2′-dichlorodiethyl ether was used crosslinked, resulting in the Pr3+ ion surface-imprinted material IIP-HQP/
SiO2. The recognition and binding characters of IIP-HQP/SiO2 towards Pr3+ ion were investigated in-depth
with La3+ and Ce3+ ions as two contrast ions. The experimental results show that the IIP-HQP/SiO2 particles pos-
sess special recognition selectivity and high binding ability for Pr3+ ion. The binding capacity of IIP-HQP/SiO2 for
Pr3+ ion reaches 0.13 mmol/g, and relative to La3+ and Ce3+ ions, the selectivity coefficients of IIP-HQP/SiO2 for
Pr3+ ion are 5.22 and 5.12, respectively. La, Ce and Pr are three neighbouring rare earth elements, and the ion ra-
dius differences between La3+, Ce3+ and Pr3+ ions are only in a range of 2–5 pm. Obviously, in this investigation,
the mutual separation of La3+, Ce3+ and Pr3+ ions at picometre scale is realized successfully by using the ion
surface-imprinted polymer material with high performance.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction because of the similarity of their chemical properties derived from

Rare earth (RE) elements are a very important group of chemical el-
ements. Owing to their peculiar physical, chemical, and nuclear proper-
ties of themselves or their compounds, the RE elements play an
important role in many fields of advanced materials science such as
electronics, magnetism, metallurgy, phosphors, catalysts, glass, laser
and ceramic technology (Abreu and Morais, 2010; Hasegawa et al.,
2011; Jia et al., 2009; Jordens et al., 2013; Lee et al., 2010). The rare
earth elements invariably occur together in the source minerals
(bastansite, monazite, and xenotime) (Banda et al., 2012; Nasab et al.,
2011). The rare earth elements are required to be mutually separated
for the industrial applications. Further, the purification of these
elements is gaining considerable attention with the ever-increasing
demand for high-purity rare earth elements and their compounds.
However, the separation and recovery of rare earths are very difficult
⁎ Corresponding author. Tel.: +86 351 3924795; fax: +86 351 3922118.
E-mail address: gaobaojiao@126.com (B. Gao).
their same valence and similar ion radii (arising from lanthanide
contraction) (Suzuki et al., 2006; Wannachod et al., 2011), especially
for the separation of those light rare earths from each other. The selec-
tive separation of mixed rare-earth (RE) metals poses glaring challenge
to the industry. The separation methods are variously conducted, but
there are the two basic types, solvent extraction and ion exchange tech-
nologies (Belova et al., 2009; Hubicka and Kołodyńska, 2008; Lee et al.,
2009). In both conventional separation methods, there are some prob-
lems, such as complicated operation, lack of selectivity, tight separabil-
ity condition, remain of organic material, and restriction on separable
rare earth elements (Lee et al., 2009; Suzuki et al., 2006). Therefore, it
is needed to develop new methods and materials for facilitating the sep-
aration and purification of rare earth elements.
In the present work, we propose a more simple and highly effective
separation technique based on the rare earth ion surface-imprinted ma-
terial, and try to conduct the separation of the three neighbouring light
rare earth ions, lanthanum (La3+), cerium (Ce3+) and praseodymium
(Pr3+) ions, so as to realize their mutual separation at picometre scale
(the difference of their ionic radii is in a range of 2–5 pm).

