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Journal of Hazardous Materials 353 (2018) 496–504

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Journal of Hazardous Materials

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Dual-template docking oriented ionic imprinted bilayer mesoporous films T

with efficient recovery of neodymium and dysprosium

Xudong Zhenga, Yi Zhanga, Fusheng Zhangb, Zhongyu Lia, Yongsheng Yanb,
School of Environmental & Safety Engineering, Changzhou University, Changzhou, PR China
School of Chemistry & Chemical Engineering, Jiangsu University, Zhenjiang, PR China


Keywords: Rare earth elements (REEs) are critical materials to many cutting-edge technologies but are difficult to separate
Dual-template docking oriented ionic from one another because of their chemical similarity. We present ionic imprinted mesoporous bilayer films
imprinting (IIBFs) as an ideal adsorbent for selective separation of neodymium (Nd) and dysprosium (Dy) from sintered
Janus films neodymium magnets. IIBFs were prepared according to dual-template docking oriented ionic imprinting (DTD-
OII). Due to different imprinted compositions of bilayer films, IIBFs exhibited high specific surface area, fast
binding equilibrium, and Janus properties for simultaneous selective adsorption of different rare earth ions,
Selective adsorption
which made our imprinted bilayer mesoporous films a specialized adsorbent for adsorption of Nd(III) and Dy(III)
at the same time. The adsorption capacities of optimized IIBFs were 17.50 mg g−1 for Dy(III) and 12.15 mg g−1
for Nd(III) at pH = 4.0. Moreover, we grafted thermo-responsive polymer on the one surface of IIBFs to realize
controlled release of Nd(III) and Dy(III) by temperature. IIBFs demonstrate a high degree of reusability by
cycling experiments by DTD-OII, which develop their promising applications for the REE recycling and se-
paration industry.

1. Introduction Therefore, it is crucial to develop an efficient strategy for recovery of

certain and high-priced REEs from mining waste or end-of-life rare
Rare earth elements (REEs) are frequently cited critical materials for earth products. NdFeB magnets are comprised of an Nd2Fe14B matrix
electronic devices, fluorescence and metallurgy [1–3]. The unique phase with minor admixtures of praseodymium, gadolinium, terbium,
properties of REEs have led to their application in more consumer and especially Dy [4]. Among these elements, only recovery of Nd and
products than nearly any other element group. Among them, Neody- Dy are practically applicable considering composition of NdFeB mag-
mium (Nd) is a key component of sintered neodymium magnets nets and the economic viability. Industrial recovery of REEs mostly is
(NdFeB) [4]. Dysprosium (Dy) are also a key element of this permanent based on hydrometallurgy [12]. However, such technique requires or-
magnets which can increase its intrinsic coercivity [5]. Especially, some ganic solvents and leads to significant amounts of undesired wastes. In
high-performance NdFeB magnets include up to 9% Dy by total magnet comparison, liquid-solid extraction is recognized as a greener alter-
weight [6]. Since the increasing demand for the NdFeB magnets and native and has received increasing attention [13]. Currently, some
tightening export of China, Dy and Nd has been categorized as “critical studies using resins as adsorbents have been reported [14–17]. Our
materials” by European Commission and the U.S. Department of Energy group has successfully synthesized different functional mesoporous si-
because of their supply problems and importance to technology [3,7,8]. lica materials with respect to gadolinium and Dy adsorption [18,19].
With a large number of applications of REE products, the environ- However, the major bottleneck of adsorbents lies in their low adsorp-
mental problems caused by the REE production has received substantial tion selectivity and poor adsorption capacity. Moreover, most of the
media coverage during these years. Numerous newspaper reported adsorbents only can adsorb one certain rare earth ion selectively. Se-
appalling conditions such as natural environment devastated by pri- lective separation and recovery of two or more REEs simultaneously
mitive metallurgy. In order to alleviate scarcity of REEs and environ- (such as recovery of Nd and Dy from NdFeB magnets) cannot be
mental burden, recycling REEs were announced [9,10]. However, re- achieved now.
covery of REEs are notoriously difficult, and only several kind of REEs Bilayer films that can undergo property changes based on differ-
(Nd or Dy, etc.) in supply crisis are economically valuable [11]. ential component of the layers can be designed as Janus film materials.

