Preparation of Core–Shell Magnetic Molecularly Imprinted Polymer

Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Preparation of Core−Shell Magnetic Molecularly Imprinted Polymer with Uniform Thin Polymer Layer for Adsorption of Dichlorophen Jifeng Guo,*,†,‡ Miaomiao Yu,†,‡ Xiao Wei,*,†,‡ and Lihui Huang†,‡ Key Laboratory of Subsurface Hydrology and Ecological Effects in Arid Region, Ministry of Education and ‡School of Environmental Science and Engineering, Chang’an University, Xi’an 710054, China

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ABSTRACT: In this work, the magnetic Fe3O4 imprinted polymers were prepared with the precipitation polymerization method. The polymers were used to selectively identify dichlorophen in complex environmental system. The scanning electron microscopy and transmission electron microscopy scans of magnetic Fe3O4 molecularly imprinted polymers (MMIPs) were carried out. The adsorption properties of MMIPs were examined by adsorption isotherms, kinetics, and selectivity experiments. The Langmuir adsorption isotherm well fitted the adsorption experimental data, and an increase of temperature enhanced the adsorption capacity. The equilibrium adsorption capacity of MMIPs at 318 K was 50.45 mg g−1. The data of kinetics experiments were well fitted by pseudo-second-order equation. Compared to nonimprinted polymer, the MMIPs had more specific selectivity and higher adsorption performance for chlorophene with similar structure. In addition, the regeneration experiments demonstrated that MMIPs have stable adsorption capacity for target molecules and can be quickly recovered in applied magnetic field. Therefore, our study provided an appropriate imprinted polymer material for the adsorption of dichlorophen in water.

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INTRODUCTION Chlorinated disinfectants, such as dichlorophen, are widely used in pharmaceuticals personal care products (PPCPs),1,2 agricultural production.3 The hydrophobicity of chlorinated disinfectants suggests the bioaccumulation of these pollutants in an organism.4,5 As a result, trace residues of chlorinated disinfectants in water and soil are potentially harmful to the environment.6 The detection limit of the existing detection method for dichlorophen is still low. The existing removal methods for these new trace organic pollutants mainly include activated sludge,7 carbon adsorption,8 ozone oxidation,9 advanced catalytic oxidation,10 and membrane treatment technologies.11 Some studies have shown that activated carbon, a traditional adsorbent, has strong adsorption capacity and thereby removal effect of PPCPs in water.12 However, the above traditional adsorbents has limited specificity on the adsorption of organic matter. On the other hand, an imprinted polymer prepared with the surface imprinting method, which has easily obtained a three-dimensional binding site, can selectively adsorb dichlorophen. Target molecules can rapidly migrate on the surface of a polymer so as to accelerate the binding process and reduce the adsorption of nonspecific molecules and embedding phenomenon.13 Molecular imprinting is a technique that can be used to selectively recognize a substance in a complex system.14 Therefore, it is often used to get rid of organic substances that are difficult to remove by traditional methods.15 Molecularly imprinted polymers (MIPs) with three-dimensional binding sites facilitate the adsorption of target molecules in terms of their © XXXX American Chemical Society

shape, size and function. The preparation of MIPs is an innovative application of molecular imprinting technology, especially when used as an effective adsorbent to remove trace organic pollutants.16,17 The MIPs are easy to prepare and have high selectivity for contaminants of large molecule-weight. Because of the stable physical and chemical properties as well as low cost of MIPs, they have been widely used in many fields.18 Recently, magnetic nanoparticles drive much research interests, given that they can be quickly separated using an external magnetic field.19,20 The polymer prepared by traditional bulk polymerization method usually results in irregular shape and deeply buried binding sites, leading to low polymer adsorption capacity.21,22 Surface imprinting is a technology that attempts to keep the binding site of blotting on the surface of imprinted polymer as much as possible. As a result, template molecules can easily approach the binding site, so that it is favorable for the elution and recombination of template molecules.23,24 In combination with special recognition with magnetization properties, the introduction of imprint layer on the surface can overcome the disadvantages of traditional adsorption methods. In this study, magnetic molecularly imprinted polymers (MMIPs) were prepared using magnetic Fe3O4 as a support material and a convenient recycling function. The synthetic route is shown in Figure 1. The polymerization layer evenly distributed in the vinyl modified nanoparticles surface via a Received: April 21, 2018 Accepted: July 16, 2018

