Controllable Synthesis of Polar Modified Hyper-Cross-Linked Resins

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Controllable Synthesis of Polar Modified Hyper-crosslinked Resins and Their Adsorption toward 2-Naphthol and 4-Hydroxybenzoic Acid from Aqueous Solution Lishu Shao, Yong Li, Ting Zhang, Mingqiang Liu, and Jianhan Huang Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.6b04953 • Publication Date (Web): 24 Feb 2017 Downloaded from http://pubs.acs.org on February 27, 2017

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Industrial & Engineering Chemistry Research

Controllable Synthesis of Polar Modified Hyper-cross-linked Resins and Their Adsorption toward 2-Naphthol and 4-Hydroxybenzoic Acid from Aqueous Solution

Lishu Shao, Yong Li, Ting Zhang, Mingqiang Liu, and Jianhan Huang*

College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, People’s Republic of China ________________ * Corresponding author. Fax: 86-731-88879616. E-mail address: [email protected] (J. Huang)

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ABSTRACT: Here, we synthesized a series of polar hyper-cross-linked resins, and the porosity and polarity of these resins were effectively tuned by feeding different amounts of glycidyl methacrylate (GMA). As the feeding amount of GMA increased, the Brunauer-Emmett-Teller (BET) surface area, pore volume, micropore area, and micropore volume sharply decreased, while the pore size distribution (PSD) of the resins showed a large population of pores in the microporous region extending to a higher part of the mesoporous region, and the O content increased while the static contact angle (CA) lowered. The adsorption experiments indicated that these resins were efficient for adsorption of 2-naphthol and 4-hydroxybenzoic acid (4-HBA). The adsorption process was very fast, and the kinetic data for the adsorption of 2-naphthol could be well fitted by the pseudo-second-order rate equation, while those for the adsorption of 4-HBA could be characterized by the pseudo-first-order rate equation. 1. INTRODUCTION Although they are widely used as the raw materials for production of various organic industrial products, many aromatic compounds are highly toxic and persistent in the environment.1 In this study, we select two typical aromatic compounds, 2-naphthol and 4-hydroxybenzoic acid (4-HBA), to investigate the removal process. 2-Naphthol is a widely used intermediate for the production of dyes, spices, pharmaceuticals, insecticides, fungicides, and antiseptics. 4-HBA is primarily known as the basis for the preparation of its esters, such as parabens, which are used as preservatives in cosmetics and some ophthalmic solutions. However, 2-naphthol has a very bad effect on liver, kidney through the skin.2 It is harmful when inhaled or swallowed, and damages our environment. 4-HBA has estrogenic activity both in vitro and in vivo, but it can stimulate the growth of human breast cancer cell lines.3 As a result, before discharging to the environment, wastewater containing these aromatic compounds

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must be treated. Various methods including catalysis,4 membrane separation,5 biological method,6 oxidation,7 extraction,8 and adsorption9,10 are considered, among which adsorption is proven the most simple and efficient method, and it has been attracting many attentions in recent years.11,12 Hyper-cross-linked resins, first synthesized in 1969 by Davankov et al.,13 are recognized as the efficient polymeric adsorbents for adsorption of aromatic compounds. Compared with the adsorbents like active carbon and zeolite,19 the hyper-cross-linked resins have high Brunauer-Emmett-Teller (BET) surface area and predominant micropores/mesopores.14-18. Especially, they can be repeated used for more than 50 cycles, and they are considered as the potential replacements of active carbon for removal of the aromatic compounds. The common preparation method of the hyper-cross-linked resins is performing the Friedel-Crafts reaction under Lewis acid catalysts, which further cross-link the chloromethylated styrene-divinylbenzene copolymers.20,21 According to the considered reaction, the -CH2Cl groups are converted into the rigid methylene bridges, and the hyper-cross-linked resins with three-dimensional microporous structure are achieved.22 However, the common hyper-cross-linked resins are extremely hydrophobic, making it unfavorable for adsorption of polar aromatic compounds.23,24 For this purpose, in recent years, Huang et al.18,25 introduced polar monomer glycidyl methacrylate (GMA) for the synthesis of polar modified post-cross-linked resins. Wang et al.26 prepared two novel multi-functional magnetic adsorbents for effective removal of hydrophilic and hydrophobic nitroaromatic compounds. They found that the prepared resins were partly hydrophilic, which enhanced their adsorption toward the polar aromatic compounds. The controllable synthesis of hyper-cross-linked resins has been attracting