Corresponding author.
E-mail address: (Y. Yan).
Received 13 December 2017; Received in revised form 20 March 2018; Accepted 11 April 2018
Available online 13 April 2018
0304-3894/ © 2018 Elsevier B.V. All rights reserved.
X. Zheng et al. Journal of Hazardous Materials 353 (2018) 496–504

These innovative films are attractive for applications in drug delivery 2.2. Preparation of IIBFs
and dual-adsorption [20–22]. To simultaneous extract Nd and Dy from
NdFeB magnets by Janus films, critical strategy is to reach highly se- 2.2.1. Preparation of CNCs
lective adsorption of individual rare earth for each domains of Janus CNCs were prepared in a typical procedure based on our previously
films. However, separation of the rare earths is extraordinarily difficult reported [31]. Briefly, the milled cotton was hydrolyzed in sulphuric
because of their almost identical physicochemical properties. To make acid (50 wt%) with vigorous stirring for 120 min at 45 °C. The suspen-
up for this deficiency, we inducted ionic imprinted technology to im- sion was then diluted with cold deionized water for the termination of
prove the adsorption capacity and adsorption selectivity of materials hydrolysis. The supernatant was decanted and the resulting thick
[23]. Recently, ionic imprinted polymers (IIPs) have found important cloudy layer was washed by deionized water 3 times to remove all
applications such as separation due to their artificial specific selection soluble cellulosic materials. The thick white suspension gained after
to recognize certain ions and tolerance to acid and base [24–27]. Tra- centrifugation was placed inside dialysis membrane tubes
ditional IIPs prepared by a bulk imprinting approach exhibit low ca- (12,000–14,000 molecular weight cut-off) and dialyzed until the value
pacity and poor accessibility. Thus, new materials that can fully de- of pH equals 2.4. The suspension was dispersed by subjecting it to ul-
monstrate the usefulness of IIPs are highly desirable. Mesoporous trasound treatment for 10 min and then diluted to the desired con-
materials with highly ordered pore structure can solve above problem. centration (3 wt%).
Rong successfully prepared imprinted mesoporous silica by structure-
directing agents [28]. Our group also successfully synthesized im- 2.2.2. Preparation of dual-template docking oriented ionic imprinted
printed SBA-15 for selective recovery dysprosium ions form acidic so- mesoporous bilayer films (IIBFs)
lution [19]. Mesoporous imprinted materials have showed promising For the preparation of IIBFs, iminodiacetic acid derivative of the
features in research of recovery of REEs. However, the benefits of me- silane and acetylacetone modified silane were prepared firstly. The
soporous imprinted Janus materials in adsorption of two different REE iminodiacetic acid derivative of silane was obtained following the
ions have never been explored. Incorporation of mesoporous imprinted procedure reported by published work [32]. The synthesis is briefed as
materials and Janus materials could advance prospective practical ap- follows: 4.25 g of iminodiacetic acid (IDA) was dissolved in 50 mL of
plications of materials because of dual-compartment Janus mesoporous DDW, whose pH was then adjusted to 11.0 with 10 M NaOH. The so-
imprinted structure. This inspired us to design imprinted mesoporous lution was placed in an ice-bath and 1.4 mL of (3-glycidyloxypropyl)
Janus films for dual-adsorption of Nd(III) and Dy(III). trimethoxysilane (GLYMO) was slowly added to the mixture with stir-
Herein, we reported ionic imprinted mesoporous bilayer films that ring. The mixed solution reacts for 6 h with stirring at 65 °C, followed
allowed for a unique combination of high adsorption capacity and si- by cooling the resultant solution in an ice-bath for 10 min. When the
multaneous dual-adsorption. Imprinted mesoporous bilayer films se- temperature of the solution was 0 °C, 1.6 mL of GLYMO was further
lectively adsorbed two different ions due to different imprinted sites on added slowly with vigorous stirring. The temperature of above solution
surface of different layers. Our approach for preparation of imprinted was raised to 65 C for further reaction for 6 h under stirring. Similarly,