A

DOI: 10.1021/acs.jced.8b00321 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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g of polyethylene glycol was then added. The mixed solution was stirred vigorously for 30 min, sealed in 100 mL Teflon-lined stainless steel autoclave, heated to 200 °C for 8.0 h in an oven, and then cooled at room temperature. The generated magnetic nano-Fe3O4 particles were collected under an applied magnetic field. The collected nano-Fe3O4 particles were washed repeatedly with ethanol and water and then dried at 60 °C in vacuum overnight. The vinyl groups were used to modify the surface of magnetic nano-Fe3O4 particles. The detailed steps are presented as follows: 0.5 g of nano-Fe3O4 particles was dissolved in 50 mL of ethanol and the solution was sonicated for 10−20 min when stirring the solution; 2.0 mL of 3-(methacryloyloxy) propyl trimethoxysilane (KH570) was added dropwise, and the mixed solution was heated in a 50 °C water bath for 12 h to obtain modified magnetic particles. The modified magnetic particles were washed with ethanol several times and the washed particles were centrifuged and dried at 60 °C for 12 h in a vacuum. Preparation of Magnetic Molecularly Imprinted Polymer. The method of precipitation polymerization was used to synthesize magnetic imprinted polymer. The procedure was as follows: 60 mL of ethanol was added into a 100 mL flask into which 0.1 mmol dichlorophenol, 0.4 mmol MAA, 1.6 mmol EGDMA, and 10 mg of AIBN were added; after prepolymerization for a period of time, 0.1 g of modified Fe3O4 was added into the mixed solution and sonicated for 15 min. After removal of oxygen by nitrogen purging, the flask was placed in a thermostatic water bath shaker, and the products were obtained through two-step polymerization: a first step of prepolymerization at 50 °C for 6.0 h and a second step of polymerization at 60 °C for 24 h. When the reaction was completed, the products were washed with anhydrous ethanol several times to remove unreacted material. The products were then dried at 60 °C for 12 h in a vacuum oven and subjected to Soxhlet extraction for 22 h with a methanol and acetic acid mixture (9:1, V/V) 3−5 times. The template molecules were completely removed and dried in vacuum to obtain magnetic imprinted polymer. Magnetic nonimprinted polymers (MNIPs) were synthesized in the same manner except that no template molecules were added. Batch Binding Experiments. To investigate the adsorption capacity of the polymers, batch binding experiments were carried out in this study. In the adsorption experiment, 2.0 mg of MMIPs or MNIPs were added into 10 mL of dichlorophen solution of different initial concentrations (10−80 mg/L), which were prepared with ethanol and deionized water (1:3, V/ V). The solutions were placed for 12 h at 298, 308, and 318 K to reach adsorption equilibrium, respectively. The concentrations of free dichlorophen in the solutions were measured by a UV− vis spectrophotometer at 285 nm (the maximum absorption wavelength of dichlorophen). The amount of adsorbed dichlorophen can be calculated by the reduction of the remaining concentration from the initial concentration. The binding amount of dichlorophen Qe (mg/g) at equilibrium was calculated according to the following equation:

Figure 1. Schematic illustration of the preparation of magnetic molecularly imprinted polymers (MMIPs).

simple two-stage precipitation polymerization process. These synthetic magnetic imprinted polymers can time-saving recognize and adsorb target molecules.25 Wang et al.26 prepared unique magnetic mesoporous core−shell molecularly imprinted polymers via surface precipitation polymerization from the functionalized Fe3O4 support. The physical and chemical properties of the prepared nanoparticles were mainly characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Meanwhile, the adsorption isotherms, adsorption kinetics, selectivity experiments, and reuse experiments were studied. The results are presented in detail in this article.

