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Synthesis of cadmium(ii) ion-imprinted composite membrane with a pyridine functional monomer and characterization of its adsorption performance

  • Yuwen Hong , Xin Wang , Dongxue Fu , Guifang Wang , Li Zhao and Huiling Cheng EMAIL logo
Published/Copyright: August 22, 2023
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e-Polymers
From the journal e-Polymers Volume 23 Issue 1

Abstract

Cd(ii) ion was used as template ion, and N,N'-pyridine-2,6-di(2-methacrylamide) was used as the functional monomer. The experimental conditions for the synthesis of Cd(ii) ion-imprinted composite membranes (Cd(ii)-IICMs) were optimized by the surface-imprinting method, and 25 Cd(ii)-IICM1–25 and their corresponding non-imprinted composite membranes (NICM1–25) were prepared. Then, the structures of the optimal membranes Cd(ii)-IICM17 and NICM17 were characterized by scanning electron microscopy, Brunner–Emmett–Teller, thermogravimetric analysis, contact angle analysis, and the effects of different adsorption conditions were studied. The adsorption behavior was analyzed by isothermal adsorption models and kinetic models. The permeation selectivity of Cd(ii)-IICM17 towards Cd(ii) ions was studied. Results of the experiment indicate that Cd(ii)-IICM17 had excellent adsorption properties for Cd(ii) ions with an imprinting factor of 2.15. The adsorption of Cd(ii) ions in solution by Cd(ii)-IICM17 and NICM17 was in accordance with the Freundlich isothermal adsorption model and the pseudo-second-order kinetic model. In addition, in the presence of the competing ions Co(ii), Ni(ii), and Cu(ii), Cd(ii)-IICM17 showed good permeation selectivity for Cd(ii) ions, and the permeation process followed a facilitated permeation mass-transfer mechanism. In summary, the Cd(ii)-IICM17 prepared in this study has good application prospects for the separation and removal of Cd(ii) ions from wastewater.

Keywords: Cd(ii); ion-imprinted composite membrane; pyridine functional monomer; surface-imprinting; permeation selectivity

1 Introduction

Surface imprinting (1) is a technique based on molecular imprinting, in which imprinted ions or molecules are controlled so that polymerization occurs on the surface or outer layer of an imprinted material. This increases the number of imprinting sites, as well as the adsorption capacity of the resulting materials. Imprinted materials prepared by surface imprinting readily elute template ions or molecules that are not easily embedded (2), and the imprinting sites are mostly located on or near the surface of the material. This increases the adsorption capacity of the imprinted material and improves its specific recognition ability. Because of its high stability and selective separation, surface imprinting has been used in many subjects such as biological isolation (3), solid-phase extraction (4), food safety (5), sensors (6), and biomedicine (7).

Cadmium (Cd) is the most biologically toxic heavy metal element and has strong chemical activity (8) in the natural environment and long-term toxicity. The WHO and the EPA set the maximum permissible intake of Cd(ii) ions in humans at 1 μg·kg−1·day−1 (9). Cd(ii) ions tend to accumulate in the kidneys, bone tissues, eyes, and other organ tissues in humans (10). In the early twentieth century, Cd contamination attracted widespread attention after Cd poisoning was reported in Japan. Li et al. (11) designed a beneficiation backfilling method to control cadmium contamination produced during mining activities and verified the effectiveness of the method through engineering examples. Sharma and Naushad (12) prepared asbestos-activated carbon-loaded zirconium oxide composites and used them for the removal of Cd(ii) ions from water.

To obtain ion-imprinted composite membranes (IICMs) with good performance, it is important to select suitable functional monomers; however, conventional functional monomers contain few functional groups and limited recognition sites (13). Therefore, a new functional monomer N,N'-pyridine-2,6-bis(2-methacrylamide) (PMA) containing a nitrogen heterocycle with pyridine as the parent molecule was synthesized whose N and O atoms could coordinate with Cd(ii) ions. Using PMA as the functional monomer and Cd(ii) ion as the template ion, 25 Cd(ii) ion-imprinted composite membrane (Cd(ii)-IICM1–25) and their corresponding non-imprinted composite membranes (NICM1–25) were prepared by surface imprinting. The experimental conditions such as the base membrane type, functional monomer dosage, cross-linking agent dosage, porogenic agent type, porogenic agent ratio, and membrane immersion time were optimized. Equilibrium adsorption experiments were conducted to test the adsorption capacity of the prepared series of imprinted membranes (Cd(ii)-IICM1–25) and the best imprinted composite membrane Cd(ii)-IICM within the experimental range was screened based on the experimental results. Scanning electron microscopy (SEM), Brunner–Emmett–Teller (BET), thermogravimetric, contact angle, adsorption, and permeation experiments were used to study the structural characteristics, adsorption properties, and permeation selectivity of the optimal imprinted composite membranes, Cd(ii)-IICM17, and its corresponding non-imprinted membrane, NICM17. The influence of different adsorption conditions on the adsorption performances of Cd(ii)-IICM17 were also investigated. The results showed that Cd(ii)-IICM17 had a high imprinting factor (IF) and good permeation selectivity for Cd(ii) ions, indicating that Cd(ii)-IICM17 is expected to be used for the removal of Cd(ii) ions from wastewater.