mesoporous bilayer films was based on a simple layer-by-layer fabri- as above, 1.7 mL of GLYMO was again added into the above solution
cation method. We proposed dual-template docking oriented ionic im- and incubated overnight with stirring at 65 °C. Finally, the pH of pre-
printing (DTD-OII) for each layer based on the development of dual- pared GLYMO-IDA-silane solution was adjusted to 2.4 by using con-
template docking oriented molecular imprinting [29,30]. This method centrated HNO3. For synthesis of acetylacetone modified silane was
is simpler than traditional imprinted mesoporous materials just based based on our previous studies [19]. Briefly, (3-Chloropropyl)-triethox-
on evaporation-induced self-assembly (EISA). As illustrated in scheme, ysilane (CPTES, 50 mmol, 12.0 g) and sodium iodide (60 mmol, 9.0 g)
imprinted template was docked onto the surface of cellulose nano- were allowed to react in 125 mL of acetone for 48 h in nitrogen, opaque
crystallines (CNCs, structure-directing templates) to form the template- background, and reflux conditions. Then the acetone was removed
template docking configuration through electrostatic attraction. Then, under vacuum and n-hexane was added. The resulting suspension was
Si precursor and functional monomers were introduced to form ionic stirred for another 30 min and then filtered at nitrogen atmosphere to
imprinted mesoporous single films by EISA. Because of DTD-OII and remove the precipitate. The n-hexane was removed under vacuum and
EISA, all the imprinted sites were on the surface of the mesoporous the product distilled under reduced pressure. (Et3O)3Si(CH2)3I was
films, which improved imprinted efficiency and adsorption selectivity obtained as a yellow oil. Subsequently, 5.6 g of potassium was added in
apparently. The bottom layer remains intact and stable during deposi- 97 mL of dried tBuOH. After the potassium had dissolved, 4.5 g of
tion of the upper layer. Two layers differ only in selective functional acetylacetone (ACAC) was added. After stirring for 30 min at 50 °C,
monomers and REE ions. Subsequently, both the structure-directing 14.6 g of yellow liquid (Et3O)3Si(CH2)3I was added and the mixture was
template and imprinted template were removed to obtain dual-template reacted at reflux for 20 h. The solvent was removed under vacuum and
docking oriented ionic imprinted mesoporous bilayer films (IIBFs). The n-hexane was added, the suspension was stirred for another 10 min.
resulting IIBFs exhibit high selectivity, dual-adsorption, fast binding Then the suspension was filtered at nitrogen atmosphere. The filtrate
equilibrium, and excellent reusability in an acidic system. Further, we was concentrated and the product distilled under reduced pressure. The
grafted thermo-responsive polymer on the surface of IIBFs to realize resulting CPTES-ACAC-silane was an orange oil. For the preparation of
controlled release of Nd(III) and Dy(III) by temperature. bottom layer of IMFs, 7 ml of 3% CNCs suspension (pH = 2.4) was
sonicated for 10 min. D(+)-Glucose (50 mg) and a series of different
concentration of Nd(NO3)3 were added into the CNCs suspension and
2. Experimental the mixture suspension was stirred at 25 °C for 1.0 h, then tetra-
methoxysilane (TEOS, 280 μL) and 110 μL of GLYMO-IDA-silane were
2.1. Materials and methods added into solution. After stirred at 60 °C for 2.0 h, a homogeneous
mixture was obtained. This mixture was left to dry for 6–8 h at room
All chemicals unless otherwise stated, were purchased from temperature on a polystyrene Petri dish. During the time, synthesizing
Sinopharm Chemical Reagent Co., Ltd. and used without further pur- the upper layer was the same as the bottom expect that Dy(III) template
ification. Dual-template docking oriented ionic imprinted mesoporous was in place of Nd(III), and the derivative of the silane was not GLYMO-
bilayer films (IIBFs) were synthesized according to a modified reported IDA-silane solution, but the CPTES-ACAC-silane. The homogeneous
method. Schematic diagram of IIBFs was showed in Scheme 1. mixture rapidly paved in the bottom film. Almost two days slow eva-
poration at room temperature, the bilayer films were obtain. For si-
multaneously removal of the CNCs, Nd(III) and Dy(III) templates,