http://dx.doi.org/10.1016/j.hydromet.2014.09.017
0304-386X/© 2014 Elsevier B.V. All rights reserved.
84 B. Gao et al. / Hydrometallurgy 150 (2014) 83–91
Molecular imprinting is a technique for creating polymeric matri-
ces containing tailor-made receptors and having special recognition
ability and predesigned selectivity for the template molecule
(Athikomrattanakul et al., 2009; Okutucu and Önal, 2011; Qi et al.,
2010), and so molecularly imprinted polymers (MIPs) are described
as artificial antibodies or receptors. Within the particles of MIPs, a
great deal of imprinted cavities is distributed and these cavities are
complementary to the template molecule in shape, size and func-
tionality, and it is the fundamental reason that MIPs have the special
recognition selectivity for the template molecule. As the template is
an ion in the preparation process of MIPs, the resultant products are
called ion-imprinted polymers (IIPs) that especially recognize the
template ion (Otero-Romaní et al., 2009; Vatanpour et al., 2011). In
recent years, the molecular imprinting solid-phase extraction
(MISPE) technique with MIPs as well as IIPs as solid adsorbents
with high performance has been widely used in many fields, in
which the fine selectivity for the target substances is required, such
as separation, purification, pre-concentration and determining, and
constructing sensors (Akdamar et al., 2009; Byun et al., 2010;
Javanbakht et al., 2009; Patel et al., 2009; Yuan et al., 2011). We
think that introducing ion-imprinting technique into hydrometallur-
gy is promising, and it is potential to use MIPSPE method with IIPs as
solid adsorbents for separating the neighbouring rare earth
elements.
The conventional method of preparing molecular imprinted poly-
mers (MIPs) is entrapment way, and the prepared MIPs have some dis-
advantages (Kitahara et al., 2010; Pan et al., 2011), such as taking time,
complicated preparation process, less recognition sites inside the matrix
particle obtained by crushing and grinding the imprinted polymeric
monolith, and greater diffusion resistance for the template molecules
because of the thick matrix. These shortcomings make MIPs prepared
with the conventional method to have poor binding property and
slow binding kinetics for the template molecules. In order to overcome
these drawbacks, recently, the various surface-imprinting methods
have been actively developed (Gai et al., 2011; Gu et al., 2011; Wang
et al., 2008), and the researchers try to build molecular recognition sys-
tems on the surface of solid particles. We also devote ourselves to devel-
op the new surface-imprinting methods. Lately, we put forward a novel
molecule (ion) surface-imprinting technique of “pre-grafting and post-
crosslinking/imprinting” (Gao et al., 2009; Gao et al., 2010; Gao et al.,
2011; Gao et al., 2013a, 2013b). Its basic points are as follows. Functional
polymers, which has strong adsorption action for the template molecule
or ion, are pre-grafted on the surfaces of micron-sized solid particles,
and subsequently, the post-crosslinking of the functional polymers,
which has adsorbed the template molecule or ion, is conducted using
special crosslinking agent so as to realize the imprinting of the template
molecule or ion. After the removal of the template molecules, a mass of
the imprinted caves capable of recognizing and re-binding the template
molecules (ions) is left and distributed within a thin polymer layer on
the surfaces of the solid particles, resulting in the surface-imprinted ma-
terial with high performance. Using the surface imprinting described
above, we prepared various molecule or ion imprinted materials, and
the prepared surface-imprinted materials have excellent recognition se-
lectivity and high binding capacity for the template molecule or ion as
well as exhibit fast mass transfer rate.
In the prior research of ours (Fang et al., 2012), by using a surface-
initiated graft-polymerization method, hydroxyethyl methylacrylate
(HEMA) was first graft-polymerized onto the surfaces of micro-sized
silica gel particles, obtaining the grafted particles PHEMA/SiO2, and
then 8-hydroxyquinoline (HQ) as a ligand with strong chelating ability
for metal ions was bonded on the side chain of the grafted macromole-
cule PHEMA, obtaining the functional grafted particles HQ-PHEMA/SiO2.
In this work, HQ-PHEMA was used as functional polymer, on which the
bonded HQ could strongly coordinate to rare earth ion as well as
other transition metal ions, and on this basis, the Pr3 + ion surface-
imprinting was carried out successfully on the surfaces of HQ-PHEMA/
SiO2 particles by using the novel ion surface-imprinting technique of
“pre-grafting and post-crosslinking/imprinting”, getting Pr3 + ion
surface-imprinted material IIP-HQP/SiO2. The ion recognition and sepa-
ration property of IIP-HQP/SiO2 for three neighbouring light rare earth
element ions, La3+, Ce3 + and Pr3+ ions, were investigated in-depth.
The imprinted material IIP-HQP/SiO2 has special recognition selectivity
for Pr3+ ion, and can separate these neighbouring light rare earth ele-
ment ions at picometre scale. It is obvious that such investigation is sig-
nificant in hydrometallurgy as well as in the purification of rare earth
elements, and it is reported for the first time.
2. Experimental section
2.1. Materials and instruments
Silica (about 125 μm of diameter, Ocean Chemical Limited
Company, Qingdao City, China) was of reagent grade. γ-
Aminopropyltrimethoxysilane (AMPS, Nanking Chuangshi Chemical
Aux Ltd., Jiangsu Province, China) was of analytical grade. Hydroxyethyl
methylacrylate (HEMA, Tianjin Institute of Chemical Reagents, Tianjin
City, China) was of analytical grade, and was purified via vacuum
distillation before use. Ammonium persulfate (APS, Tianjin Damao
Chemical Reagent Plant, Tianjin City, China) was of analytical grade. 5-
Chloromethyl-8-hydroxyquinoline (CHQ) was self-prepared (Gao
et al., 2013a, 2013b). 2,2′-Dichlorodiethyl ether (Wuxi Fanrong
Supplies Co. Ltd., Jiangsu Province). N,N-dimethyl formamide (DMF,
Tientsin University Chemical Reagent Plant, Tientsin City, China) was
of analytical grade. Lanthanum nitrate and cerium nitrate (Tianjin
Damao Chemical Reagent Plant, Tianjin City, China) were of analytical
grade. Praseodymium oxide (Pr2O3) was supplied by Beijing General
Research Institute for Nonferrous Metals. Other reagents were all
commercial chemicals with analytical pure grade and purchased from
Chinese companies.
The instruments used in this study were as follows: Perkin-Elmer
1700 infrared spectrometer (Perkin-Elmer Company, USA); LEO-438VP
scanning electronic microscope (SEM, LEO Company, UK), STA449
thermogravimetry analyzer (TGA, Netzsch Company, Germany); PHS-
3C pH meter (Shanghai Precision Scientific Apparatus Inc., Shanghai,
China); THZ-92C constant temperature shaker equipped with water
bath (Shanghai Boxun Medical Treatment Equipment Factory, Shanghai,
China); Unic-2602 UV/vis spectrophotometer (Unic Company, Shanghai).
2.2. Preparation and characterization of functional particles HQ-PHEMA/SiO2
According to the procedure described by Fang et al. (2012), the func-
tional particles HQ-PHEMA/SiO2 were prepared through two sets of par-
tial reactions, graft-polymerization of PHEMA and functionalization
transforming of the grafted particles. (1) The graft-polymerization of
HEMA on the surfaces of silica gel particles was effectively carried out
with a surface-initiated graft-polymerization method, and the process
is briefly stated as follows. The micro-sized silica gel particles were
surface-modified with coupling agent AMPS to introduce amino groups
onto the surfaces of silica gel particles, getting the surface-modified par-
ticles AMPS-SiO2. (2) A redox initiating system was constituted by the
amino group on SiO2 and the APS in the solution of DMF, and the
surface-initiated graft-polymerization of HEMA was conducted under
N2 atmosphere, obtaining the grafted particles PHEMA/SiO2 with a
high grafting degree (40 g/100 g). The grafted particles PHEMA/SiO2
were fully characterized by using several means, such as FTIR, SEM
and TGA (Fang et al., 2012). (3) The HQ-functionalization transforming
of the grafted particles PHEMA/SiO2 was realized through the nucleophilic
substitution reaction between CHQ and the side hydroxyl groups of the
grafted macromolecules PHEMA. The substitution reaction was conduct-
ed at 90 °C and under N2 atmosphere for 7 h with Na2CO3 as acid accep-
tor, preparing the functional grafted particles HQ-PHEMA/SiO2. The
infrared spectrum of HQ-PHEMA/SiO2 particles were determined with
 B. Gao et al. / Hydrometallurgy 150 (2014) 83–91
KBr pellet method to confirm their structure, and the bonding amount of
HQ (1.85 mmol/g) on HQ-PHEMA/SiO2 particles was measured by ultra-
