Preparation of Ion-Imprinted Material Based on 2-Ethylhexylamino Methyl Phosphonic Acid Mono-2-Ethylhexyl Ester Extractant and Its Application for the Removal of Trace Scandium

doi:10.19894/j.issn.1000-0518.250086

Chinese Journal of Applied Chemistry ›› 2025, Vol. 42 ›› Issue (9): 1245-1256.DOI: 10.19894/j.issn.1000-0518.250086

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Preparation of Ion-Imprinted Material Based on 2-Ethylhexylamino Methyl Phosphonic Acid Mono-2-Ethylhexyl Ester Extractant and Its Application for the Removal of Trace Scandium

Cheng LI¹, Yan-Ling LI²(), Song-Song LI², Xiao-Long LUO¹(), Bi-Cheng DENG³^,⁴, Wu-Ping LIAO²^,³^,⁴

^1.College of Chemistry and Life Sciences，Changchun University of Technology，Changchun 130022，China
^2.State Key Laboratory of Rare Earth Resources Utilization，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China
^3.Institute of Material and Chemistry，Ganjiang Innovation Academy，Chinese Academy of Sciences，Ganzhou 341000，China
^4.Institute of Rare Earths Material and Chemistry，Jiangxi Institute of Rare Earths，Chinese Academy of Sciences，Ganzhou 341000，China

Received:2025-02-28 Accepted:2025-07-24 Published:2025-09-01 Online:2025-09-28
Contact: Yan-Ling LI,Xiao-Long LUO
About author:luoxiaolong890419@163.com
liyanling@ciac.ac.cn；
Supported by:
the National Key Research and Development Project(2022YFC2905201)

Abstract

Abstract:

Ion-imprinted material P-IIM was prepared using Sc³⁺-2-ethylhexylamino methyl phosphonic acid mono-2-ethylhexyl ester （HEHAMP） chelate as a template for the selective adsorption of scandium and characterized by Fourier transform infrared （FT-IR） spectrometer， thermal gravimetric analyzer （TGA）， and scanning electron microscopy （SEM）， etc. P-IIM can not be obtained when the percentage of HEHAMP extractant is more than 50%. The adsorption of Sc³⁺ ions in chloride solution by P-IIM was investigated and the effects of extractant mass， initial pH value， time， initial Sc³⁺ concentration and other coexisting metals were evaluated. The adsorption of Sc³⁺ by P-IIM increases gradually with the increasing content of HEHAMP extractant， while it first increases and then decreases as the initial pH of the solution increases. The adsorption capacity is the highest when the pH is 2. The adsorption of Sc³⁺ follows a quasi-two-stage kinetic model and is dominated by monolayer adsorption. P-IIM can be applied in the removal of trace scandium from rare earth solutions. The removal rate of scandium is more than 98%.

Key words: 2-Ethylhexylamino methyl phosphonic acid mono-2-ethylhexyl ester, Ion-imprinted material, Adsorption, Scandium, Selectivity

CLC Number:

O658.2

Cheng LI, Yan-Ling LI, Song-Song LI, Xiao-Long LUO, Bi-Cheng DENG, Wu-Ping LIAO. Preparation of Ion-Imprinted Material Based on 2-Ethylhexylamino Methyl Phosphonic Acid Mono-2-Ethylhexyl Ester Extractant and Its Application for the Removal of Trace Scandium[J]. Chinese Journal of Applied Chemistry, 2025, 42(9): 1245-1256.

Figures/Tables 16

Fig.1 Flow chart of P-IIM preparation

Fig.2 FT-IR spectra of （a） PVDF/PVA/CAT，（b） P-PIM，（c） P-IIM，（d） Sc3+-P-IIM and （e） HEHAMP

Fig.3 Plots of the TGA-DTA results for PVDF/PVA/CAT and P-IIM （A） and N2 adsorption isotherm for P-IIM （B）

Fig.4 SEM images of PVDF/PVA/CAT （A）， P-IIM （B） and Sc3+-P-IIM （C）； EDS mapping images of P， Sc and Cl of Sc3+-P-IIM （D-F）

Table 1 Determine the a（P）/（Sc） ratio of different materials

Serial number	m/g	n_HEHAMP/mmol	a_{（P）/（Sc）}
Ⅰ	0.040 7	0.048 53	66.64
Ⅱ	0.208 5	0.033 6	2.70
Ⅲ	0.043 5	0.034 3	2.76

Fig.5 Effect of the content of HEHAMP on the Sc3+ adsorption by P-IIM

Fig.6 Effect of initial pH of the solution on the adsorption of Sc3+ by P-PIM and P-IIM

Fig.7 Effect of the adsorption time on the adsorption of Sc3+ and the fitting of quasi-first-order kinetics （A）， quasi-second-order kinetics （B） and intraparticle diffusion model （C）