X. Zheng et al. Journal of Hazardous Materials 353 (2018) 496–504

Scheme 1. Schematic diagram of the free-standing dual-template docking oriented ionic imprinted bilayer films.

CNCs/silica composite films were placed in 900 mL of 6 M sulfuric acid 22 h. Finally, the NIPAM modified imprinted bilayer films were ob-
and heated to between 80–90 °C. Both the structure-oriented templates tained, noted as IIBFs. X-ray diffraction (XRD) of CNCs/silica composite
and the imprinted templates were efficiently removed simultaneously. film, IIBFs, and NIIBFs were measured to determine whether the tem-
The bilayer films were then fetched, washed with deionized water. The plates is removed completely. XRD pattern of CNCs/silica composite
films were then rinsed with 1 L of deionized water and air-dried. The film shows two peaks characteristic of crystalline cellulose at 2θ ≈ 16°
resulting films were named as p-IIBFs. and 24°. After removal of CNCs, only a broad peak characteristic of
Grafting the N-isopropylacrylamide (NIPAM) in upper layer amorphous silica and no peaks associated with the CNCs according with
achieved the purpose of dual-selective desorption in stripping tests. previous research (See Fig. S1) [34]. For preparation of non-imprinted
Firstly, we used the easily change of phase paraffin to protect the mesoporous bilayer films (NIIBFs) for comparison, the NIIBFs were
bottom layer from the influence of the grafting. Next, surface hydroxyl synthesized same with IMBFs except that no Nd(III) and Dy(III) tem-
groups of bilayers films were reacted with α-bromoisobutyryl bromide plates were added.
(BIBB) catalyzed by 4-dimethylaminopyridine (4-DMAP) and triethy-
lamine in dimethylformamide (DMF) [33]. Briefly, 0.5 g p-IIBFs was
solvent-exchanged from water to acetone to dry DMF by slightly stirring 2.3. Optimization of imprinting conditions
at room temperature for 12 h. then, the resulted films were placed in
50 mL of dry DMF with 0.0564 g of 4-DMAP under a nitrogen atmo- In order to optimize imprinted bilayer films, bottom layer films and
sphere. Then, 640 μL of TEA was slowly added. Subsequently, 571 μL of upper layer films were single prepared for study. Molar ratio of CPTES-
BIBB was added. The solution was left to react for 24 h at room tem- ACAC-silane to TEOS was changed and evaluated in terms of imprinted
perature and then washed by vast deionized water. The obtained p- factor (IF). The IF was calculated according to the ratio of the adsorp-
IIBFs were modified by surface-initiated atom transfer radical poly- tion capacity of templates captured by imprinted materials over that by
merization (SI-ATRP). polymerizations were carried out with ratio of non-imprinted materials. For details, totally 4 different molar ratios of
100/1/0.3/2 NIPAM/CuBr/CuBr2/PMDETA. In briefly, 0.0142 g of CPTES-ACAC-silane/TEOS were investigated from 0.6/9.4 to 0.1/9.9.
CuBr2, 2.2858 g of NIPAM, and 84 μL of N,N,N′,N″,N″-penta- 10 mg of different four films were immersed into 10 mL of Dy(III) stock
methyldiethylenetriamine (PMDETA) were mixed in 100 mL of water solution (50 mg L−1) with initial pH = 4 at 298 K. When adsorption
aqueous solution under nitrogen atmosphere. After which 0.0290 g of equilibrium was reached, final concentrations of Dy(III) were de-
CuBr was added to initiate polymerization at room temperature for termined by ICP-OES (ICP spectrometer, VARIAN America).

X. Zheng et al. Journal of Hazardous Materials 353 (2018) 496–504

2.4. Batch adsorption experiments

Adsorption performance (effect of pH, kinetics and adsorption iso-

therms) of IIBFs were researched by batch experiments. Further, se-
lectivity experiment, stripping test and reusability were also carried out
to evaluate adsorbents. The details of the batch experiments can be seen
in ESI.