violet spectrophotometry at 251 nm (the bonding amount of HQ was in-
directly determined by measuring the residual HQ amount in the
solution) (Fang et al., 2012).
2.3. Examination of adsorption property of HQ-PHEMA/SiO2 for Pr3+ ion
2.3.1. Isothermal adsorption experiments
Pr3+ ion solutions with different concentrations were prepared in a
range of 0.001–0.1 mol/L by dissolving Pr2O3 using diluted hydrochloric
acid solution and then diluting quantitatively with distilled water. Based
on testing the adsorption kinetics behaviour of HQ-PHEMA/SiO2 for
Pr3+ ion (the adsorption equilibrium time was about 4 h), the isother-
mal adsorption experiments of HQ-PHEMA/SiO2 for Pr3+ ion were car-
ried out in a constant temperature shaker to evaluate the chelating
adsorption ability of HQ-PHEMA/SiO2 for Pr3+ ion and to explore the
chelating adsorption mechanism. The equilibrium concentration of
Pr3 + ion was determined with EDTA complex titration method, and
the adsorption isotherm was figured.
2.3.2. Isothermal adsorption experiments at different pH values
The pH values of Pr3+ ion solutions were adjusted with diluted solu-
tions of NaOH or HCl, and the isothermal adsorption experiments of HQ-
PHEMA/SiO2 for Pr3+ ion were carried out at different pH values to ex-
amine the effect of pH value on the chelating adsorption property of
HQ-PHEMA/SiO2 and to determine the suitable pH value for the Pr3+
ion surface-imprinting process.
2.4. Preparation and characterization of Pr3+ ion surface-imprinted mate-
rial IIP-HQP/SiO2
The functional particles HQ-PHEMA/SiO2 (1 g) were placed into
500 mL of a Pr3 + ion solution, whose concentration was 0.01 mol/L,
and the pH of the solution was adjusted to 4.5 with a diluted NaOH so-
lution. The mixture was placed in a constant temperature oscillator, and
was shaken at 25 °C for 4 h, making the adsorption of HQ-PHEMA/SiO2
particles for Pr3+ ion to reach saturation. The HQ-PHEMA/SiO2 particles
having adsorbed Pr3 + ion in a saturated state were filtered out and
dried under vacuum. Such HQ-PHEMA/SiO2 particles (0.5 g) were
placed in a mixed solution of water and ethanol (V:V = 7:3), in which
Pr3 + ion with a concentration of 0.01 mol/L was contained, and the
pH value was adjusted to 4.5, followed by adding 4.30 mL of ethanol
solution of the crosslinker 2,2′-dichlorodiethyl ether with a concen-
tration of 1%. The crosslinking reaction and the imprinting process
were carried out at 45 °C for 24 h with stirring. After finishing the
crosslinking and imprinting process, the product particles were
washed repeatedly with the aqueous solution of HCl to remove the
template ion. By drying under vacuum, the final product particles
were namely Pr3 + ion surface-imprinted particles IIP-HQ-PHEMA/
SiO2 , and it is abbreviated as IIP-HQP/SiO2 . The infrared spectrum
of the imprinted particles IIP-HQP/SiO2 was determined with KBr
pellet method to confirm their chemical structure, and their mor-
phology was also observed with SEM.
2.5. Examining binding property of IIP-HQP/SiO2 particles towards Pr3+ ion
2.5.1. Evaluating binding property of IIP-HQP/SiO2 with static method
The binding property of IIP-HQP/SiO2 for Pr3+ ion was first exam-
ined with batch method (static method). Aqueous solutions of Pr3 +
ion were prepared in a concentration range of 0.001–0.01 mol/L, and
the pH values of these solutions were adjusted to pH 4.5. The adsorption
kinetics experiments were first conducted to determine the time of
equilibrium adsorption, and it was also about 4 h. On that basis, the iso-
thermal binding property of IIP-HQP/SiO2 particles for Pr3+ ion was in-
vestigated. At the constant temperature of 25 °C, Pr3+ ion solutions of
85
20 mL with different concentrations were placed into a number of con-
ical flasks with cover, and about 0.05 g of IIP-HQP/SiO2 particles weight-
ed accurately was added into these solutions, respectively. These
mixtures were shaken in a constant temperature oscillator for 4 h, and
the binding process was allowed to reach equilibrium. After standing
for layering, the Pr3+ ion concentrations of those supernatants were de-
termined with EDTA complex titration method. The equilibrium adsorp-
tion amount of Pr3 + ion, Qe (mmol/g), was calculated according to
Eq. (1), and the relationship curve between Qe and the equilibrium con-
centration of Pr3+ ion, namely binding isotherm was figured.
V ðC 0 −C e Þ
Qe ¼ ð1Þ
m
where C0 (mol/L) and Ce (mol/L) are the initial and equilibrium concen-
trations of Pr3+ ion, respectively, V (mL) is the volume of Pr3+ ion solu-
tion, and m (g) is the mass of the used adsorbent IIP-HQP/SiO2 particles.
La, Ce and Pr are the three neighbouring light rare earth elements,
and so for the three ions, La3+, Ce3+ and Pr3+, electron configurations
are similar, physicochemical properties resemble each other, and ion
radii are similar. Furthermore, by affecting of lanthanide contraction,
the ion radii of the three ions are very close to each other, and the differ-
ences only are in a range of 2–5 pm. The structure data of the three light
rare earth ions are listed in Table 1. It is very apparent that the separa-
tion between them is very difficult. In this investigation, by selecting
La3+ and Ce3+ ions as contrast ions, the recognition character of IIP-
HQP/SiO2 particles for Pr3+ ion was examined in-depth, and the feasi-
bility of mutual separation of the three ions at picometre scale with
IIP-HQP/SiO2 as solid phase extracting agent was explored. Therefore,
similar to Pr3 + ion, the isothermal binding experiments of IIP-HQP/
SiO2 particles for La3 + and Ce3 + ions were also carried out, and the
binding isotherms were also figured.
2.5.2. Evaluating binding property of IIP-HQP/SiO2 with dynamic method
The binding property of IIP-HQP/SiO2 for Pr3+ ion was further exam-
ined with column method (dynamic method). At room temperature,
IIP-HQP/SiO2 particles (about 1.5 g) were packed into a piece of glass
pipe with an internal diameter of 1.0 cm, and the bed volume (BV) of
the packed column was 2 mL. The Pr3+ ion solution (pH = 4.5) with a
concentration of 0.008 mol/L was allowed to flow gradually through
the packed column at a rate of four bed volumes per hour (4 BV/h) in
the countercurrent manner. The effluents with two volume (2 BV) in-
terval were collected, and the concentrations of Pr3+ ion in these efflu-
ents were determined. The dynamic binding curve was plotted, and the
break binding amount and saturated binding amount were calculated
with the data of the concentration and bed number of these effluents,
respectively. Using the same method, the dynamic binding curves of
IIP-HQP/SiO2 particles towards two contrast ions, La3+ and Ce3+ ions,
were also determined.
2.5.3. Experiments of adsorption selectivity
In order to further examine the recognition specificity of IIP-HQP/
SiO2 particles for Pr3 + ion, the competitive adsorption experiments
were carried out. Two binary mixed solutions, Pr3 +/La3 + and Pr3 +/
Ce3 +, were prepared, and the concentration of each ion in the two
mixed solutions was the same, 0.006 mol/L. Furthermore, the pH values
of the two solutions were adjusted to pH 4.5. The two binary mixed so-
lutions (20 mL) were placed into two conical flasks with cover, respec-
tively, and 0.05 g of IIP-HQP/SiO2 particles weighted accurately was
added into the two solutions, respectively. The static adsorption exper-
iments were conducted. After reaching binding equilibriums (4 h), the
concentration of each ion in the two supernatants was determined,
and the distribution coefficient for each anion was calculated according
to Eq. (2) (Ersöz et al., 2004; Say et al., 2004). The method of determin-
ing the concentration of each ion in the two supernatants was explained
86 B. Gao et al. / Hydrometallurgy 150 (2014) 83–91
Table 1
Structure data of three rare earth ions.
Rare earth ion La3+ Ce3+
Atomic number 57 58
Electronic configuration 5d1 6s2 4f2 6s2
Ionic radius/pm 106.1 103.4
as follows by taking pr3+/La3+ system as an example. The total concen-
tration of Pr3+ and La3+ ions in the supernatants was determined with
EDTA complex titration method. Then concentration of Pr3+ ion in the
supernatants was determined by spectrophotometry at 445 nm, and
the concentration of La3+ ion was obtained by subtracting the concen-
tration of Pr3+ ion from the total concentration of Pr3+ and La3+ ions.
Qe
Kd ¼
Ce
where Kd represents the distribution coefficient (mL/g) of a certain ion;
Qe (mmol/g) is its equilibrium adsorption quantity; Ce (mol/L) is its
equilibrium concentration.
The selectivity coefficient k of IIP-HQP/SiO2 particles for Pr3+ ion rel-
ative to a certain competition ion, La3+ or Ce3 + ion, can be obtained
from the distribution coefficient data according to Eq. (3), and the
value of k marks the recognition selectivity of IIP-HQP/SiO2 for Pr3 +
ion (Ersöz et al., 2004; Say et al., 2004).
 