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increased attention in recent years. Davankov et al.27-29 have extensively studied the preparation methods, pore structure, and swelling properties of the hyper-cross-linked resins, and they found that these resins held excellent swelling properties both in the thermodynamically good solvent for polystyrene (1,2-chloroethane, toluene, etc) as well as the thermodynamically poor solvent for polystyrene (cyclohexane, etc). In 2006, Sherrington et al.30,31 incorporated the third monomer 4-vinylbenzyl chloride (VBC) into the polymer chains, and prepared the hyper-cross-linked resins with bimodal pore size distribution (PSD). They also investigated the effects of the catalysts, reaction time, and the feeding amount of VBC on the pore structure. However, it is still a challenging issue to prepare hyper-cross-linked resins with controllable porosity and polarity via a simple and effective approach. In this paper, we used the polar monomer, GMA, to replace divinylbenzene (DVB), and GMA was copolymerized with VBC in situ according to the suspension polymerization. Moreover, we used different feeding amounts of GMA in the polymerization, and hence prepared a series of linear precursor resins. Then these precursor resins were subsequently performed the Friedel-Crafts reaction, and a series of novel polar hyper-cross-linked resins were synthesized with controllable porosity and polarity. After characterization of these resins, the comparative adsorption, including the equilibrium and kinetics, was evaluated using 2-naphthol and 4-HBA as the specific adsorbates. 2. MATERIALS AND METHODS 2.1. Materials. GMA and VBC were purchased from Gray West Chengdu Chemical Co. Ltd, and they were purified with 5 wt% NaOH aqueous solution for three times to remove the inhibitors, and then they were dried using anhydrous magnesium

sulfate.

2,2-Azobisisobutyronitrile

(AIBN)

4


was

purified

by

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recrystallization and dried under vacuum before use. Poly(vinyl alcohol) (PVA, Aldrich) was used as the stabilizing agent in the polymerization, and the 1 wt% of PVA aqueous solution was used. Anhydrous ferric (III) chloride, toluene, 1,2-dichloroethane (DCE), 2-naphthol, and 4-hydroxybenzoic acid (4-HBA) were purchased from Yongda Chemical Company, and they were analytical reagent and used without further purification. 2.2. Synthesis of Polar Modified Hyper-cross-linked Resins. Scheme 1 showed the synthetic procedure of the polar modified hyper-cross-linked resins. In a 250 mL of three-necked flask, the aqueous phase including 30 mL of PVA aqueous solution (the concentration was 1 wt%), sodium chloride (12 mmol), and deionized water (50 mL) was stirred at a speed of 250 rpm at 318 K. The organic phase contained the monomer VBC, the polar monomer GMA, the solvent toluene (110 mmol), and the initiator AIBN (1.83 mmol). The total feeding amount of VBC and GMA was 100 mmol, and the feeding ratios (nGMA:nVBC) were preset to be 1:9, 2:8, 3:7, 4:6, and 5:5, respectively. Under N2 protection, the organic phase poured into the aqueous phase, and then the temperature of the reaction mixture gradually increased to 348 K, and the reaction mixture retained at this temperature for 2 h, 358 K for 3 h, and 368 K for 3 h. The linear precursor resins, abbreviated PVG-10%, PVG-20%, PVG-30%, PVG-40%, and PVG-50%, respectively, were washed by hot water, extracted by petroleum ether for 12 h, and finally dried in a vacuum oven at 333 K for 18 h. After that, the Friedel-Crafts reaction was performed for the linear precursor resins according to the method in the ref. 32, and hence the polar modified hyper-cross-linked resins, named PVG-10%-pc, PVG-20%-pc, PVG-30%-pc, PVG-40%-pc, and PVG-50%-pc, respectively, were prepared. (Scheme 1 can be inserted here)