2 Materials and methods

2.1 Reagents and materials

Cadmium nitrate (Cd(NO3)2·4H2O) anhydrous dichloromethane, anhydrous sodium sulfate, glacial acetic acid, methanol, ethanol, acetonitrile, isopropanol, and N,N-dimethylformamide (DMF) were procured from Tianjin, China. Triethylamine, methylacryloyl chloride, 2,2-azobisisobutyronitrile (AIBN), and ethylene glycol dimethacrylate (EDGMA) were purchased from Shanghai, China. The functional monomer PMA was designed and synthesized in the laboratory. The other reagents were analytically pure, and the water used during the experiments was deionized water.

2.2 Instrument

The measurements were carried out using a UV-2500 spectrophotometer (Shimadzu, Japan) and an ICP-OES (Leeman, USA), respectively. The remaining instruments used for the experimental procedures were as follows: GF-254 silica gel plate (Qingdao, China), SHZ-82 thermostatic oscillator, SHZ-82A water bath thermostatic oscillator (Changzhou, China), Phenom electron microscope and energy dispersive spectrometer (Shanghai. China), electronic balance (Beijing, China), ultrasonic cleaner (Tianjin, China), laboratory pH meter (Shanghai, China), digital display thermostat water bath (Changzhou, China), NMR spectrometer (Bruker, Germany), and 200–300 mesh chromatography silica gel plate (Qingdao, China).

2.3 Synthesis of new functional monomer PMA

The synthesis conditions for PMA were optimized according to Table A1 (in Appendix), resulting in the following optimal synthesis conditions: Triethylamine (3 mL, 30 mmol), 3 mL of methacryloyl chloride, and 50 mL of anhydrous dichloromethane were added to a round bottom flask (100 mL), which was placed in an ice-water bath and stirred until completely dissolved. 10 mmol of 2,6-diaminopyridine was added in batches, and the reaction was continued for 24 h. After using thin layer chromatography to detect the product, 20 mL saturated aqueous potassium carbonate solution was slowly added and mixed for 30 min, and extracted three times with 20 mL dichloromethane. After extraction, the product was dried using anhydrous sodium sulphate and concentrated under vacuum. The resulting product was recrystallized using petroleum ether/ethyl acetate (1/1, v /v) to give a light yellow solid, as N,N'-pyridine-2,6-bis(2-methylacrylamide)(N,N'-(1,2-dihydropyridine-2,6-diyl) bis (2-methylacrylamide)). The synthetic route is shown in Scheme 1.

Scheme 1 Synthesis of PMA.
Scheme 1

Synthesis of PMA.

2.4 Preparation of composite membranes

According to the experimental conditions shown in Table 1, 25 imprinted composite membranes Cd(ii)-IICM1-25 and their corresponding NICM1–25 were prepared. Template ion Cd(NO3)2·4H2O (0.1 mmol) and a specified amount of PMA were dissolved in 10 mL porogenic solvent to form a mixed solution that was shaken at 25°C for 3 h. Subsequently, the crosslinker EDGMA and initiator AIBN were added and ultrasonicated after degassing for 5 min. The corresponding base membrane was placed in this mixed solution and soaked for a certain time (see Figure 1 for specific soaking time). It was then removed and placed between two glass plates, then put in a 60°C constant-temperature oscillator, and polymerized for 12 h to obtain an imprinted composite membrane. The template ions were eluted with a methanol/acetic acid mixed solution with a volume ratio of 9:1, then washed with methanol to neutrality, and vacuum dried for 12 h to obtain Cd(ii)-IICM1–25. A schematic diagram of the preparation of Cd(II)-IICM is shown in Figure 1.