3þ
K d Pr
k¼
ð3Þ
K d M3þ
where Kd(π Pr3+) is the distribution coefficient of Pr3+ ion, whereas Kd
(πM3+) represents the distribution coefficient of a certain competition
ion.
2.6. Desorption experiment
IIP-HQP/SiO2 particles (1.5 g), which had adsorbed Pr3+ ion in a sat-
uration state, were packed into a piece of glass pipe with an internal di-
ameter of 1.0 cm, and the bed volume (BV) of the packed column was
about 2 mL. An aqueous solution of HCl with a concentration of
0.1 mol/L was used as eluent. The eluent was allowed to flow gradually
through the column at a rate of two bed volumes per hour (2 BV/h) up-
stream. The effluents with one volume (1 BV) interval were collected,
and the concentrations of Pr3+ ion in these effluents were determined.
The dynamic desorption curve was plotted, and the elution property of
IIP-HQP/SiO2 particles was estimated.
3. Results and discussions
3.1. Process of preparing functional grafted particles HQ-PHEMA/SiO2 and
their chemical structure
As described by Fang et al. (2012), in this work, the functional
grafted particles HQ-PHEMA/SiO2 were prepared by a two-step method.
Micro-sized silica gel particles were surface-modified with coupling
agent AMPS, and amino groups (primary amino groups) were intro-
duced onto the surfaces of silica gel particles. A surface-initiating system
was constituted by the amino group on the modified silica gel particles
and persulfate in the solution. As a result, HEMA was graft-polymerized
on micro-sized silica gel particles by a surface-initiated graft-
polymerization way, obtaining the grafted particles PHEMA/SiO2 with
a high grafting degree of 40 g/100 g. Subsequently, ligand HQ was bond-
ed on the side chains of the grafted macromolecule PHEMA with CHQ as
reagent and through a polymer reaction, nucleophilic substitution, and
the functional grafted particles HQ-PHEMA/SiO2 with strong chelating
functionality for metal ions were obtained. The preparing process and
Pr3+ chemical structures of the above two particles are briefly and schemat-
59
ically expressed in Scheme 1.
4f3 6s2
101.3 3.2. Interaction between HQ-PHEMA/SiO2 particles and Pr3+ ion
3.2.1. Chelating adsorption property of HQ-PHEMA/SiO2 for Pr3+ ion
Fig. 1 gives the adsorption isotherms of the grafted particles PHEMA/
SiO2 and the functional grafted particles HQ-PHEMA/SiO2 for Pr3+ ion.
It can be observed clearly that the grafted particles PHEMA/SiO2
have weak adsorption ability for Pr3 + ion. However, after HQ-
functionalizing, the functional grafted particles HQ-PHEMA/SiO2 exhibit
much stronger adsorption action for Pr3+ ion, and the adsorption capac-
ity can get up to 0.13 mmol/g. Furthermore, it was found by treating the
adsorption data that the adsorption isotherm of IIP-HQP/SiO2 particles
for Pr3+ ion belongs to Langmuir type. HQ is a bidentate chelating ligand
ð2Þ
with very strong chelation for metal ions, and there are the bonded HQ
groups with a high density on the surfaces of HQ-PHEMA/SiO2 particles,
resulting in the strong adsorption action of HQ-PHEMA/SiO2 for Pr3+
ion. This lays a sufficient foundation for preparing the Pr3 + ion
surface-imprinted material by using the “pre-grafting and post-
crosslinking/imprinting” method. The possible chelation model of HQ-
PHEMA/SiO2 for Pr3+ ion is shown schematically in Scheme 2.
3.2.2. Effect of pH on adsorption property of HQ-PHEMA/SiO2
The pH values of Pr3+ ion solutions were changed, and the adsorp-
tion experiments of HQ-PHEMA/SiO2 particles for Pr3 + ion were
allowed to be carried out under different pH conditions. Fig. 2 presents
the adsorption isotherms at different pH values. In order to more clearly
display the effect of pH on adsorption property of HQ-PHEMA/SiO2, the
saturated adsorption amounts (Qm) were taken from Fig. 2, and the re-
lationship curve between Qm and pH value is given in Fig. 3. It can be
found from Fig. 3 as well as from Fig. 2 that the adsorption capacity of
HQ-PHEMA/SiO2 particles for Pr3 + ion first increases and then de-
creases with increasing pH value, and at pH 4.5 there is a maximum ad-
sorption amount (0.13 mmol/g).
The above-mentioned variation trend reflects the change of the che-
lation of HQ-PHEMA/SiO2 particles towards Pr3+ ion with pH value. At
lower pH, the N atoms of the HQ groups bonded on HQ-PHEMA/SiO2
particles are highly protonized, and it will significantly weaken the elec-
tron pair-donating ability of N atoms, leading to the weak coordination
ability of HQ to Pr3+ ion and to low adsorption capacity of HQ-PHEMA/
SiO2 particles. Along with the increase of pH value, the protonation de-
gree of the N atoms of HQ groups weakens, and the coordination ability
of HQ to Pr3+ ion is strengthened, leading to the increase of the adsorp-
tion capacity of HQ-PHEMA/SiO2 particles for Pr3+ ion and resulting in a
maximum adsorption capacity of 0.13 mmol/g at pH 4.5. However, the
rare earth ions are easy to be hydrolyzed, and for Pr3 + ion, the first-
order hydrolysis constant K1 at 25 °C is equal to 0.25 × 10− 8. As
pH N 4.5, the hydrolysis of Pr3+ ion will occur obviously, and the hydro-
lysis product depositing on the surfaces of HQ-PHEMA/SiO2 particles
will seriously affect their adsorption property, leading to the decrease
of the adsorption capacity. The above experimental result supplies the
suitable pH condition for the following Pr3+ ion surface-imprinting pro-
cess, namely in this investigation, the Pr3+ ion surface-imprinting was
conducted under the condition of pH 4.5.
3.3. Preparation processes and structure of Pr3 + ion surface-imprinted
material IIP-HQP/SiO2
(1) Firstly, the chelating adsorption of HQ-PHEMA/SiO2 for Pr3+ ion
was made to reach saturation at pH 4.5. (2) Afterwards, such HQ-
PHEMA/SiO2 particles were placed into the mixed solution of water
and ethanol, in which Pr3+ ion was contained, followed by adding the
ethanol solution of the crosslinker 2,2′-dichlorodiethyl ether. By right
 B. Gao et al. / Hydrometallurgy 150 (2014) 83–91
Scheme 1. Preparation process and chemical structure of PHEMA/SiO2 and HQ-PHEMA/SiO2 particles.
of the quarterisation reaction between the two terminal chloroalkane
groups and N atom of HQ bonded on the side chains of the grafted
PHEMA, the grafted macromolecules HQ-PHEMA are crosslinked. At
the same time, Pr3+ ions are packaged in the crosslinking networks so
that Pr3 + ion surface-imprinting is realized. (3) Finally, the template
Pr3 + ions are eluted, and a great deal of the imprinted caves of Pr3 +
ions leaves and is distributed within the thin polymer layer around
the silica gel particles, forming Pr3 + ion surface-imprinted material
IIP-HQP/SiO2. The entire preparation processes of IIP-HQP/SiO2 can be
schematically illustrated in Scheme 3.
The infrared spectrum of IIP-HQP/SiO2 particles is presented in Fig. 4,
and for comparison, the spectrum of HQ-PHEMA/SiO2 particles, which
was analyzed Fang et al. (2012), is also given in Fig. 4.
In comparison with the spectrum of HQ-PHEMA/SiO2 particles, in
the spectrum of IIP-HQP/SiO2 particles, the stretching vibration band
at 2850 cm−1 and out-plane flexural vibration band at 721 cm−1 for
methylene group \CH2\ have strengthened obviously, and it is caused