3. Result and discussion

3.1. Characterization of IIBFs

Appropriate monomers will improve the adsorption capacity and

adsorption selectivity of designed materials. Based on hard and soft
acids and bases theory, IDA has an excellent adsorption of Nd(III) and
ACAC also can adsorb Dy(III). We choose GLYMO-IDA-silane as Fig. 2. N2 adsorption-desorption isotherms and pore size distributions (insert)
monomer for adsorption of Nd(III) and choose CPTES-ACAC-silane as for p-IIBFs, IIBFs, and NIIBFs.
another monomer for adsorption of Dy(III), which will effectively en-
hance imprinting properties based on our previous reports [19,35].
polymer layer on the upper layer with the thickness of about 1 μm. TEM
Functional monomer plays an equally important role in the imprinting
image of pore structure of IIBFs were shown in Fig. 1c. Films showed
procedure. In our previous study, we optimized concentration of
obviously long spindle-shaped pores, which is in agreement with our
GLYMO-IDA, so in this study, we directly used previous data of GLYMO-
previous study. The morphology of NIIBFs is similar with IIBFs (Fig. S3,
IDA-silane for preparation of bottom layer. Subsequently, molar ratio of
ESI). All the results indicate that dual-template docking oriented ionic
CPTES-ACAC-silane/TEOS was optimized of upper layer. For the opti-
imprinted bilayer films had been successfully prepared templated by
mization procedure (see ESI for details), the molar ratio of Dy(III) to
CPTES-ACAC-silane was fixed at 1/2. The molar ratio of CPTES-ACAC-
Nitrogen adsorption-desorption test were employed to characterize
silane to TEOS was investigated. Adsorption capacity of imprinted films
obtained IIBFs, NIIBFs, and pristine IIBFs (p-IIBFs) without thermo-re-
gradually dropped with the CPTES-ACAC-silane/TEOS molar ratio
sponsive polymer modification (Fig. 2). The corresponding parameters
range from 0.4/9.6 to 0.1/9.9. Non-imprinted films showed a dramatic
were also listed in Table 1. IIBFs, NIIBFs, and p-IIBFs exhibit typical
drop in adsorption when the ratio exceeded 0.4/9.6. The reduction of
type IV isotherms and distinctive H2 hysteresis loop [36]. From the
silane directly leads to the reduction of the selective adsorption site. But
Table 2, p-IIBFs possesses a high BET surface area of 522.04 m2 g−1,
for imprinted films, dual-template docking oriented ionic imprinting
with pore size of 2.005 nm and Vproe of 0.5105 cm3 g−1. BET surface
make all the imprinted sites on the surface of films, while not all the
area of IIBFs was 479.01 m3 g−1 which slightly deceased with p-IIBFs,
silane sites are on the surface of non-imprinted films. This leads to a
and similar phenomenon can be found for BET surface area of NIIBFs.
rapid decline in adsorption capacity for non-imprinted films. So the best
The reason for BET surface area decrease of IIBFs and NIIBFs possibly is
CPTES-ACAC-silane/TEOS molar ratio was 0.2/9.8, which gave an IF
polymer modification during the synthesis process.
value of 11.3 (Fig. S2, ESI).
The FT-IR spectra of bottom layer, upper layer, p-IIBFs, IIBFs, and
SEM images showed clearly the replication of two layer chiral ne-
NIIBFs were showed in Fig. 3. The adsorption bands of five films at
matic organization in IIBFs (Fig. 1a), which indicated dual-template
1089 cm−1 corresponded to the SieOeSi asymmetric stretching vi-
docking oriented ionic imprinted bilayer films were successfully syn-
brations. The broad bands 3425 cm−1 in the hydroxyl region for all the
thesized. In the magnification SEM of IIBFs (Fig. 1b), we can observe a

Fig. 1. SEM images of IIBFs (a), IIBFs magnification (b), TEM image of IIBFs (c), and real film photo (d).

X. Zheng et al. Journal of Hazardous Materials 353 (2018) 496–504

Table 1
Physicochemical parameters obtained by N2 adsorption-desorption measure-
ments for IIBFs, NIIBFs, and p-IIBFs.
Materials SBET (m2 g−1) Pore size (nm) Vproe (cm3 g−1)