Table 1

Experimental conditions for the preparation of Cd(ii)-IICM1–25 and NICM1–25

Membrane Membrane type Dosage of the function monomer (mmol) Crosslinking agent (mmol) Type of porogenic agent Porogenic agent ratio (v/v) Membrane soaking time (s)
Cd(ii)-IICM1 PTFE 0.4 2 Methanol/water 1/1 360
Cd(ii)-IICM2 PVDF 0.4 2 Methanol/water 1/1 360
Cd(ii)-IICM3 Nylon-6 0.4 2 Methanol/water 1/1 360
Cd(ii)-IICM4 PTFE 0.2 2 Methanol/water 1/1 360
Cd(ii)-IICM5 PTFE 0.6 2 Methanol/water 1/1 360
Cd(ii)-IICM6 PTFE 0.8 2 Methanol/water 1/1 360
Cd(ii)-IICM7 PTFE 0.4 1 Methanol/water 1/1 360
Cd(ii)-IICM8 PTFE 0.4 3 Methanol/water 1/1 360
Cd(ii)-IICM9 PTFE 0.4 4 Methanol/water 1/1 360
Cd(ii)-IICM10 PTFE 0.4 5 Methanol/water 1/1 360
Cd(ii)-IICM11 PTFE 0.4 6 Methanol/water 1/1 360
Cd(ii)-IICM12 PTFE 0.4 7 Methanol/water 1/1 360
Cd(ii)-IICM13 PTFE 0.4 5 Ethanol/water 1/1 360
Cd(ii)-IICM14 PTFE 0.4 5 DMF/water 1/1 360
Cd()-IICM15 PTFE 0.4 5 Acetonitrile/water 1/1 360
Cd(ii)-IICM16 PTFE 0.4 5 Isopropanol/water 1/1 360
Cd(ii)-IICM17 PTFE 0.4 5 Methanol/water 1/3 360
Cd(ii)-IICM18 PTFE 0.4 5 Methanol/water 2/3 360
Cd(ii)-IICM19 PTFE 0.4 5 Methanol/water 3/2 360
Cd(ii)-IICM20 PTFE 0.4 5 Methanol/water 3/1 360
Cd(ii)-IICM21 PTFE 0.4 5 Methanol/water 1/3 30
Cd(ii)-IICM22 PTFE 0.4 5 Methanol/water 1/3 60
Cd(ii)-IICM23 PTFE 0.4 5 Methanol/water 1/3 180
Cd(ii)-IICM24 PTFE 0.4 5 Methanol/water 1/3 1,200
Cd(ii)-IICM25 PTFE 0.4 5 Methanol/water 1/3 3,600
Figure 1 Schematic diagram of the preparation of Cd(ii)-IICM.
Figure 1

Schematic diagram of the preparation of Cd(ii)-IICM.

The preparation process of the corresponding NICM1–25 is the same as the above method, except no template ions were added.

2.5 Equilibrium adsorption experiment

20 mg each of the Cd(ii)-IICM and NICM were placed in a 25 mL conical flask with a stopper and then 10 mL of 25.6 mg·mL−1 Cd(ii) ion was added. The solution was shaken at room temperature for 12 h and then filtered. The corresponding porogen was used to dilute the volume to 10 mL, and its absorbance was measured at 302 nm. Finally, the equilibrium adsorption capacity Q and IF of Cd(ii) on the Cd(ii)-IICM were calculated by Eqs. 1 and 2 as follows:

(1) Q = ( C 0 – C ) V m

(2) IF = Q Cd ( II ) − IICM / Q NICM

where C 0 is the initial concentration of the Cd(ii) solution (mg·mL−1); C is the concentration of Cd(ii) ion in solution at adsorption equilibrium (mg·mL−1); V is the volume of the Cd(ii) ion solution (mL); m is the mass of Cd(ii)-IICM (g); Q Cd(ii)-IICM is the adsorption amount of Cd(ii)-IICM (mg·g−1); and Q NICM is the adsorption amount of NICM (mg·g−1). The reported value of Q is the average of three parallel experiments performed under the same conditions.

3 Results and discussion

3.1 Optimization of the preparation conditions of imprinted composite membranes

In this study, the experimental conditions were optimized for the preparation of Cd(ii)-IICMs, including the base membrane type, the amount of functional monomer, the amount of crosslinking agent (EDGMA), the solvent type, the ratio of solvents, and the membrane soaking time. It can be seen from Table 2 that the best experimental conditions for preparing Cd(ii)-IICMs are as follows: a polytetrafluoroethylene (PTFE) microporous membrane as the support, CH3OH/H2O (v/v = 1/3) as the pore-forming solvent, the molar ratio of Cd(ii) ion:PMA:EDGMA of 1:4:50, and the supporting membranes immersion time of 360 s. The adsorption capacity of Cd(ii)-IICM17 prepared under these conditions was 509.93 mg·g−1, and the adsorption factor was 2.15.