by the great deal of methylene group in the crosslinking bridge. While
the characteristic vibration absorption of the ether bond C\O\C in
the crosslinking bridge is covered by the strong absorption background
of SiO2. The above spectrum data demonstrate that the crosslinking and
0.16
0.12
Qe/(mmol/g)
0.08
HQ-PHEMA/SiO2
PHEMA/SiO2
0.04
0.00
0.000 0.002 0.004 0.006 0.008 0.010
Ce/(mol/L)
Fig. 1. Adsorption isotherms of PHEMA/SiO2 and HQ-PHEMA/SiO2 particles for Pr3+ ion.
Temperature: 25 °C; pH = 4.5.
87
imprinting processes have been realized successfully, and Pr3 + ion
surface-imprinted material IIP-HQP/SiO2 has been formed.
3.4. Binding character of IIP-HQP/SiO2 for Pr3+ ion
3.4.1. Binding isotherm
The adsorption experiments with batch method were first
performed in the solutions with pH 4.5, and HQ-PHEMA/SiO2 and IIP-
HQP/SiO2 particles were used, respectively. Fig. 5 and Fig. 6 give the ad-
sorption isotherms of HQ-PHEMA/SiO2 (non-imprinted material) and
the binding isotherms of IIP-HQP/SiO2 (imprinted material) for La3+,
Ce3+ and Pr3+ ions, respectively.
Fig. 5 displays that for all of the three neighbouring light rare earth
ions, the functional grafted particles HQ-PHEMA/SiO2 (non-imprinted
material) have high adsorption capacities (about 0.13 mmol/g), and
further they are much the same, showing no adsorption selectivity.
The high adsorption capacities arise from the strong chelating adsorp-
tion action of the functional grafted particles HQ-PHEMA/SiO2 for rare
earth ions, whereas the same adsorption capacities are caused by the
very similar physicochemical properties of La3+, Ce3+ and Pr3+ ions.
However, it can be seen clearly from Fig. 6 that after Pr3 + ion
surface-imprinting, the binding capacity of the imprinted material IIP-
HQP/SiO2 for La3 + and Ce3 + ions drastically decreases, and the
maximum adsorption amount decreases from 0.13 mmol/g to
0.04 mmol/g, indicating that the imprinted material IIP-HQP/SiO2
lacks the recognition selectivity and binding ability for La3+ and Ce3+
ions. While for the template Pr3+ ion, the imprinted material IIP-HQP/
SiO2 still maintains a higher binding capacity, and even has some
improvement (the maximum adsorption amount increases from
0.13 mmol/g to 0.15 mmol/g), fully showing the special recognition se-
lectivity and high binding affinity of IIP-HQP/SiO2 for Pr3+ ion. For the
Pr3+ ion surface-imprinted material IIP-HQP/SiO2, a great quantity of
Pr3 + ion-imprinted caves are distributed within the thin polymer
layer on the surfaces of silica gel particles. These caves are highly
matched with Pr3+ ion in size (with a ion radius of 101.3 pm) and action
sites, and they are unmatched with La3+ and Ce3+ ions, whose ion radii
are 106.1 pm for La3+ ion and 103.4 pm for Ce3+ ion, respectively. Ob-
viously, the ion radii of La3+ and Ce3+ ions are 2–5 pm larger than that
of Pr3+ ion, and so the Pr3+ ion-imprinted caves cannot accommodate
La3 + and Ce3 + ions, or La3 + and Ce3 + ions cannot enter into these
88 B. Gao et al. / Hydrometallurgy 150 (2014) 83–91
Scheme 2. Schematic expression of chelating adsorption of HQ-PHEMA/SiO2 particles towards Pr3+ ion.
imprinted caves. It is precisely because of the above reason that the Pr3+
ion surface-imprinted material IIP-HQP/SiO2 exhibits the specific recog-
nition selectivity for Pr3 + ion, and displays its separation ability at
picometre scale for the three neighbouring light rare earth ions. There-
fore, the Pr3+ ion surface-imprinted material IIP-HQP/SiO2 as well as
other rare earth-imprinted materials is a solid extracting material with
high performance, and it is promising to use them in hydrometallurgy.
In Fig. 5 and Fig. 6, the adsorption isotherms of Nd3 + ion on HQ-
PHEMA/SiO2 (non-imprinted material) and IIP-HQP/SiO2 (imprinted
material) are also given. Similarly, the adsorption capacity of Nd3+ ion
on HQ-PHEMA/SiO2 particles is the same as that of La3 +, Ce3 + and
Pr3+ ions because of without adsorption selectivity of these particles.
Whereas Fig. 6 displays that the binding capacity of Nd3 + ion on IIP-
HQP/SiO2 particles is much smaller than that of Pr3 + ion, displaying
the recognition selectivity of IIP-HQP/SiO2 particles for Pr3+. However,
the binding capacity of Nd3 + ion is obviously higher than La3 + and
Ce3 + ions. Ion radius of Nd3 + ion is 98.5 pm, and it is smaller than
that of the template ion, Pr3+ ion.
Therefore, greater Nd3+ ions may enter into the Pr3+ ion-imprinted
caves, leading a higher binding capacity. Even so, these caves are still
mismatched with Nd3 + ions to a certain degree in size and action
sites, so the binding capacity of Nd3+ ion on IIP-HQP/SiO2 particles is
also much smaller than that of Pr3+ ion.
3.4.2. Dynamic binding curve
The adsorption experiments with column method were also per-
formed, and the columns were packed with the non-imprinted material
HQ-PHEMA/SiO2 and the imprinted material IIP-HQP/SiO2, respectively.
0.14 pH=4.5
pH=4.0
0.12 pH=5.0
pH=3.0
0.10 pH=2.0
Qe/(mmol/g)
0.08
0.06
0.04
0.02
0.00
0.000 0.002 0.004 0.006 0.008
Ce/(mol/L)
Fig. 2. Adsorption isotherms of HQ-PHEMA/SiO2 for Pr3+ ion at different pH values. Tem-
perature: 25 °C.
Fig. 7 and Fig. 8 present the dynamic adsorption curves of HQ-PHEMA/
SiO2 and the dynamic binding curves of IIP-HQP/SiO2 for the three
ions, La3+, Ce3+ and Pr3+ ions, respectively.
It can be observed from Fig. 7 that as the solutions of the three ions
with the same concentration (0.008 mol/L) flow upstream through
the column packed with HQ-PHEMA/SiO2, respectively, their leaking
volumes are the same and are about 12 BV, again showing that HQ-
PHEMA/SiO2 particles are non-selective for the adsorptions of the
three ions.
However, it can be found from Fig. 8 that for the column packed with
IIP-HQP/SiO2 particles, the breakthrough curves of La3+ and Ce3+ ions
are obviously different from that of Pr3+ ion. The leaking volumes of
La3+ and Ce3+ ions have fallen substantially, and decrease from 12 BV
to 2 BV, fully showing that the column packed with IIP-HQP/SiO2 parti-
cles basically does not recognize and does not bind La3+ and Ce3+ ions.
By calculating, for La3 + ion, the leaking and saturated adsorption
amounts are only about 0.021 mmol/g and 0.038 mmol/g, respectively,
and for Ce3+ ion, the leaking and saturated adsorption amounts are only
about 0.021 mmol/g and 0.041 mmol/g, respectively. While for Pr3+
ion, the leaking still maintains a higher level (14 BV), again displaying
the special recognition selectivity of IIP-HQP/SiO2 particles for Pr3 +
ion. By calculating, the leaking and saturated adsorption amounts of
Pr3 + ion reach up to 0.12 mmol/g and 0.16 mmol/g, and they are
much higher than those of La3+ and Ce3+ ions.
3.4.3. Selectivity coefficient
Two binary mixed solutions of pH 4.5, Pr3+/Ln3+ and Pr3 +/Ce3+,
were prepared, and the competitive adsorption experiments of IIP-
HQP/SiO2 particles in the two solutions were conducted. The data of
0.14
0.12
0.10
Qm/(mmol/g)
0.08
0.06
0.04
0.02
0.010 2.0 2.5 3.0 3.5 4.0 4.5 5.0
pH
Fig. 3. Relationship curve between saturated adsorption amount of HQ-PHEMA/SiO2 for
Pr3+ ion and pH.
 B. Gao et al. / Hydrometallurgy 150 (2014) 83–91 89