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MATERIAL AND METHODS Materials. Dichlorophen (assay 98%, Product no. D11482225G, CAS registry no. 97-23-4), 2,4-dichlorophenol (2,4-DCP, assay >98%, Product and Batch no. D104289-25G K1703069, CAS registry no. 120-83-2), 2,6-dichlorophenol (2,6-DCP, assay 99%, Product and Batch no. D104318-25G A1810023, CAS registry no. 87-65-0), chlorophene (assay >97.0%, Product no. B152826-25G, CAS registry no. 120-32-1), and ethylene glycoldimethacrylate (EGDMA, assay >99%, Product and Batch no. M102640-500 mL J1731179, CAS registry no. 7941-4) were purchased from Aladdin Reagent CO. Ltd. (Shanghai, China). Methacrylic acid (MAA, assay ≥99%, CAS registry no. 79-06-1) was purchased from Tianjin Damao Chemical Reagent Factory. Ethanol (≥99.7%, CAS registry no. 64-17-5) and tetraethylorthosilicate (TEOs, CAS registry no. 78-10-4) were purchased from Tianjin Fuchen Chemical Reagent. 2,2′-Azobis (2-methyl-propionitrile) (AIBN, assay ≥98%, CAS registry no. 78-67-1) was purchased from Chengdu Kelong Chemical Reagent Factory. 3-(Methacryloyloxy) propyltrimethoxysilane (KH570, CAS registry no. 2530-85-0) was purchased from Shandong Yousuo Chemical Technology Co., Ltd. Ferric chloride hexahydrate (Fecl3·6H2O, CAS registry no. 10025-77-1), acetonitrile (≥99.5%, CAS registry no. 75-058), methanol (≥99.5%, CAS registry no. 67-56-1), acetic acid (≥99.5%, CAS registry no. 64-19-7), ethylene glycol (EG, CAS registry no. 107-21-1), sodium acetate (≥99%, CAS registry no. 127-09-3), water−ammonia (CAS registry no. 1336-21-6), and polyethylene glycol (PEG, CAS registry no. 25322-68-3) were all analytical reagents and purchased from Guangzhou Jinhuada Chemical Reagent Co. Ltd. Deionized water was obtained in the laboratory. Preparation and Modification of Magnetic Fe3O4 Nanoparticles. Briefly, 1.35 g FeCl3·6H2O was dissolved in 40 mL of ethylene glycol in which 3.6 g of sodium acetate and 1.0

Qe =

(C0 − Ce)V m

(1)

where C0 and Ce (mg/L) were the initial and equilibrium concentration of dichlorophen, respectively, V (L) was the volume of the solution, and m (g) was the mass of polymers. In the study of binding kinetics, 2.0 mg of MMIPs or MNIPs were added into 40 mg/L dichlorophen solution (ethanol and deionized water 1:3, V/V). The soluions were then incubated at B

DOI: 10.1021/acs.jced.8b00321 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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298, 308, and 318 K for time intervals ranging from 5 to 60 min, respectively. The adsorption capacities of dichlorophen Qt (mg/ g) were calculated as follows: Qt =

V (C 0 − C t ) m

(2)

where Ct (mg/L) was the free concentration of dichlorophen at any time t (min). In order to study the selectivity of the dichlorophen magnetic imprinted polymers, 2.0 mg of MMIPs or MNIPs was added into 10 mL of solution containing 40 mg/L of 2,4-dichlorophenol, 2,6-dichlorophenol, chlorophene, and dichlorophen. The adsorption properties of nonimprinted polymers were examined in the same way as those of MMIPs. Triplicates were prepared for all experiments, and the mean values were used for data analysis. Regeneration Performance of MMIP. In order to study the stability of adsorption capacity of MMIPs, 2.0 mg of MMIPs was added into 40 mg/L of dichlorophen solution, and the solution was incubated at 298 K for 0.5 h. The amount of remaining dichlorophen in the solution was measured. The template molecule was then eluted and the above experimental procedure was repeated 7 times to verify the regeneration experiment.

Figure 3. TEM image of Fe3O4 (a) and MMIPs (b).

nm. The images demonstrated the rough spherical particles of MMIPs with a thin film on the outer surface. It suggested that the imprinted layer was formed by surface precipitation polymerization in the surface polymerization of magnetic Fe3O4. The results were in agreement with those of Dai et al.27 Adsorption Isotherms. To investigate the adsorption capacity of MMIPs for dichlorophen at equilibrium state, the static adsorption data were fitted by Langmuir and Freundlich isotherm models.28 The nonlinear forms of isotherm model are shown as the eqs 3 and 4 Qe =

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RESULT AND DISCUSSION Characterization of MMIPs. The morphology of Fe3O4 and MMIPs were characterized by SEM (Figure 2). As shown in

KLQ mCe 1 + KLCe

Q e = KFCe1/ n

(3) (4)