Table 2

Adsorption properties of Cd(ii)-IICMs

Serial number Q IICM (mg·g−1) Q NICM (mg·g−1) α (Q IICM/Q NICM)
1 258.65 174.44 1.48
2 258.65 210.53 1.23
3 234.59 222.56 1.05
4 294.35 234.19 1.26
5 318.41 258.25 1.23
6 330.44 258.25 1.28
7 342.47 258.25 1.33
8 342.47 318.41 1.08
9 378.56 318.41 1.19
10 354.50 234.19 1.51
11 234.19 186.07 1.26
12 246.22 198.10 1.24
13 398.16 340.52 1.17
14 637.38 568.13 1.12
15 409.52 361.85 1.13
16 295.98 271.68 1.09
17 509.93 237.20 2.15
18 385.43 363.03 1.06
19 297.80 200.00 1.49
20 251.27 189.42 1.33
21 348.34 280.16 1.24
22 382.43 291.52 1.31
23 336.98 268.80 1.25
24 348.34 291.52 1.19
25 336.98 291.52 1.16

3.2 Adsorption studies of Cd(ii)-IICM17 and NICM17

3.2.1 Isothermal adsorption

Cd(II)-IICM17 and NICM17 (20 mg each) were accurately weighed and placed in separate conical flasks, then 10 mL of Cd(ii) ion solution with a mass concentration of 5–30 mg·mL−1 was accurately measured and added to the conical flasks. The solutions were shaken at room temperature for 12 h. The absorbance of the solutions was measured, and the adsorption amounts were calculated. The adsorption isotherms were plotted with the adsorption amount as the vertical coordinate and the initial concentration of Cd(ii) as the horizontal coordinate. The results are shown in Figure 2.

Figure 2 Impact of initial Cd(ii) ion concentration on the adsorption capacity of Cd(ii)-IICM17 and NICM17.
Figure 2

Impact of initial Cd(ii) ion concentration on the adsorption capacity of Cd(ii)-IICM17 and NICM17.

The Cd(ii) adsorption of Cd(ii)-IICM17 was higher than that of NICM17 when placed in solutions with the same concentration. This may be due to the addition of the template ion Cd(ii) ion during the synthesis of Cd(ii)-IICM17. After removing the Cadmium ions, Cd(ii)-IICM17 retained imprinted pores with similar shape and size as that of the Cd(ii) ion, allowing them to specifically recognize the Cd(ii) ion (14). In contrast, there was no cavity in NICM17 that matched Cd(ii) ion, so there was no specific recognition of Cd(ii) ion; therefore, NICM17 is much less capable than Cd(ii)-IICM17 to recognize Cd(ii) ion for adsorption. This also indicates that the recognition cavity of the template ion was successfully imprinted during the synthesis of Cd(ii)-IICM17.

To further explore the adsorption behavior of Cd(ii)-IICM17, the experimental data were analyzed using the Langmuir and Freundlich adsorption isotherm models whose formulas are given in Eqs. 3 and 4, respectively.

(3) C Q = 1 q m K L + C q m

(4) ln Q = ln C n + ln K F

where Q is the amount of Cd(ii) adsorbed by Cd(ii)-IICM at adsorption equilibrium (mg·g−1); C 0 is the initial concentration of the Cd(ii) ion solution (mg·mL−1); C is the concentration of the Cd(ii) solution at adsorption equilibrium (mg·mL−1); K L is the Langmuir adsorption equilibrium constant; q m is the theoretical maximum adsorption capacity (mg·g−1); K F is the Freundlich adsorption equilibrium constant.

It can be seen from Figure 3 that the Freundlich linear fits of Cd(ii)-IICM17 and NICM17 were better, which shows that the adsorption process of Cd(ii)-IICM17 on Cd(ii) ions is closer to bilayer adsorption.

Figure 3 Langmuir isotherm adsorption model (a), and Freundlich isotherm adsorption model (b).
Figure 3

Langmuir isotherm adsorption model (a), and Freundlich isotherm adsorption model (b).

3.2.2 Adsorption kinetics

Cd(ii)-IICM17 and NICM17 (10.00 mg each) were accurately weighed in a conical flask and 10 mL of a 50 mg·mL−1 solution of Cd(II) ion (methanol/water [v/v = 1/1]) was added to it. Cd(ii)-IICM17 and NICM17 (10 mg each) were weighed in a series of conical flasks, and 50 mg·mL−1 of Cd(ii) ion solution (methanol/water [v/v = 1/1]) was added to the solution. The absorbance of Cd(ii) ion was measured at different times after shaking for 5–150 min at room temperature, and the adsorption amount was calculated. Then, the adsorption time was then plotted against the amount of adsorption based on the experimental results.