Scheme 3. Schematic expression of chemical reaction process to prepare IIP-HQP/SiO2.

the distribution coefficients Kd of each ion and the selectivity coeffi-

cients k of IIP-HQP/SiO2 for Pr3 + ion are summarized in Table 2 and
Table 3.
IIP-HQ-HEMA/SiO2 The data in Table 2 and Table 3 reveal the following facts. (1) The se-
721

lectivity coefficients of the non-imprinted material, HQ-PHEMA/SiO2

particles, for Pr3 + ion relative to Ln3+ and Ce3+ ions are very closed
to 1, and are 0.968 and 0.973, respectively, implying that the adsorption
2850

T/%
HQ-HEMA/SiO2 of HQ-PHEMA/SiO2 particles for Pr3+ ion has no any selectivity. (2) The
selectivity coefficients of the imprinted material, IIP-HQP/SiO2 particles,
for Pr3+ ion relative to Ln3+ and Ce3+ ions reach up to 5.22 and 5.12,
respectively, showing the very high recognition selectivity for Pr3+ ion.
2850

3500 3000 2500 2000 1500 1000 500

0.16
Wavenumber/cm-1

0.12
Qe/(mmol/g)

IIP-HQ-HEMA/SiO2
721

0.08
3+
Nd
2850

T/% 3+
0.04 Pr
3+
HQ-HEMA/SiO2 Ce
3+
La
0.00
2850

0.000 0.002 0.004 0.006 0.008 0.010

3200 3000 2800 750 700 650 Ce/(mol/L)
Wavenumber/cm-1
Fig. 5. Adsorption isotherms of HQ-PHEMA/SiO2 for lanthanide ions. Temperature: 25 °C;
Fig. 4. IR spectra of HQ-PHEMA/SiO2 and IIP-HQ-PHEMA/SiO2 particles. pH = 4.5.
90 B. Gao et al. / Hydrometallurgy 150 (2014) 83–91

0.16
8

3+
0.12
Pr
3+ 6
Nd

c/(mmol/L)
Qe/(mmol/g)