IIBFs 479.0076 1.981 0.506873

NIIBFs 457.6447 1.975 0.504492
p-IIBFs 522.0404 2.005 0.510455

materials were assigned to the SieOH stretching vibration. In the

spectra of bottom layer and p-IIBFs, there was a small peak at
1739 cm−1 attributed to the stretching vibrations of C]O. For upper
layer and p-IIBFs, adsorption bands at 1685 cm−1, 2979 cm−1 and
2910 cm−1 are corresponded to C]O stretching vibration and the CH3
stretching vibration, respectively. These spectra confirmed that orga-
nosilane (CPTES-ACAC-silane and GLYMO-IDA-silane) has been suc-
Fig. 3. FT-IR spectra for the bottom layer, upper layer, p-IIBFs, IIBFs, and
cessfully involved in the skeleton of the IIBFs. Due to surface mod-
ification, IIBFs and NIIBFs just shows distinctive adsorption peaks at
about 1637 cm−1 (the stretching vibrations of C]O) and
2919 cm−1(the stretching vibrations of CH3). All the observation sug-
gests that IIBFs was synthesized successfully.
Thermogravimetric analysis (TGA) under nitrogen atmosphere of
bottom layer, upper layer, p-IIBFs, IIBFs, and NIIBFs were showed in
Fig. 4. The weight losses (about 10%) at the initial temperature
(< 100 °C) of all the samples mainly attributed to the loss of water. The
thermal decomposition of the functionalized absorbents (bottom layer,
upper layer, and p-IIBFs) occurred in the interval of temperatures be-
tween 150 and 750 °C. For IIBFs and NIIBFs, main weight losses about
30% was due to thermal decomposition of thermo-responsive polymer
in the temperatures range from 200 to 400 °C. The CHN elemental
analysis for bottom layer and upper layer were shown in Table S1 (ESI).
For both bottom and upper layers, the contents in C and H are similar.
Upper layer of IIBFs was modified by thermo-responsive polymer, so
the water contact angle of upper and bottom layer of IIBFs was further
studied to give more detailed and visual evaluation of the surface
wettability. As seen in Fig. S4, the water contact angle of upper layer Fig. 4. Thermogravimetric analysis curves of the bottom layer, upper layer, p-
was measured as 94.5°, which was larger than bottom layer (30.3°) IIBFs, IIBFs, and NIIBFs.
confirmed its hydrophobic nature. Thermo-responsive polymer changes
the surface wettability of upper layer obviously. solution. NIIBFs do not have imprinted cavities, which lead reduction of
adsorption capacity under acid condition. So, based on the IF of IIBFs
and NIIBFs under different pH, the best adsorption condition of pH was
3.2. The effect of pH chosen to be 4.0.

IIBFs can adsorb Nd(III) and Dy(III) simultaneously due to Janus

structure. So follow-up adsorption experiments were carried out in Nd 3.3. Adsorption kinetics
(III) and Dy(III) mixed solution.
Solution pH is a key parameter for REE recovery. So, the effect of pH Adsorption kinetic study of IIBFs and NIIBFs for Nd(III) and Dy(III)
on the IIBFs was investigated first. Adsorption capacities and the im- were in mixed stock solutions. It can be found from the Fig. 6, the
printing IF of IIBFs and NIIBFs are presented in Fig. 5. With increasing adsorption capacity of IIBFs for Nd(III) and Dy(III) increase in two
pH, adsorption capacities of Nd(III) and Dy(III) are both increasing, steps: first fast rise gets about 70% of total adsorption in the 30 min;
which indicates that acidic system can influence the imprinted sites due and second gradual increase lasts for 2–6 h to reach equilibrium. This is
to lower dissociation extent of the functional groups of IIBFs. For due to imprinted sites are all on the surface of IIBFs by dual-template
NIIBFs, a dramatic decrease can be found in pH lower than 5.0. Im- docking oriented ionic imprinting, which led to easier access of Nd(III)
printed cavities of IIBFs formed by dual-template docking orienting and Dy(III) to the binding sites on imprinting cavities. The pseudo-first-
provide specific spatial selectivity for Nd(III) and Dy(III) even in acidic order kinetic model (PFOKM) and pseudo-second-order kinetic model

Table 2
Kinetic constants for the Pseudo-first-order and Pseudo-second-order models.
Materials REEs Qe,exp (mg g−1) Pseudo-first-order kinetic model Pseudo-second-order kinetic model

−1 −1
Qe,c (mg g ) k1 (min ) R 2
Qe,c (mg g−1) k2×10−2(g mg−1 min−1) h (mg g−1 min−1) t1/2 (min) R2

IIBFs Dy(III) 14.21 13.50 0.0469 0.983 14.44 0.457 0.953 15.16 0.996
Nd(III) 10.01 9.53 0.0623 0.971 10.15 0.896 0.924 10.99 0.996

NIIBFs Dy(III) 1.24 1.17 0.0821 0.942 1.239 10.15 0.156 7.95 0.988
Nd (III) 1.30 1.23 0.0578 0.949 1.304 6.666 0.113 11.51 0.98445