where Qm (mg/g) was the maximum adsorption capacity of the polymers, KL (L/mg) was the Langmuir adsorption equilibrium constant, KF and n were the adsorption equilibrium constant of Freundlich, respectively. The adsorption of dichlorophen on the polymer was simulated using Langmuir and Freundlich isotherm models at three different temperatures (Figure 4). The parameters of isotherm equations are summarized in Table 1. As shown in Figure 4, the amount of adsorbed dichlorophen began to increase rapidly with the increase of initial concentration during the adsorption process regardless of temperature. After a period of time, the adsorption reached equilibrium. It is obvious that a higher temperature favored the increase of binding amount. The maximum binding capacities for MMIPs were 46.083 and 54.645 mg g−1 at 298 and 308 K, respectively. When the temperature was 318 K, the MMIPs exhibited the highest adsorption capacities 63.291 mg g−1. Compared with that of MNIPs 33.113 mg g−1, the imprinting site dramatically increased the adsorption capacity. Langmuir isotherm adsorption model (R2 > 0.98) well fit the process of adsorption of dichlorophen on the imprinted polymer, suggesting the adsorption process to be monolayer molecular layer adsorption. Adsorption Kinetics. The adsorption kinetic data of MMIPs and MNIPs for dichlorophen at 298, 308, and 318 K are shown in Figure 5. The adsorption rate was faster at the beginning, and the adsorption equilibrium was achieved within 40 min. The study of the kinetics of the adsorption reaction at different temperatures and different reaction times shows that as the temperature and time increase, the amount of adsorption also increases. Compared with MNIPs, the adsorption rates of MMIPs were always higher because of the presence of a large number of imprinted sites on the surface of Fe3O4. The adsorption kinetics of MMIPs for dichlorophen was studied by pseudo-first-order and pseudo-second-order kinetics,29 the nonlinear forms of which were respectively expressed as the eqs 5 and 6

Figure 2. SEM images of the Fe3O4 (a,b) and MMIPs (c,d).

Figure 2a,b, the spherical Fe3O4 nanoparticles with rough surface have an average diameter of ∼150 nm, and he MMIPs particles were also spherical (Figures 2c,d); however, their surfaces are smooth and the average size increased to ∼165 nm compared to the Fe3O4 nanoparticles. It implies that the imprinted layer was successfully grafted onto the Fe3O4 nanoparticles. The properties of MMIPs were characterized by TEM. The results are shown in Figure 3. It can be seen from the image a that the diameter of synthesized Fe3O4 nanoparticles was approximately 70−150 nm with a regular shape and rough surface. The prepared MMIPs are still spherical nanoparticles with smaller diameter and smoother surface than Fe3O4. From Figure 3b, we can calculate that the thickness of the polymer layer was ∼14 C

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Figure 4. Fitting curves to the Langmuir and Freundlich isotherm of dichlorophen MMIPs (a) and MNIPs (b) toward dichlorophen at different temperatures.

Table 1. Isotherm Constants for Dichlorophen Adsorption onto MMIPs and MNIPs Langmuir

Freundlich

samples

T (K)

Qe (mg g−1)

Qm (mg g−1)

KL (L mg−1)

R2

KF[(mg g−1)(L mg−1)]

1/n

R2

MMIPs

298 308 318 298 308 318

36.12 43.72 50.45 26.54 32.91 40.90

46.083 54.645 63.291 33.113 44.250 54.640

0.0632 0.0728 0.0705 0.0654 0.0492 0.0500

0.9842 0.9854 0.9808 0.9929 0.9751 0.9630

5.842 8.012 8.527 5.1987 6.4637 8.3461

0.4617 0.4319 0.456 0.4039 0.3982 0.3879

0.8920 0.8987 0.8998 0.9533 0.9862 0.9395

MNIPs

Figure 5. Adsorption kinetic polts of MMIPs (a) and MNIPs (b) toward dichlorophen and fitting curves to the pseudo-second-order kinetic model at three temperature.

Table 2. Constants of the Adsorption Kinetic Constants for Dichlorophen onto MMIPs and MNIPs pseudo-first-order

pseudo-second-order

adsorption

T (K)

Qe,exp (mg g−1)

Qe,c (mg g−1)

k1 (min−1)

R2

Qe,c (mg g−1)

k2 (g mg−1 min−1)

R2

MMIPs

298 308 318 298 308 318

35.36 40.52 51.06 25.56 33.47 43.30

30.47 35.23 43.71 22.26 29.40 37.97

0.0321 0.0311 0.0299 0.0326 0.0285 0.0294

0.8521 0.8619 0.8839 0.8527 0.8901 0.9192

35.28 40.05 50.37 25.52 33.27 43.13

0.00635 0.00365 0.00340 0.00775 0.00301 0.00268

0.9972 0.9964 0.9931 0.9977 0.9918 0.9988

MNIPs

Q t = Q e − Q ee−kt

Qt =

The values of kinetic model parameters are listed in Table 2. The pseudo-second-order kinetic model performed better than pseudo-first-order. Hence, the pseudo-second-order model can better fit the adsorption process, and the values of Qe,c are calculated by the pseudo-second-order model. At three temperatures are closer to the Qe,exp value obtained from the experiment, which also supported that pseudo-second-order

(5)

k 2Q e2t 1 + k 2Q et

(6)

where k1 (min−1) was the pseudo-first-order rate constant, and k2 (g μmol−1 min−1) was the pseudo-second-order rate constant. D