3+
Ce
3+ 4
0.08 La

2 3+
Pr
0.04 3+
Ce
0 3+
La

0.00
0.000 0.002 0.004 0.006 0.008 0.010
Ce/(mol/L)
Fig. 6. Binding isotherms of IIP-HQP/SiO2 for lanthanide ions. Temperature: 25 °C; pH =
4.5.
The ion radius differences between Pr3+ ion and Ce3+ ion and be-
tween Pr3 + ion and La3 + ion are only 2.1 pm and 4.8 pm (see
Table 1), respectively, but the selectivity coefficients of IIP-HQP/SiO2
particles for Pr3+ ion relative to Ce3+ ion and La3+ ion actually reach
up to 5.12 and 5.22. This experimental fact fully demonstrates that the
mutual separation of the three neighbouring rare earth ions at
picometre scale can be realized by using the Pr3 + ion surface-
imprinted material IIP-HQP/SiO2. It can be expected that a more effi-
cient separation technique of rare earth elements is probably developed
by introducing rare earth ion-imprinted materials in hydrometallurgy
and in the purification of rare earth elements.
3.5. Elution property of IIP-HQP/SiO2
An aqueous solution of HCl with a concentration of 0.1 mol/L was
used as the eluent. The eluent was made to upstream pass through
the column packed with IIP-HQP/SiO2 particles having bound Pr3+ ion
in a saturated state, and the dynamic desorption experiment was con-
ducted. The experiment indicated that IIP-HQP/SiO2 particles have ex-
cellent eluting property due to the fact that those Pr3 + ion-imprinted
caves are distributed within the thin polymer layer on the surfaces of
IIP-HQP/SiO2, which is advantageous in the recovering and reusing of
IIP-HQP/SiO2 particles.
0 10 20 30 40
Bed volume
Fig. 8. Dynamic binding curves of IIP-HQP/SiO2 for three anions. BV: 2 mL; temperature:
25 °C; pH = 4.5; flow rate: 4 BV/h.
4. Conclusions
In this paper, HEMA was first graft-polymerized onto micro-sized
silica gel particles by initiating of a surface-initiating system, getting
the grafted particles PHEMA/SiO2, and then through a polymer reaction,
the grafted particles PHEMA/SiO2 were transformed into the functional
particles HQ-PHEMA/SiO2, on which HQ groups with strong chelation
for metal ions were bonded. Imprinting Pr3+ ion towards the grafted
macromolecule HQ-PHEMA was carried out smoothly using 2,2′-
dichlorodiethyl ether as crosslinker, and Pr3 + ion surface-imprinted
material IIP-HQP/SiO2 was obtained successfully, namely, by using the
effective surface-imprinting technique of “pre-grafting and post-
crosslinking/imprinting”, the rare earth ion surface-imprinted material
was prepared successfully. IIP-HQP/SiO2 possesses high recognition se-
lectivity and high binding affinity for Pr3+ ion, whereas its adsorption
properties for the contrast ions, La3 + and Ce3 + ions, which are the
neighbouring elements with Pr in lanthanides, are very poor. Relative
to La3+ and Ce3+ ions, the selectivity coefficients of IIP-HQP/SiO2 for
Pr3+ ion are 5.22 and 5.12, respectively. The ion radius differences be-
tween La3+, Ce3+ and Pr3 + ions are only in a range of 2–5 pm. Such
high selectivity coefficients imply that in this investigation, the mutual
separation of La3+, Ce3 + and Pr3 + ions at picometre scale is realized
successfully by using the ion surface-imprinted polymer material.
Acknowledgement

We would like to express our gratitude to the National Science Foun-

dation for Young Scientists of China (grant No. 51104023) which sup-
ported this research.
8

Table 2
6 Distribution coefficient and selectivity coefficient data for Pr3+/La3+ system.
c/(mmol/L)

Adsorb material HQ-PHEMA/SiO2 IIP-HQP/SiO2

4 Adsorbate Pr 3+
La3+
Pr3+ La3+

Kd/(mL/g) 25.071 25.912 26.685 5.112

3+
2 Pr k 0.968 5.22
3+
Ce
3+
La Table 3
0
Distribution coefficient and selectivity coefficient data for Pr3+/Ce3+ system.