X. Zheng et al. Journal of Hazardous Materials 353 (2018) 496–504

capacity of IIBFs is a significantly greater than that of NIIBFs at the

same condition. The result proves dual-template docking oriented ionic
imprinting can enhance the affinity for adsorption of Nd(III) and Dy
(III). Langmuir and Freundlich isotherm models [37,38] were used to fit
equilibrium data expressed as follows:
KL Qm Ce
Qe =
1 + KL Ce (5)

Qe = KF Ce1/ n (6)
where Qm (mg g−1) is maximum adsorption capacity of adsorbents. KL
(L g−1) is Langmuir affinity constant. KF (mg g−1) represents Freun-
dlich isotherm constant, and 1/n indicates favorable adsorption con-
The parameters of the Langmuir and Freundlich were compiled in
Fig. 5. The effect of pH on the adsorption capacity and IF of IIBFs. Error bar
Table 3. From Table 3, it confirms that the Langmuir model fits the
represents the standard deviation of the adsorption capacity.
experimental data better than the Freundlich model. This indicates the
binding sites of IIBFs and NIIBFs are uniformly distributed on their
(PSOKM) were modelled the experimental uptake kinetics of IIBFs and surfaces, resulting in finite ionic adsorption. The “favorability’’ of the
NIIBFs. The PFOKM and PSOKM are reported in Eqs. (1) and (2), re- adsorption can be evaluated using the separation factor
spectively: RL(dimensionless), which was calculated by Eq. (7).
Qt = Qe−Qe e−k1 t (1) 1
RL =
1 + Cm KL (7)
k2 Qe2 t
Qt =
1 + k2 Qe t (2) where Cm is the maximum initial concentration of the REE. The smaller
−1 −1
the value of RL is, the adsorbent is more favorable for the adsorption of
where Qt (mg g ) and Qe (mg g ) are adsorption capacities at time t, the given ions. The calculated values of RL of IIBFs is 0.1321 for Dy(III)
and at equilibrium, respectively. k1 (min−1) and k2 (g mg−1 min−1) are and 0.1167 for Nd(III), which are much less than 0.1659 for Dy(III) and
the rate constants of the PFOKM and PSOKM, respectively. The initial 0.1485 for Nd(III) of NIIBFs. It confirms the adsorption effect of IIBFs is
adsorption rate h (mg g−1 min−1) and half equilibrium time t1/2 (min) better than NIIBFs.
of the PSOKM were also analyzed, according to the Eqs. (3) and (4)
3.5. Selectivity
h = k2 Qe2 (3)
In order to evaluate the selective adsorption ability of IIBFs for re-
t1/2 = covery of Nd(III) and Dy(III), competitive experiments were studied
k2 Qe (4) with three interfering species (Tb(III), Pr(III), and Fe(III), major com-
Table 2 showed the corresponding parameters of adsorption ki- ponents of NdFeB). The selectivity of IIBFs was evaluated by distribu-
netics. From the table, PSORM fits the experimental data better than tion coefficients (Kd, mL g−1) which were based on following Eq. (8):
PFORM, which suggests the chemical process likely to be the rate- Co−Cf V
limiting step. The h and t1/2 of IIBFs were found to be superior to NIIBFs kd = ×
Cf m (8)
in Table 2. It indicates that dual-template docking oriented ionic im-
printing advances the kinetic properties of the IIBFs. where, Co and Cf are the initial and final concentration of metal ions,
3.4. Adsorption isotherms Fig. 8 showed the results of selective experiments for IIBFs and
NIIBFs. Kd of IIBFs for Nd(III) and Dy(III) are higher than those of
The adsorption isotherms of IIBFs and NIIBFs with respect to Nd(III) NIIBFs. The greater Kd value of IIBFs has attributed to the combination
and Dy(III) were shown in Fig. 7. The equilibrium curves of IIBFs show of the organosilane chelation and dual-template docking oriented ionic
a sharp increase, then adsorption capacity progressively reached to imprinting. In the NdFeB leachate, rare earth ions have the same charge
saturated adsorption capacity (17.50 mg g−1 for Dy(III) and and similar chelation ability with organosilane, so the dual-template
12.15 mg g−1 for Nd(III)). This asymptotic plateau appearance is con- docking oriented ionic imprinting plays a key role in selectivity ad-
sistent with a characteristic of monolayer adsorption. The adsorption sorption of Nd(III) and Dy(III). It provides an oriented selective cavities

Fig. 6. Kinetic data and modelling for the adsorption of Dy(III) and Nd(III) on IIBFs and NIIBFs. Error bar represents the standard deviation of the kinetic data.