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kinetic model to be better for the adsorption of dichlorophen by MMIPs and MNIPs. Pseudo-second-order kinetic equation can better fit the Fe3O4 surface imprinted polymer selective identification of dichlorophen kinetic data, indicating that the selective recognition was chemical adsorption process. Meanwhile, the adsorption kinetics of dichlorophen highly depends on temperature and initial concentration, given that the pseudosecond-order rate constant k2 increased with increasing temperature and the initial concentration of dichlorophen. Selectivity Property of MMIPs. The most prominent feature of MMIPs is that it has special selection recognition toward template molecule, which is an important index to evaluate its performance. In this study, we used chlorophene, 2,6-DCP, and 2,4-DCP, which also have greater impact on the environment, to evaluate the selectivity of MMIPs. Figure 6

Table 3. Morphology and Adsorption Property of Various MIPs

Figure 6. Experimental data of selective adsorption.

Figure 7. Stability and reuse of MMIPs.

shows the adsorption capacity of MMIPs and MNIPs to the three substances under the same conditions. It can be seen that the adsorption capacities of MMIPs for dichlorophen is noticeably higher than those for chlorophene, 2,6-DCP, and 2,4-DCP. It is because the surface of MMIPs has sites that can completely match the function group spots of dichlorophen. Thus, these sites have the ability to selectively recognize and bind dichlorophen. In addition, it can also be seen from the figure that the adsorption capacity of MMIPs to any substance is higher than the counterpart of MNIPs. Moreover, the adsorption capacity of MMIPs for chlorophene is greater than those for 2,4-DCP and 2,6-DCP, probably due to the similar chemical structure of cholophene with dichlorophen. However, there is a large difference between the adsorption amounts of dichlorophen, chlorophene, 2,6-DCP and 2,4-DCP by MMIP and MNIP. The adsorption of dichlorophene by MMIP and MNIP is much greater than that of 2,6-DCP and 2,4-DCP. In summary, MMIPs have strong selective selectivity for the template molecule dichlorophen. In Table 3, the morphology and binding characteristics of MIPs collected from various references are listed. Therefore, it can be concluded that the core−shell structure MMIPs prepared by us not only has excellent binding ability but also has a faster binding dynamics. Regeneration Property of MMIPs. Repeated seven experiments can be used to demonstrate the regeneration and stability of MMIPs. The adsorption results of MMIPs after each adsorption in the experiment were listed in Figure 7. As can be

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morphology irregular irregular core−shell

core−shell nanosphere

bulk polymerization cocktail polymerization surface initiated radical polymerization precipitation polymerization

equilibrium time

Qm

methodology

−1

reference

3h

30

24 h

31

1.6 mg g−1

1h

32

63.3 mg g−1

40 min

this study

21.65 mg g 3.84 mg g

−1

seen from the figure, MMIPs can good be used in practical applications recycled.

CONCLUSIONS Surface imprinting was employed to synthesize magnetic imprinted polymers in this study. It was found that a polymer layer with template molecules was successfully imprinted on the Fe3O4. The batch adsorption experiments demonstrated that the increase of temperature can improve the adsorption capacities of polymer. The adsorption isotherms and kinetics studies showed that the adsorption of dichlorophen complied with monolayer adsorption and was subject to pseudo-second-order kinetics. Selectivity experiments showed that MMIPs had significantly higher adsorption capacity for dichlorophen than MNIPs. In addition, MMIPs had higher adsorption capacity for chlorophene than 2,4-DCP and 2,6-DCP due to similar chemical structure of chlorophene with dichlorophen. Moreover, the regeneration experiments indicated that MMIPs had good stability. Upon the basis of the results of this study, MMIPs is a promising material to remove trace levels of dichlorophen in aqueous environment.

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AUTHOR INFORMATION

Corresponding Authors

*Tel: +86 029 82339956. Fax: +86 029 82339281. E-mail: [email protected] (J.F.G.). *Tel: +86 029 82339956. Fax: +86 029 82339281. E-mail: [email protected] (X.W.). E

DOI: 10.1021/acs.jced.8b00321 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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ORCID

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Xiao Wei: 0000-0002-4092-3059 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This study was financially supported by the special fund for basic scientific research of central colleges, Chang’an University (310829172002, 310829163406, 310829161002), Chang’an university students innovation program (201710710098, 201810710101), Natural Science Foundation of China (21607015), Science & Technology Support Foundation of Shaanxi Province (2018JQ2025, 2016JQ2008).

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DOI: 10.1021/acs.jced.8b00321 J. Chem. Eng. Data XXXX, XXX, XXX−XXX