0 10 20 30 40 Adsorb material HQ-HEMA/SiO2 IIP-HQP/SiO2

Bed volume Adsorbate Pr3+ Ce3+ Pr3+ Ce3+

Kd/(mL/g) 25.071 25.780 26.685 5.212

Fig. 7. Dynamic adsorption curves of HQ-PHEMA/SiO2 for lanthanide ions. BV: 2 mL; Tem-
k 0.973 5.12
perature: 25 °C; pH = 4.5; flow rate: 4 BV/h.
 B. Gao et al. / Hydrometallurgy 150 (2014) 83–91
References
Abreu, R.D., Morais, C.A., 2010. Purification of rare earth elements from monazite
sulphuric acid leach liquor and the production of high-purity ceric oxide. Miner.
Eng. 23, 536–540.
Akdamar, H.A., Sarıözlü, N.Y., Özcan, A., Ersöz, A., Denizli, A., Say, R., 2009. Separation and
purification of hyaluronic acid by glucuronic acid imprinted microbeads. Mater. Sci.
Eng. C 29, 1404–1408.
Athikomrattanakul, U., Katterle, M., Gajovic-Eichelmann, N., Scheller, F.W., 2009. Develop-
ment of molecularly imprinted polymers for the binding of nitrofurantoin. Biosens.
Bioelectron. 25, 82–87.
Banda, R., Jeon, H.S., Lee, M.S., 2012. Solvent extraction separation of La from chloride so-
lution containing Pr and Nd with Cyanex 272. Hydrometallurgy 121–124, 74–80.
Belova, V.V., Voshkin, A.A., Kholkin, A.I., Payrtman, A.K., 2009. Solvent extraction of some
lanthanides from chloride and nitrate solutions by binary extractants. Hydrometal-
lurgy 97, 198–203.
Byun, H.S., Youn, Y., Yun, Y.H., Yoon, S.D., 2010. Selective separation of aspirin using mo-
lecularly imprinted polymers. Sep. Purif. Technol. 74, 144–153.
Ersöz, A., Say, R., Denizli, A., 2004. Ni(II) ion-imprinted solid-phase extraction and
preconcentration in aqueous solutions by packed-bed columns. Anal. Chim. Acta.
502, 91–97.
Fang, X., Gao, B., Huang, X., Zhang, Y., Gu, L., 2012. Studies on preparation of grafted par-
ticles of PHMA/SiO2 and their 8-hydroxyquinoline-functionalization transform. Acta
Polym. Sin. 12, 1472–1481 (In Chinese).
Gai, Q., Qu, F., Zhang, T., Zhang, Y.K., 2011. The preparation of bovine serum albumin
surface-imprinted superparamagnetic polymer with the assistance of basic functional
monomer and its application for protein separation. J. Chromatogr. A 1218,
3489–3495.
Gao, B., Lu, J., Chen, Z., Guo, J., 2009. Polymer, preparation and recognition performance of
cholic acid-imprinted material prepared with novel surface-imprinting technique.
50, 3275–3284.
Gao, B., Liu, S., Li, Y., 2010. Preparation and recognition performance of uric acid-
imprinted material prepared with novel surface imprinting technique. J. Chromatogr.
A 1217, 2226–2236.
Gao, B., Chen, Y., Men, J., 2011. Constructing chiral caves and efficiently separating enan-
tiomers of glutamic acid with novel surface-imprinting technique. J. Chromatogr. A
1218, 5441–5448.
Gao, B., Wang, X., Zhang, Y., 2013a. Preparation of chromate anion surface-imprinted ma-
terial IIP-PVI/SiO2 based on polyvinylimidazole-grafted particles PVI/SiO2 and its
ionic recognition characteristic. Mater. Chem. Phys. 140, 478–486.
Gao, B., Zhang, W., Lei, Q., Men, J., 2013b. Preparation and characterization of 8-
hydroxyquinoline-functionalized polysulfone and preliminary study on lumines-
cence property of its complex with Al(III). Macromol. Res. 21, 599–607.
Gu, J., Zhang, H., Yuan, G., Chen, L., Xu, X., 2011. Surface-initiated molecularly imprinted
polymeric column: in situ synthesis and application for semi-preparative separation
by high performance liquid chromatography. J. Chromatogr. A 1218, 8150–8155.
Hasegawa, Y., Tamaki, S., Yajima, H., Hashimoto, B., Yaita, T., 2011. Selective sepa-
ration of samarium(III) by synergistic extraction with β-diketone and
methylphenylphenanthroline carboxamide. Talanta 85, 1543–1548.
Hubicka, H., Kołodyńska, D., 2008. Application of monodispersive anion exchangers in
sorption and separation of Y3+ from Nd3+ and Sm3+ complexes with dcta. J. Rare
Earths 26, 619–625.
Javanbakht, M., Namjumanesh, M.H., Akbari-Adergani, B., 2009. Molecularly imprinted
solid-phase extraction for the selective determination of bromhexine in human
serum and urine with high performance liquid chromatography. Talanta 80,
133–138.
91
Jia, Q., Tong, S., Li, Z., Zhou, W., Li, H., Meng, S., 2009. Solvent extraction of rare earth ele-
ments with mixtures of sec-octylphenoxy acetic acid and bis(2,4,4-trimethylpentyl)
dithiophosphinic acid. Sep. Purif. Technol. 64, 345–350.
Jordens, A., Cheng, Y.P., Waters, K.E., 2013. A review of the beneficiation of rare earth el-
ement bearing minerals. Miner. Eng. 41, 97–114.
Kitahara, K.-I., Yoshihama, I., Hanada, T., Kokuba, H., Arai, S., 2010. Synthesis of
monodispersed molecularly imprinted polymer particles for high-performance liquid
chromatographic separation of cholesterol using templating polymerization in po-
rous silica gel bound with cholesterol molecules on its surface. J. Chromatogr. A
1217, 7249–7254.
Lee, G.S., Uchikoshi, M., Mimura, K., Isshiki, M., 2009. Distribution coefficients of La, Ce, Pr,
Nd, and Sm on Cyanex 923-, D2EHPA-, and PC88A-impregnated resins. Sep. Purif.
Technol. 67, 79–85.
Lee, G.S., Uchikoshi, M., Mimura, K., Isshiki, M., 2010. Separation of major impurities Ce,
Pr, Nd, Sm, Al, Ca, Fe, and Zn from La using bis(2-ethylhexyl)phosphoric acid
(D2EHPA)-impregnated resin in a hydrochloric acid medium. Sep. Purif. Technol.
71, 186–191.
Nasab, M.E., Sam, A., Milani, S.A., 2011. Determination of optimum process conditions for
the separation of thorium and rare earth elements by solvent extraction. Hydromet-
allurgy 106, 141–147.
Okutucu, B., Önal, S., 2011. Molecularly imprinted polymers for separation of various
sugars from human urine. Talanta 87, 74–79.
Otero-Romaní, J., Moreda-Piñeiro, A., Bermejo-Barrera, P., 2009. Ionic imprinted polymer
for nickel recognition by using the bi-functionalized 5-vinyl-8-hydroxyquinoline as a
monomer: application as a new solid phase extraction support. Microchem. J. 93,
225–231.
Pan, J., Yao, H., Guan, W., Ou, H., Huo, P., Wang, X., Zou, X., Li, C., 2011. Selective adsorption
of 2,6-dichlorophenol by surface imprinted polymers using polyaniline/silica gel
composites as functional support: equilibrium, kinetics, thermodynamics modeling.
Chem. Eng. J. 172, 847–855.
Patel, A.K., Sharma, P.S., Prasad, B.B., 2009. Voltammetric sensor for barbituric acid based
on a sol–gel derivated molecularly imprinted polymer brush grafted to graphite elec-
trode. Int. J. Pharm. 371, 47–55.
Qi, P., Wang, J., Wang, L., Li, Y., Jin, J., Su, F., Tian, Y., Chen, J., 2010. Molecularly imprinted
polymers synthesized via semi-covalent imprinting with sacrificial spacer for im-
printing phenols. Polymer 51, 5417–5423.
Say, R., Ersöz, A., Türk, H., Denizli, A., 2004. Selective separation and preconcentration of
cyanide by a column packed with cyanide-imprinted polymeric microbeads. Sep.
Purif. Technol. 40, 9–14.
Suzuki, T., Itoh, K., Ikeda, A., Aida, M., Ozawa, M., Fujii, Y., 2006. Separation of rare earth
elements by tertiary pyridine type resin. J. Alloys Compd. 408–412, 1013–1016.
Vatanpour, V., Madaeni, S.S., Zinadini, S., Rajabi, H.R., 2011. Development of ion imprinted
technique for designing nickel ion selective membrane. J. Membrane Sci. 373, 36–42.
Wang, Y., Zhou, Y., Sokolov, J., Rigas, B., Levon, K., Rafailovich, M., 2008. A potentiometric
protein sensor built with surface molecular imprinting method. Biosens. Bioelectron.
24, 162–166.
Wannachod, P., Chaturabul, S., Pancharoena, U., Lothongkum, A.W., Patthaveekongka, W.,
2011. The effective recovery of praseodymium from mixed rare earths via a hollow
fiber supported liquid membrane and its mass transfer related. J. Alloys Compd.
509, 354–361.
Yuan, Y., Wang, Y., Huang, M., Xu, R., Zeng, H., Nie, C., Kong, J., 2011. Development and
characterization of molecularly imprinted polymers for the selective enrichment of
podophyllotoxin from traditional Chinese medicines. Anal. Chim. Acta. 695, 63–72.