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2.3. Characterization. Fourier transform infrared (FT-IR) spectra of the resins were recorded on a Nicolet 6700 Fourier transform infrared spectrophotometer (Thermo Scientific Co., USA), using KBr pellets ranged 4000-400 cm-1 with a resolution of 1 cm-1, and the ratio of the sample to KBr was 1:100. The pore structure of the resins was determined by the N2 adsorption-desorption isotherms, which was measured at 77 K by Micromeritics ASAP 2020 surface area and porosity analyzer. Before the measurement, the samples were degassed at 363 K for 6 h to remove the impurities in the samples. The quantitative O analysis was detected using the elemental analyzer (EA, Vario Micro cube, Germany). The contact angle (CA) of the resins was measured by a contact-angle meter (CA, JC 2000D1, China). The morphology of the resins was detected using the scanning electron microscopy (SEM, PW-100-011, Netherlands). The chlorine content of the resins was measured according to the Volhard method.33 2.4. Equilibrium Isotherms and Kinetics. Approximately 0.05 g of the resins was mixed with 50 mL of the adsorbate aqueous solution. The initial concentrations of the adsorbate were preset to be 100.4, 200.8, 301.2, 401.6, and 502.0 mg/L. The mixtures were then continuously shaken in a thermostatic oscillator at 298, 308 and 318 K, respectively, for 4 h until equilibrium was attained. To examine the equilibrium concentration of the adsorbate, the working curve was first measured by UV absorbency on the Model UV 2450 spectrophotometer. The equilibrium concentration of the adsorbate, Ce (mg/L), was then determined based on the working curve, and the equilibrium capacity, Qe (mg/g), was calculated as, Qe=(C0-Ce)V/W

(1)

where C0 is the initial concentration (mg/L), V is the volume of the solution (L) and W is the mass of the resins (g). The kinetic adsorption was similar to the equilibrium

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isotherms, while the capacity at contact time t, Qt (mg/g) was calculated in real time until equilibrium was attained. 3. RESULTS AND DISCUSSION 3.1. Characterization of the Polar Modified Hyper-cross-linked Resins. Figure 1 displays the FT-IR spectra of the linear precursor resins (PVG-10%, PVG-20%, PVG-30%, PVG-40%, and PVG-50%) and the corresponding polar modified hyper-cross-linked resins (PVG-10%-pc, PVG-20%-pc, PVG-30%-pc, PVG-40%-pc, and PVG-50%-pc). The vibrations at 1265 and 671 cm-1 were attributed to the C-Cl stretching of the -CH2Cl groups of VBC,34 and the strong characteristic band at 1729 cm-1 could be assigned to the C=O stretching of the ester carbonyl groups of GMA.10 These results indicate that VBC and GMA were copolymerized successfully. Particularly, as the feeding amount of GMA increased, the intensity of the C=O stretching was strengthened (Figure 1a), while that of the C-Cl stretching was slightly weakened. The chlorine content of the linear precursor resins revealed similar results. The chlorine content of PVG-10%, PVG-20%, PVG-30%, PVG-40%, and PVG-50% were measured to be 15.39, 12.79, 10.93, 10.27, and 9.85% (w/w), respectively. After the Friedel-Crafts reaction, Figure 1b shows that the vibration at 1265 cm-1 was much weakened, and that at 671 cm-1 was almost disappeared. In addition, the chlorine content sharply decreased to 2.29, 2.9, 4.20, 4.21, and 4.52% (w/w), respectively, for PVG-10%-pc, PVG-20%-pc, PVG-30%-pc, PVG-40%-pc, and PVG-50%-pc. These results imply that the -CH2Cl groups were almost consumed, and they were transformed to the rigid methylene cross-linking bridges. (Figure 1 can be inserted here) Table 1 indicates that the BET surface area of the linear precursor resins was zero, while the polar modified hyper-cross-linked resins had a much greater BET surface