Figure 4 shows the effect of adsorption time on the adsorption capacities of Cd(ii)-IICM17 and NICM17. In the first 30 min, the adsorption rates of Cd(ii) ions by Cd(ii)-IICM17 and NICM17 were fast but slowed down and nearly reached adsorption equilibrium at about 45 min. This was because at the beginning of adsorption, only the surface of the imprinted pores adsorbed Cd(ii) ions, but as the surface pores became saturated, the resistance to the transfer of imprinted ions into the membrane interior increased, thus reducing the adsorption rate (15).

Figure 4 The variation curve of the adsorption of Cd(ii)-IICM17 and NICM17 with time.
Figure 4

The variation curve of the adsorption of Cd(ii)-IICM17 and NICM17 with time.

The increase in the adsorption by Cd(ii)-IICM17 was much larger than that of NICM17 because there were no imprinted pores in NICM17 that matched with the Cd(ii) ion, so its adsorption was non-specific; therefore, the adsorption affinity and adsorption rate of Cd(ii) ions by Cd(ii)-IICM17 were larger than those by NICM17.

Adsorption kinetics is primarily used to describe the rate at which a solute is adsorbed by an adsorbent and to investigate the interaction between the adsorbent and the substance being adsorbed (16). To study the Cd(ii) ion adsorption behavior and mechanism of Cd(ii)-IICM17 and NICM17, the kinetic data were fitted with the pseudo-first-order and pseudo-second-order kinetic models, and their corresponding rate constants were calculated. The fitting results in Figure 5 show that the correlation coefficients of the pseudo-second-order kinetic model fits for Cd(II)-IICM17 and NICM17 (0.9998 and 0.9999, respectively) are much closer to 1 than those of the pseudo-first-order kinetic model fits (0.8621 and 0.7282, respectively), which can better describe the adsorption of Cd(ii) ions by Cd(ii)-IICM17 and NICM17, demonstrating that the process of Cd(ii)-IICM17 adsorption of Cd(ii) is mainly chemisorption.

Figure 5 pseudo-first-order kinetic (a) and pseudo-second-order kinetic models (b).
Figure 5

pseudo-first-order kinetic (a) and pseudo-second-order kinetic models (b).

3.2.3 pH

Figure 6 shows the variation in the amount of Cd(ii)-IICM17 and NICM17 adsorbed on Cd(II) ions over the pH range of the adsorbent solution from 3 to 10. When the pH was in the range of 3–8, as the pH increased, the adsorption capacity of Cd(ii)-IICM17 increased and reached the maximum at pH = 8. At pH > 8, the adsorption of Cd(ii)-IICM17 on Cd(ii) gradually decreases with the increase in the pH. This may be because the concentration of H+ in the solution was too low or too high, which affected the stability of Cd(ii)-IICM17 and changed the structure of the Cd(ii) ion-imprinted pores, leading to a decrease in the adsorption amount.

Figure 6 Effect of pH on the adsorption performance of Cd(ii)-IICM17 and NICM17.
Figure 6

Effect of pH on the adsorption performance of Cd(ii)-IICM17 and NICM17.

3.3 Structural characterization of Cd(ii)-IICM17 and NICM17

3.3.1 SEM

The apparent structures of the base membrane (PTFE), Cd(ii)-IICM17, and NICM17 were characterized by SEM, and the results are shown in Figure 7. The apparent structures and cavity structure of Cd(ii)-IICM17 and NICM17 are slightly different from that of the PTFE base membrane. The surface of the PTFE base membrane showed a symmetrical and flat mesh structure, while the surface of Cd(ii)-IICM17 and NICM17 were rougher. This indicates that a layer of polymer was deposited on the surface of the base membrane to form Cd(ii)-IICM17 and NICM17. The surface pores of Cd(ii)-IICM17 were larger than those of NICM17, probably due to the presence of the imprinted ion Cd(ii) (17).

Figure 7 SEM images of the base membrane (a), Cd(ii)-IICM17 (b), and NICM17 (c).
Figure 7

SEM images of the base membrane (a), Cd(ii)-IICM17 (b), and NICM17 (c).

3.3.2 Nitrogen adsorption–desorption

To study the Cd(ii) ion absorption properties of Cd(ii)-IICM17, the pore size distribution and surface area of Cd(ii)-IICM17 and NICM17 were tested, and the results are shown in Figure 8. The nitrogen adsorption-desorption isotherms of Cd(ii)-IICM17 and NICM17 are type Ⅳ isotherms, indicating that both are mesoporous materials. Furthermore, the slopes of the adsorption-desorption isotherms of Cd(ii)-IICM17 and NICM17 do not agree at all. This inconsistency indicates major differences in the membrane pore structures of Cd(ii)-IICM17 and NICM17.