Table 2 Kinetic parameters of Sc3+ adsorption by P-PIM and P-IIM

Adsorbents	PFOM			PSOM
Adsorbents	Q_e/（mg·g^-1）	k₁/min^-1	R²	Q_e/（mg·g^-1）	k₂/（g·mg^-1·min^-1）	R²
P-PIM	13.08	0.008 7	0.966 3	15.37	0.000 71	0.993 2
P-IIM	15.99	0.011 0	0.979 9	18.83	0.000 64	0.990 3

Table 3 Intraparticle diffusion model parameters for Sc3+ adsorption by P-PIM and P-IIM

Adsorbents	Intraparticle diffusion model
Adsorbents	k_d1/（mg·g^-1·min^-1/2）	k_d2/（mg·g^-1·min^-1/2）	k_d3/（mg·g^-1·min^-1/2）	C/（mg·g^-1）	$R 12$	$R 22$	$R 32$
P-PIM	0.885 2	0.438 4	0.124 5	10.35	0.937 2	0.972 5	0.937 4
P-IIM	1.297 3	0.514 4	0.006 2	14.84	0.985 4	0.985 6	0.928 4

Table 3 Intraparticle diffusion model parameters for Sc3+ adsorption by P-PIM and P-IIM

Adsorbents	Intraparticle diffusion model
Adsorbents	k_d1/（mg·g^-1·min^-1/2）	k_d2/（mg·g^-1·min^-1/2）	k_d3/（mg·g^-1·min^-1/2）	C/（mg·g^-1）	$R 12$	$R 22$	$R 32$
P-PIM	0.885 2	0.438 4	0.124 5	10.35	0.937 2	0.972 5	0.937 4
P-IIM	1.297 3	0.514 4	0.006 2	14.84	0.985 4	0.985 6	0.928 4

Fig.8 Influence of the initial Sc3+ concentration on P-IIM adsorption （A）， fitting curves of the Langmuir isotherm model and （B）， the Freundlich isotherm model （C）

Table 4 Adsorption isotherm parameters of Sc3+ by P-PIM and P-IIM

T/K	Adsorbents	Langmuir model			Freundlich model
T/K	Adsorbents	Q_m/（mg·g^-1）	K_L/（L·mg^-1）	R²	K_F/（L·mg^-1）	1/n	R²
301	P-PIM	15.21	0.089 6	0.986 0	1.721	0.461 3	0.922 7
301	P-IIM	16.92	0.060 5	0.980 1	2.257	0.407 1	0.954 2

Fig.9 Effect of coexisting ion on the adsorption of Sc3+ at a mass concentration ratio of 1∶1 （A） and 1∶500 （B）

Table 5 Adsorption capacity and selectivity of Sc3+ by different materials

Adsorbents	Q_e/（mg·g^-1）	ρ（Sc³⁺）/ρ（coexisting ions）	Selectivity factor （K_Sc/M） of Sc³⁺ to coexisting ions		Ref.
Adsorbents	Q_e/（mg·g^-1）	ρ（Sc³⁺）/ρ（coexisting ions）	Fe³⁺	La³⁺， Gd³⁺， Y³⁺， Yb³⁺	Ref.
IIP-BT/CoFe₂O₄@SiO₂	128.02	1∶1	1.740	/	［15］
IIP-BT/CoFe₂O₄@SiO₂	128.02	1∶2	1.632	/	［15］
P40-750	20.77	1∶1	27.04	Y³⁺： 208.25， Dy³⁺： 77.74	［32］
PLS MTS9580	—	1∶4	6.9	—	［33］
TRPO/SiO₂-P	13.3	1∶1	＞4 089	Y³⁺＞4 089， La³⁺＞4 089， Ce³⁺＞4 089	［34］
P-IIM	16.54	1∶1	7.38	La³⁺： 130.81， Gd³⁺： 30.27， Yb³⁺： 16.52， Y³⁺： 132.2	This paper
P-IIM	16.54	1∶500	55.2	La³⁺： 90.1， Gd³⁺： 73.1 Yb³⁺： 86.4， Y³⁺： 26.0	This paper

Table 6 Concentration and removal rate of metal ions from mixed rare earth solutions

Concentration of the solution	Components
Concentration of the solution	La	Sc	Gd	Sc	Yb	Sc	Y	Sc
ρ_before/（mg·L^-1）	329.7	2.98	409.6	4.22	404.0	3.24	317.0	3.55
ρ_after/（mg·L^-1）	328.0	0.053	412.0	0.072	396.4	0.063	315.6	0.04
Removal rate/%	0.52	98.22	0.59	98.29	1.88	98.87	0.44	98.06

Fig.10 Desorption of Sc3+ by different concentrations of EDTA disodium salt （A） and the recycling and regeneration of Sc3+ by P-IIM （B）

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Preparation of Ion-Imprinted Material Based on 2-Ethylhexylamino Methyl Phosphonic Acid Mono-2-Ethylhexyl Ester Extractant and Its Application for the Removal of Trace Scandium

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