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area, suggesting that the Friedel-Crafts reaction generated a large number of rigid methylene cross-linking bridges, and produced plentiful micropores/mesopores.35 In addition, as the feeding amount of VBC decreased, the BET surface area sharply decreased. PVG-10%-pc with 90% of VBC (mol/mol) had the greatest BET surface area (1053 m2/g), while PVG-50%-pc with 50% of VBC (mol/mol) owned the least (107.1 m2/g). Particularly interesting, as plotting the incremental BET surface area before and after the Friedel-Crafts reaction on dependence of the chlorine consumption (Figure 2a), it is obvious that this figure held a good linear relationship with a high correlation coefficient (R2=0.9942). Therefore, we conclude that VBC was the fundamental source for the increased BET surface area and the BET surface area of the resins could be accurately tuned by the feeding amount of VBC. (Table 1 and Figure 2 can be inserted here) To examine the different polarity of the polar modified hyper-cross-linked resins, the elemental analysis and the contact angle (CA) were measured for these resins. The O content was 6.94, 7.47, 9.40, 12.1 and 14.9% (w/w), respectively, for PVG-10%-pc, PVG-20%-pc,

PVG-30%-pc,

PVG-40%-pc,

and

PVG-50%-pc

(Table

1).

Simultaneously, the contact angle (CA) was 48.5°, 45.0°, 40.5°, 35.0°, and 31.5°, respectively. Compared to the chloromethyl polystyrene (CA>129°),36 these resins were strongly hydrophilic (0.98), confirming that the kinetic behavior for the adsorption of 2-naphthol on the resins was different from 4-HBA. In addition, for the adsorption of

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2-naphthol, the k1 values on PVG-30%-pc and PVG-50%-pc (0.2188 and 0.2721 min-1) were slightly greater than the residual resins, accordant with the fact that PVG-30%-pc and PVG-50%-pc needed less time to attain equilibrium. Whilst for the adsorption of 4-HBA, the k2 values on PVG-30%-pc, PVG-40%-pc and PVG-50%-pc (2.554×10-2, 1.932×10-2, and 1.834×10-2 g/(mg·min)) were greater than those on PVG-10%-pc and PVG-20%-pc (4.000×10-3 and 4.590×10-3 g/(mg·min)), agreed with the fact that PVG-30%-pc, PVG-40%-pc and PVG-50%-pc needed less time to attain equilibrium. The intra-particle diffusion model is commonly used to identify the possible adsorption mechanism. According to Weber and Morris,57 the adsorption capacity varies proportionately with t1/2 and it can be represented as, (4) where kd is the adsorption rate constant and C reflects the thickness of the boundary layer. As can be observed in Table S5 and Figure S2 in the Supporting Information, all of the plots were distributed in two linear segments presenting two different stages. If the plots pass through the origin, the intra-particle diffusion is the sole rate-limiting step. As shown in Figure S2 in the Supporting Information, the first stage gives a straight line, but the plots for PVG-10%-pc, PVG-20%-pc, PVG-30%-pc, and PVG-50%-pc do not pass through the origin, while the straight line for PVG-40%-pc passes through the origin, which suggested that the intra-particle diffusion was the sole rate-limiting step for the adsorption on PVG-40%-pc.47 Meanwhile, the micropore diffusion model developed by Krishna58 was also employed to analyze the kinetic data, which was expressed as, (5) 15