Figure 8 BET curves of Cd(ii)-IICM17 (a) and NICM17 (b).
Figure 8

BET curves of Cd(ii)-IICM17 (a) and NICM17 (b).

Table 3 shows the surface area, pore volume, and average pore size of Cd(ii)-IICM17 and NICM17. As can be seen from Table 3, all structural parameters of Cd(ii)-IICM17 were greater than those of NICM17 due to the presence of the template effect in Cd(ii)-IICM17 but not in NICM17. In general, the specific surface area of an adsorbent is related to its adsorption capacity, and the pore volume is related to the mass transfer rate (18). In other words, the larger the specific surface area of an adsorbent, the greater its adsorption capacity. In addition, the larger the volume of the pore structure of the adsorbent material, the faster the mass transfer rate of the analyte (imprinted ion) through the material (19). Permeation selectivity experiments have successfully demonstrated that the mass transfer rate of Cd(ii) ion in Cd(ii)-IICM17 is much higher than that of NICM17.

Table 3

Structural parameters of Cd(ii)-IICM17 and NICM17

Membrane Surface area (m2·g−1) Pore volume (cm3·g−1) Average pore size (nm)
Cd(ii)-IICM17 11.694 0.038 11.195
NICM17 11.015 0.036 10.967

The adsorption capacities of the adsorbents were compared with most of those reported in the literature and the results are shown in Table 4. The performance of an adsorbent is related to its surface functional groups and specific surface area. Cd(ii)-IICM not only has a large specific surface area, but also contains recognizable functional groups. In this respect, the Cd(ii)-IICM surface has specific recognition sites for selective recognition of adsorbed Cd(ii), which explains the higher adsorption capacity of the Cd(ii)-IICM prepared in this study for Cd(ii).

Table 4

Comparison of the adsorption of Cd(ii)-IICM17 with other adsorbents reported in the literature

Adsorbents Template ions Adsorption capacity (mg·g−1) Reference
IIM Hg(ii) 21.6 (20)
SiO2@SP-PDA-IIM Li(i) 231.77 (21)
Li-IIMs Li(i) 50.872 (22)
Cd-IIMs Cd(ii) 162.44 (23)
Ru(iii)-IIM Ru(iii) 53.52 (24)
Cd(ii)-IICM Cd(ii) 509.93 This work

3.3.3 Thermogravimetric analysis

Figure 9 shows the results of TGA analysis of Cd(ii)-PMA-IICM17. The pictures show that the PTFE base membrane exhibits one main stage of mass loss: the decomposition of the base membrane material itself at 400–500°C and the loss of carbon combustion at 500–620°C. These two stages remained after imprinting, indicating that the imprinting did not change the intrinsic composition of the base membrane. However, Cd(ii)-PMA-IICM17 showed some amount of mass loss at 200–400°C due to the decomposition of the organic imprinted polymer on the surface of the base membrane (PTFE), confirming the success of the imprint.

Figure 9 TGA analyses of PTFE and Cd(ii)-PMA-IICM.
Figure 9

TGA analyses of PTFE and Cd(ii)-PMA-IICM.

3.3.4 Contact angle analysis

Figure 10 and Table 5 show the variation in the contact angle of the base membrane and Cd(ii)-IICM17 in aqueous solution with time, respectively. From the experimental results, it can be seen that at 0 s, the contact angle of the PTFE base membrane is 59.8°, which is less than 90°, indicating that the surface of the base membrane is hydrophilic and is more easily wetted by the liquid; and at 700 ms, the liquid can completely spread on the surface of the base membrane. The contact angle of the Cd(ii)-PMA-IICM17 was 113.3°, which was greater than 90°, indicating that the surface of the imprinted membrane was hydrophobic and the imprinted layer on its surface changed the hydrophilicity of the membrane, making the imprinted membrane less susceptible to wetting by the solution. This experimental result successfully indicates that the imprinted polymer was successfully loaded onto the PTFE base membrane surface, which is consistent with the experimental results of thermogravimetric analysis.

Figure 10 Contact angle of base membrane (a)–(c) and Cd(ii)-IICM17 (d)–(f).
Figure 10

Contact angle of base membrane (a)–(c) and Cd(ii)-IICM17 (d)–(f).

