static-content.springer.com10.1007... · Web viewThe peaks at 1370 cm-1 and 1440 cm-1 as well as the peaks at 1580 cm-1 and 1630 cm-1 correspond to the symmetric and asymmetric stretching

Electronic Supplementary Material

Magnetization of a Cu(II)-1,3,5-benzenetricarboxylate metal-organic framework for efficient solid-phase extraction of Congo Red

Yan Xu,a, * Jingjie Jin,a Xianliang Li,b Yide Han,a Hao Meng,a Chaosheng Song,a Xia Zhanga, *

aDepartment of Chemistry, College of Science, Northeastern University, Shenyang, Liaoning 110819, China

bCollege of Materials Science and Engineering, Shenyang University of Chemical Technology, Shenyang,

Liaoning 110142, China

*Corresponding Authors: [email protected] (Yan Xu);[email protected] (Xia Zhang); Fax: +86-024-

83684533; Tel.: +86-024-83684533.

Fig. S1 FT-IR spectra of Fe3O4, Fe3O4@SiO2, and Fe3O4@SiO2-Cu-BTC (Note: The peak at 570 cm-1 is a characteristic peak of Fe3O4. The peaks at 1094 cm-1 and 3406 cm-1 can be assigned to the Si–O and –OH groups. Various peaks observed in the region of 600–800 cm-1 are attributed to the out-of-plane vibrations of BTC. The peaks at 1370 cm-1 and 1440 cm-1 as well as the peaks at 1580 cm-1 and 1630 cm-1 correspond to the symmetric and asymmetric stretching vibrations of the carboxylate groups in BTC [1–2]).

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Fig. S2 N2 adsorption-desorption isotherms of as-prepared MOF Cu-BTC.

Fig. S3 DLS curve of Fe3O4@SiO2.

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Table S1 Figures of merit of recently reported methods for determination or preconcentration of Congo Red

Material/method used Removal efficiency

Optimum pH

Adsorption capacity(mg g-1)

Interferences Ref.

Ionic liquid (IL)/Liquie-liquid extraction ― 5 6 A: pHB: Type and amount of ILC: Initial concentration of dyeD: Type and volume of solventE: Concentration of salt

[3]

Bifunctional moleculary imprinted polymer/Solid-phase extraction

― ― ― ― [4]

Hierarchical NiO spheres 93 % ― 440 ― [5]Porous Pr(OH)3 nanostructures ― ― 873.4 ― [6]Polyaniline-lignocellulose composite 99.85 % 4.29 1672.5 A: pH

B: TemperatureC: Initial concentration of dye

[7]

Starch-AlOOH-FeS2 nanocomposite ― 5 346 A: pHB: TemperatureC: Initial concentration of dyeD: Contact time

[8]

Graphene oxide/chitosan/silica fibers 89.8 % 3 294.12 A: pHB: Initial concentration of dyeC: Contact timeD: Adsorbent dose

[9]

Calixarene-functionalized polyacrylonitrile nanofiber membranes

> 80 % 7 30-35 ― [10]

Mesoporous TiO2-graphene oxide core-shell microspheres

― 6 89.95 A: pHB: Initial concentration of dye

[11]

Fe3O4@SiO2-Cu-BTC/Magnetic solid-phase extraction

> 90 % 11 ― A: Adsorbent doseB: Extraction timeC: CR concentrationD: Ionic strengthE: pH

This work

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Fig. S4 Effects of (a) extraction time, (b) initial CR concentration, (c) ionic strength, and (d) pH value on the adsorption of CR on magnetic Fe3O4@SiO2-Cu-BTC

Fig. S5 Structure of CR with (a) pH < 5.5, and (b) pH > 5.5

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Fig. S6. Adsorption isotherm by using (a) Freudlich, (b) Langmuir, and (c)Temkin models.

Table S2. Isotherm parameters of CR adsorption on magnetic Fe3O4@SiO2-Cu-BTC materials

Initial CR(mg L-1)

qe (exp)(mg g-1)

Freundlich Langmuir TemkinKF 1/n R2 KL qL(mg g-1) R2 bT KT R2

60 19.1090 28.71 9.47 0.761 0.953 0.0477 171.82 0.963 0.1022 0.8258 0.998150 47.16

Note: 28 mg of Fe3O4@SiO2-Cu-BTC (14 mg MOF Cu-BTC and 14 mg Fe3O4@SiO2) is used as adsorbent on MSPE of CR in aqueous solution with various concentrations (60 mg L-1, 90 mg L-1 and 150 mg L-1) in the exeperiment.