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where D is the micropore diffusion parameter (cm2/s) and r is the particle size of the resins (cm). Figure 7 shows the plotting of Qt/Qe versus t, and Table S5 in the Supporting Information lists the corresponding parameters. It suggests that the kinetic data on PVV-10%-pc, PVV-20%-pc, PVV-30%-pc, and PVV-40%-pc could be well fitted by the micropore diffusion model, while those on PVV-50%-pc could not be well fitted, further confirmed that PVV-10%-pc, PVV-20%-pc, PVV-30%-pc, and PVV-40%-pc were

microporous/mesoporous

materials,

while

PVV-50%-pc

were

mesoporous/macroporous materials. 4. CONCLUSIONS We synthesized a series of polar modified hyper-cross-linked resins by suspension polymerization of GMA and VBC, and followed by the Friedel-Crafts reaction. The porosity and polarity of these resins could be effectively adjusted by the feeding amount of the GMA in the polymerization. When the feeding amount of GMA increased from 10% to 50% (mol/mol), the BET surface area, pore volume, micropore area, and micropore volume of the obtained resins greatly decreased, but the PSD was moving toward a larger pore size direction. In addition, the O content increased from 6.94 to 14.9% (w/w), and the CA decreased from 48.0° to 31.5°. These resins were evaluated for the comparative adsorption for 2-naphthol and 4-HBA from aqueous solution, and the maximum equilibrium capacity of 2-naphthol at 298 K was 602.0 mg/g as using PVG-10%-pc as the model adsorbent, and the maximum equilibrium capacity of 4-HBA was 245 mg/g as using PVG-20%-pc as the model adsorbent. The adsorption of 2-naphthol was mainly driven by hydrophobic interaction, π-π stacking, and microporous filling, while for the adsorption of 4-HBA, hydrogen bond and electrostatic interaction played important roles. The equilibrium data could be fitted

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by the Langmuir model, and the adsorption was an exothermic process, and the adsorption of 4-HBA on PVG-20%-pc involved a possible weak chemical bond formation. The adsorptive process was very fast, the kinetic data for 2-naphthol could be well fitted by the pseudo-second-order rate equation, while those for 4-HBA could be characterized by the pseudo-first-order rate equation. ACKNOWLEDGMENTS The National Natural Science Foundation of China (Nos. 21376275 and 51673216) is gratefully acknowledged for the financial supports. SUPPORTING INFORMATION There are 6 Tables (Table S1-S6) and 2 Figures (Figure S1-S2) in the Supporting Information, which are attached in this paper. REFERENCES (1) Shapiro, J. China’s Environmental Challenges. John Wiley & Sons. 2016. (2) Krugly, E.; Martuzevicius, D.; Tichonovas, M.; Jankunaite, D.; Rumskaite, I.; Sedlina, J.; Racys, V.; Baltrusaitis, J. Decomposition of 2-Naphthol in Water Using a Non-thermal Plasma Reactor. Chem. Eng. J. 2015, 260, 188. (3) Li, H.-B.; Fu, Z.-Y.; Yan, C.; Huang, J.-H.; Liu, Y.-N.; Kirin, S. I. Hydrophobic-Hydrophilic Post-Cross-Linked Polystyrene/Poly (Methyl Acryloyl Diethylenetriamine) Interpenetrating Polymer Networks and its Adsorption Properties. J. Colloid Interf. Sci. 2016, 463, 61. (4) Marsolek, M. D.; Kirisits, M. J.; Gray, K. A.; Rittmann, B. E. Coupled Photocatalytic-Biodegradation of 2,4,5-Trichlorophenol: Effects of Photolytic and Photocatalytic Effluent Composition on Bioreactor Process Performance, Community Diversity, and Resistance and Resilience to Perturbation. Water Res. 2014, 50, 59. (5) Díaz, E.; Jiménez, J. I.; Nogales, J. Aerobic Degradation of Aromatic Compounds.

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A,

α-Naphthol

and

β-Naphthol

from

22


Aqueous

Solution

by

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(55) Azizian, S. Kinetic Models of Sorption: A Theoretical Analysis. J. Colloid Interf. Sci. 2004, 276, 47. (56) Ho, Y.S.; McKay, G. Pseudo-Second Order Model for Sorption Processes. Process Biochem. 1999, 34, 451. (57) Weber, W.J.; Morris, J.C. Kinetics of adsorption on carbon from solution. J. Sanit. Eng. Div. 1963, 89, 31. (58) Van Den Broeke, L.J.P.; Krishna, R. Experimental Verification of the Maxwell-Stefan Theory for Micropore Diffusion. Chem. Eng. Sci. 1995, 50, 2507.