Table 5

Contact angle of base membrane and Cd(ii)-IICM17

Base membrane Cd(ii)-IICM17
0 s 59.8° 0 s 113.2°
100 ms 14.7° 30 s 105.1°
700 ms 0.0° 60 s 99.2°

3.3.5 Study of osmotic mass transfer mechanism of Cd(ii)-IICM17

Cd(ii)-IICM17 was fixed on an H-type permeation device (Figure 11). The volume of the left and right sides was 200 mL, and the area at the interface of the two tubes was 1.5 cm2. A certain concentration of mixed aqueous solutions of Co(ii), Ni(ii), Cu(ii), and Cd(ii) ions (100.00 mL each) was added to the left-hand sink and the same volume of deionized water was added to the right-hand sink. Stirring was carried out at 25°C using a stirrer with a fixed speed. Finally, the solution was removed from the right-hand tube and analyzed using ICP-OES.

Figure 11 The experimental device used to determine the permeation selectivity of Cd(ii)-IICM17.
Figure 11

The experimental device used to determine the permeation selectivity of Cd(ii)-IICM17.

The permeation flux J (mg·cm−2·s−1), permeability coefficient P (cm2·s−1), and permeability selectivity factor β were calculated by Eqs. 5–7 as follows:

(5) J i = ∆ C i V ∆ t A

(6) P = J i d ( C F i – C R i )

(7) β Cd 2 + / j = P Cd 2 + P j

where C i/t is the change in the concentration of each ion in the sink solution; V is the volume of the sink solution (mL); A is the effective membrane area (cm2); d is the membrane thickness (cm); C Fi –C Ri represents the supply pool and the concentration difference between the receiving pool; i is Co(ii), Cu(ii), Ni(ii), or Cd(ii); and j is Co(ii), Cu(ii), or Ni(ii).

Co(ii), Ni(ii), and Cu(ii) ions were selected as competing ions to investigate the osmotic selectivity of Cd(ii)-IICM17 for Cd(ii) ions. The experimental results in Table 6 show that compared with Co(ii), Ni(ii), and Cu(ii) ions, Cd(ii)-IICM17 had the largest permeability coefficient towards Cd(ii) ions, indicating that it has good permeation selectivity for Cd(ii) ions and can achieve specific recognition effects. This is because the surface of Cd(ii)-IICM17 is left with imprinted cavities matching the size and spatial structure of the Cd(ii) ions after the addition of Cd(ii) ions to the imprint during the polymerization reaction. The imprinted pores allowed Cd(ii) ions to preferentially permeate via cyclic dissociation, diffusion, and binding (25); therefore, during the permeation process, Cd(ii) ions passed through Cd(ii)-IICM17 faster, and the permeation process followed the promoting penetration mechanism (26).

Table 6

Permeation selectivity of Cd(ii)-IICM17 for Cd(ii), Co(ii), Ni(ii), and Cu(ii) ions

Ion J (mg·cm−2·s−1) P (cm2·s−1) β
Cd(ii) 4.46 × 10−5 1.14 × 10−8 −
Co(ii) 3.11 × 10−5 7.06 × 10−9 1.61
Ni(ii) 8.72 × 10−6 1.67 × 10−9 6.85
Cu(ii) 3.76 × 10−6 6.94 × 10−9 16.44

3.4 Application to real sample

The water sample from the nearby living areas was filtered to remove sediment as well as algae, the pH was adjusted to neutral, and an amount of ionic solution was added to study the application of the prepared polymer in real sample. Osmotic selectivity experiments were carried out using the apparatus in Figure 11 and the change in ion concentration after 12 h of agitation was measured and the results are shown in Table 7. As can be seen from the data in Table 7, the selectivity of Cd(ii)-IICM17 for Cd(ii) in the real water sample is somewhat reduced compared to the experimental results of the simulated sample, but still has some selectivity for Cd(ii). The reason for the decreased selectivity of Cd(ii)-IICM17 in the real sample may be due to the presence of many different forms of ions in the real water sample interfering with the specific recognition of Cd(ii) by Cd(ii)-IICM17.