X. Zheng et al. Journal of Hazardous Materials 353 (2018) 496–504

Fig. 7. Equilibrium data (a, b) and modelling (c, b) for the adsorption of Dy(III) and Nd(III) on IIBFs and NIIBFs. Error bar represents the standard deviation of the
kinetic data.

Table 3
Adsorption equilibrium constants for Langmuir and Freundlich isotherm equations.
Sorbents REEs Langmuir isotherm equation Freundlich isotherm equation

−1 −1
KL (L mg ) Qm (mg g ) RL R2 KF (mg g−1) 1/n

IIBFs Dy(III) 0.995 0.1108 18.64 0.0568 0.931 4.5910 0.2908

Nd(III) 0.998 0.0935 13.21 0.0666 0.904 3.0694 0.2971

NIIBFs Dy(III) 0.993 0.0355 2.02 0.1581 0.963 0.2348 0.4092

Nd (III) 0.995 0.0456 1.63 0.1276 0.920 0.2419 0.3678

Table 4
Comparison of rare earth ion adsorption performance for different sorbents.
Sorbent Metal pH Adsorption Reference
(mg g−1)

Imprinted styrene−divinylbenzene Dy(III) 7–9 40.15 [39]

11-Molybdo-vanadophosphoric acid Dy(III) 4–5 42–53 [40]
supported on Zr modified
mesoporous silica SBA-15
Phosphonic acid-functionalized Dy(III) 4.8 32–49 [41]
porous microspheres
IIBFs Dy(III) 4.0 17.50 This work
EDTA and DTPA functionalized Nd(III) 3–6 55 [42]
Ion imprinted polymer particles Nd(III) 7.5 33 [43]
Fig. 8. Kd values of the IIBFs and NIIBFs for a mixture of Dy, Nd, Pr, Tb, and Fe. IIBFs Nd(III) 4.0 12.15 This work
IIP-HQP/SiO2 Pr(III) 4.5 18.32 [44]
Error bars represent the standard derivation.
Sc(III) ion-imprinted polymers Sc(III) 6.5 12.8 [45]

of the imprinted sites for Nd(III) or Dy(III) which is not appropriate for
other rare earth ions. To further assess the adsorption selectivity of selective adsorb two different rare earth ions at the same time. IIBFs
IIBFs, a comparison between our IIBFs and other reported adsorbents have comparable adsorption properties for Nd(III) and Dy(III) in
was conducted in Table 4. From the table, we can see almost all the pH = 4.0 [39–45]. Sophisticated design of IIBFs are perfect materials
adsorption condition of REEs are in slightly acidic to neutral solutions. for recovery of Nd(III) and Dy(III) from waste NdFeB. Moreover, IIBFs
As far as we know, there are no reports of imprinted materials can have an obvious advantage that they can be easily retrieved without

X. Zheng et al. Journal of Hazardous Materials 353 (2018) 496–504

Table 5 capacity in acidic solution but also separate Nd(III) and Dy(III) si-
The stripping result of IIBFs under different temperature. multaneously, which makes films to be ideal adsorbents for the selec-
Temperture Stripping Nd(III) (mg g−1) Stripping Dy(III) (mg g−1) tive recovery of Nd(III) and Dy(III) from NdFeB leachate. Further, we
modified the upper side of bilayer films by NIPAM to achieve release of
313 K 8.04 2.01 REEs step by step in stripping test. In addition, excellent reusability and
298 K 1.96 11.73
simple retrievable process advanced practical application of NdFeB


This work was financially supported by the National Natural Science

Foundation of China (No. 21576120, No. 21446015, No. 21507045,
U1407123, No. U1507115, and No. U1507118) and Natural Science
Foundation of Jiangsu Province (No. BK20140534, No. BK20140580,
No. BK20151350, and No. BK20131223).

Appendix A. Supplementary data

Supplementary material related to this article can be found, in the

online version, at doi:


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