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Page 25 of 34

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Scheme 1 Synthetic procedure of the polar modified hyper-cross-linked resins.

25



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Page 26 of 34

Table 1 Structural parameters of the polar modified hyper-cross-linked resins. PVG-1

PVG-20

PVG-3

PVG-40

PVG-5

0%-pc

%-pc

0%-pc

%-pc

0%-pc

SBET (m2/g) a

1053

635.4

312.0

263.1

107.1

SMicro (m2/g) b

546.8

400.6

196.2

5.4

0

SMeso (m2/g) c

504.9

234.1

115.1

256.7

103.6

V (cm3/g) d

0.68

0.38

0.19

0.23

0.19

VMicro (cm3/g) b

0.40

0.27

0.13

0.092

0

VMeso (cm3/g) c

0.28

0.11

0.054

0.12

0.14

Chlorine content (%) e

2.29

2.90

4.20

4.21

4.52

O content (%) f

6.94

7.47

9.40

12.1

14.9

The contact angle (°) g

48.5

45.0

40.5

35.0

31.5

a

Calculated using the BET method.

b

Calculated using non-local density functional theory (NL-DFT) model.

c

Calculated using Barrett, Joyner and Halenda (BJH) model.

d

Calculated at P/P0=0.99.

e

Determined by the Volhard method.

f

Obtained by the elemental analysis.

g

Measured by the contact-angle meter.

26


Page 27 of 34

Figure 1 FT-IR spectra of the linear precursor resins (a) (PVG-10%, PVG-20%, PVG-30%, PVG-40%, and PVG-50%) and the corresponding polar modified hyper-cross-linked

resins

(b)

(PVG-10%-pc,

PVG-20%-pc,

PVG-40%-pc, and PVG-50%-pc).

Transmittance /%

(a) PVG-50% PVG-40%

1729cm-1

PVG-30%

671cm-1

PVG-20% PVG-10%

-1 1450cm-1 1265cm

4000 3500 3000 2500 2000 1500 1000 500 Wavenumbers /cm-1

(b) Transmittance /%

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


PVG-50%-pc 1729cm-1 PVG-40%-pc 697cm-1

PVG-30%-pc PVG-20%-pc

1448cm-1 1265cm-1

PVG-10%-pc

4000 3500 3000 2500 2000 1500 1000 500 Wavenumbers /cm-1

27


PVG-30%-pc,


Figure 2 (a) Relationship of the incremental BET surface area before and after the Friedel-Crafts reaction with the chlorine consumption for the polar modified hyper-cross-linked resins; (b) Relationship of the O content and the contact angle (CA) with the feeding amount of GMA.

1200 (a)

PVG-10%-pc

1000

Y=403.1X-453.5 R2=0.9942

800 600

PVG-20%-pc

400 PVG-40%-pc

PVG-30%-pc

200 PVG-50%-pc 0

1 2 3 4 Consumption content of Cl /mmol/g

5

60

16 (b)

55

14

50 12

45 40

10

35

8

30 6

25

20 c c c c c p p p p p -10% VG-20% VG-30% VG-40% VG-50% P P P PVG P 4

A

28


Contact angle/(°)

0

O content/(%)

BET surface area /m2/g

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 34

Page 29 of 34

Figure 3 (a) N2 adsorption-desorption isotherms; (b) pore size distribution (PSD) of the polar modified hyper-cross-linked resins (determined by the nonlocal density functional theory (NL-DFT) method using the carbon slit pore model).