Table 7

Experimental results on the selectivity of Cd(II)-IICM17 in real water sample

Ion J (mg·cm−2·s−1) P (cm2·s−1) β Cd/Co,Ni,Cu
Cd(ii) 1.019 × 10−6 1.567 × 10−10 −
Ni(ii) 3.395 × 10−7 4.597 × 10−11 3.41
Cu(ii) 8.642 × 10−7 1.174 × 10−10 1.34

4 Conclusion

In this study, a new functional monomer PMA was designed and synthesized for the preparation of Cd(ii) ion-imprinted membranes, and the preparation conditions were optimized. The Cd(ii)-IICM17 prepared under the optimal experimental conditions had a large adsorption capacity and a good imprinting effect for Cd(ii) ions. The performance study experiments revealed that the adsorption process of Cd(ii)-IICM17 on Cd(ii) ions was in accordance with the pseudo-second order model and the adsorption behavior was in accordance with the Freundlich isothermal adsorption model. The results of the ion permeation selectivity experiments showed that Cd(ii)-IICM17 had a larger permeability and higher permeability coefficient to Cd(ii) ions compared to other Cd(ii)-IICMs and NICMs, indicating its good permeation selectivity to Cd(ii) ions. The permeation process followed the mass transfer mechanism of “promoting permeation.” The research results indicate that Cd(ii)-IICM17 prepared using the new functional monomer PMA is expected to be used for the selective removal of Cd(ii) ions in wastewater. Since the molecular structure of PMA has coordination atoms (N and O), PMA may be used to coordinate with other metal ions to prepare more metal ion-imprinted materials with high adsorption capacity and high selectivity.

tel: +8613987163182

  1. Funding information: This work was supported by the National Natural Science Foundation of China (No. 21764008)

  2. Author contributions: Yuwen Hong: conceptualization, data curation, methodology, and writing – original draft; Huiling Cheng: supervision, resources, project administration, funding acquisition, and writing – review and editing; Xin Wang: software; Dongxue Fu: investigation and visualization; Guifang Wang: formal analysis; and Li Zhao: supervision and validation.

  3. Conflict of interest: The authors state no conflict of interest.

  4. Data availability statement: All data generated or analyzed during this study are included in this published article and its supplementary information files.

Appendix
Figure A1 FTIR spectra of PMA.
Figure A1

FTIR spectra of PMA.

Figure A2 Ultraviolet and visible spectrum of Cd(ii).
Figure A2

Ultraviolet and visible spectrum of Cd(ii).

Table A1

Reaction conditions for PMA synthesis

Optimization conditions Methacryloyl chloride/2,6-diaminopyridine (n/n) Solvent Time (h)
Optimization of raw material usage 1/1 Anhydrous dichloromethane 12
1/2 Anhydrous dichloromethane 12
1/3 Anhydrous dichloromethane 12
1/4 Anhydrous dichloromethane 12
1/5 Anhydrous dichloromethane 12
Time optimization 1/3 Anhydrous dichloromethane 12
1/3 Anhydrous dichloromethane 24
1/3 Anhydrous dichloromethane 36
1/3 Anhydrous dichloromethane 48
Solvent optimization 1/3 Ethanol 24
1/3 Anhydrous dichloromethane 24
1/3 Acetonitrile 24
1/3 N,N-dimethylformamide 24

NMR spectrum data of PMA: 1H NMR (400 MHz, CDCl3) δ: 8.14 (s, 2H), 7.80–7.85 (m, 2H), 7.53–7.61 (m, 1H), 5.75 (s, 1H), 5.72 (s, 1H), 5.40 (s, 1H), 5.36 (s, 1H), 1.94 (s, 3H), 1.90 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 166.35, 149.50, 140.54, 140.45, 139.99, 120.82, 109.61, 18.38.

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Received: 2022-11-22
Revised: 2023-05-18
Accepted: 2023-05-22
Published Online: 2023-08-22

© 2023 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/epoly-2022-8103
Keywords for this article
Cd(ii); ion-imprinted composite membrane; pyridine functional monomer; surface-imprinting; permeation selectivity
Creative Commons
BY 4.0

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  82. Wood-derived high-performance cellulose structural materials
  83. Flammability properties of polymers and polymer composites combined with ionic liquids
  84. Polymer-based nanocarriers for biomedical and environmental applications
  85. A review on semi-crystalline polymer bead foams from stirring autoclave: Processing and properties
  86. Rapid Communication
  87. Preparation and characterization of magnetic microgels with linear thermosensitivity over a wide temperature range
  88. Special Issue: Biodegradable and bio-based polymers: Green approaches (Guest Editors: Kumaran Subramanian, A. Wilson Santhosh Kumar, and Venkatajothi Ramarao)
  89. Synthesis and characterization of proton-conducting membranes based on bacterial cellulose and human nail keratin
  90. Fatigue behaviour of Kevlar/carbon/basalt fibre-reinforced SiC nanofiller particulate hybrid epoxy composite
  91. Effect of citric acid on thermal, phase morphological, and mechanical properties of poly(l-lactide)-b-poly(ethylene glycol)-b-poly(l-lactide)/thermoplastic starch blends
  92. Dose-dependent cytotoxicity against lung cancer cells via green synthesized ZnFe2O4/cellulose nanocomposites
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