500

(a)

PVG-10%-pc

400

3

Quantity adsorbed /cm /g STP

300 PVG-20%-pc 200

PVG-40%-pc

PVG-30%-pc 100

PVG-50%-pc

0 0.0

0.2

0.4 0.6 0.8 Relative pressure /P/P0

(b)

1.0

PVG-50%-pc

3

Differential pore volume /cm /g

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


PVG-40%-pc

PVG-30%-pc

PVG-20%-pc PVG-10%-pc 10

100 Pore size /A

29


1000


Figure 4 Equilibrium isotherms for the adsorption of (a) 2-naphthol; and (b) 4-HBA on the polar modified hyper-cross-linked resins at 298 K.

500 PVG-10%-pc

(a)

PVG-20%-pc

400

Qe /mg/g

PVG-30%-pc 300

PVG-40%-pc PVG-50%-pc

200

100

0

Langmuir model fitting Freundlich model fitting 0

50

100

150 200 Ce /mg/L

250

300

350

(b) 120

Qe /mg/g

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 30 of 34

90

60

30

0

0

80

160

PVG-10%-pc PVG-20%-pc PVG-30%-pc PVG-40%-pc PVG-50%-pc Langmuir model fitting Freundlich model fitting 240 320 400 480 C e /mg/L

30


Page 31 of 34

Figure 5 Equilibrium isotherms for the adsorption of (a) 2-naphthol on PVG-10%-pc, and (b) 4-HBA on PVG-20%-pc with the temperature at 298, 308, and 318 K, respectively.

500 (a)

Qe /mg/g

400 300 298 K 308 K 318 K Langmuir model fitting Freundlich model fitting

200 100 0

0

20

40

60

80 100 120 140 160 180 Ce /mg/L

(b) 120

Qe /mg/g

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


90

60 298 K 308 K 318 K Langmuir model fitting Freundlich model fitting

30

0

0

100

200 300 Ce /mg/L

31


400


Figure 6 Kinetic curves for the adsorption of (a) 2-naphthol; and (b) 4-HBA on the polar modified hyper-cross-linked resins at 298 K.

500

Qt /mg/g

(a) 400

PVG-10%-pc

300

PVG-20%-pc PVG-30%-pc PVG-40%-pc

200

PVG-50%-pc Pseudo-first-order rate equation Pseudo-second-order rate equation

100 0

0

120

20 40 60 80 100 120 140 160 180 200 t /min

(b)

100 80 Q t /mg/g

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

PVG-10%-pc PVG-20%-pc PVG-30%-pc PVG-40%-pc PVG-50%-pc Pseudo-first-order rate equation Pseudo-second-order rate equation

60 40 20 0

0

10 20 30 40 50 60 70 80 90 100 110 t /min

32


Page 32 of 34

Page 33 of 34

Figure 7 Plotting of Qt/Qe versus t for the adsorption of (a) 2-naphthol; and (b) 4-HBA on the polar modified hyper-cross-linked resins at 298 K according to the micropore diffusion model.

1.0 (a) 0.8

Qt/Qe

0.6 PVG-10%-pc PVG-20%-pc PVG-30%-pc PVG-40%-pc PVG-50%-pc Micropore diffusion model

0.4 0.2 0.0

0

1.0

10

20

30 t /min

40

50

(b)

0.8 Qt/Qe

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


0.6

PVG-10%-pc PVG-20%-pc PVG-30%-pc PVG-40%-pc PVG-50%-pc Micropore diffusion model

0.4 0.2 0.0

0

5

10 t /min

15

33


20


For Table of Contents Only 700

(a)

(b)

PVG-50%-pc

Differential pore volume /cm /g

600

3

2-Naphthol 4-Hydroxybenzoic acid

500

PVG-40%-pc Qm /mg/g

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

PVG-30%-pc

400 300 200

PVG-20%-pc

100

PVG-10%-pc 0

10

100 Pore size /A

-pc -pc -pc -pc -pc -10% VG-20% VG-30% VG-40% VG-50% P P P P PVG

1000

34


Page 34 of 34

Controllable Synthesis of Polar Modified Hyper-Cross-Linked Resins

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