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Fig. S7 Adsorption kinetics of CR on Fe3O4@SiO2-Cu-BTC by using (a) pseudo-first order and (b) pseudo-second order (adsorbent dose: 15 mg MOF Cu-BTC and 15 mg Fe3O4@SiO2; initial dye concentration: 30mg L-

1, 60 mg L-1, 90 mg L-1, 150 mg L-1 and 200 mg L-1; initial pH: 7)

Fig. S8 Intra-particle diffusion plots for the adsorption of CR on magnetic Fe3O4@SiO2-Cu-BTC material (adsorbent dose: 15 mg MOF Cu-BTC and 15 mg Fe3O4@SiO2; initial CR concentration: 30 mg L-1, 60 mg L-1, 90 mg L-1, 150 mg L-1 and 200 mg L-1; initial pH: 7; time: 1–20 min)

Table S3. Kinetic parameters of CR adsorption for pseudo-first order, pseudo-second order and intra-particle diffusionmodels

Initial CR(mg L-1)

qe, exp

(mg g-1)

Pseudo-first order Pseudo-second order Intra-particle diffusion modelqe1, cal

(mg g-1)k1

(min-1) R2 Δq(%)

qe2, cal

(mg g-1)k2

(g·mg-1 min-1) R2 Δq(%)

C(mg g-1)

k3

(g mg-1 min1/2) R2

30 9.42 6.22 0.2160 0.685 33.97 10.44 0.0422 0.993 -10.83 1.42 2.3300 0.99460 19.52 9.10 0.1970 0.659 53.38 20.74 0.0319 0.989 -6.25 6.02 3.4476 0.96290 28.29 10.29 0.1488 0.556 63.63 29.30 0.0252 0.985 -3.57 8.87 6.0507 0.977

150 49.13 41.25 0.2376 0.968 16.04 54.59 0.0081 0.994 -11.11 8.92 11.7686 0.953200 64.39 57.25 0.2491 0.935 11.09 71.94 0.0059 0.992 -11.73 16.79 12.7524 0.970

Note: To investigate the applicability of different kinetic models in fitting to data, a normalized standrard deviation, Δq (%), is calculated as below:

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Δq(% )=(qe

, exp -qe, cal)

qe, exp×100 %

Fig. S9 Plot of lnKC versus 1/T for CR adsorption on Fe3O4@SiO2-Cu-BTC

Table S4. Thermodynamic parameters for the adsorption of CR by Fe3O4@SiO2-Cu-BTC at different temperature

Temperature(K)

CR removal (%)

ΔGΘ

(kJ mol -1)ΔHΘ

(kJ mol -1)ΔSΘ

(J mol K-1)

317 85.0 -4.61325 87.5 -5.17 17.70 70.37331 88.2 -5.59

Note: Concentration and volume of CR (90 mg L-1, 5 mL), adsorbent dose (5 mg MOF Cu-BTC and 5 mg Fe3O4@SiO2), and the extraction time (10 min) are kept constant in the experiment.

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Fig. S10 Cycle measurement of Fe3O4@SiO2-Cu-BTC (15 mg Fe3O4@SiO2 and 15 mg MOF Cu-BTC) for the adsorption and desorption of CR with pH of 7

Table S5 Experimental data for cycle measurement of Fe3O4@SiO2-Cu-BTC (15 mg MOF Cu-BTC and 15 mg

Fe3O4@SiO2) for the adsorption and desorption of CR (pH = 7).

Cycle time (i) Removal efficiency (%)

Cycle time (i)

Removal efficiency (%)

Cycle time (i)

Removal efficiency (%)

1 98.6 6 97.6 11 97.32 98.2 7 97.6 12 97.13 98.2 8 97.6 13 97.34 98.0 9 97.3 14 97.35 97.8 10 97.1 15 97.1

Fig. S11 XRD patterns of (a) Fe3O4@SiO2, (b) Fe3O4@SiO2-Cu-BTC, and (c) Fe3O4@SiO2-Cu-BTC after fifteen time of MSPE of Congo Red.

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Fig. S12 Structures of dye molecules used in the dye adsorption experiments.

Fig. 13 Removal efficiencies for cationic dyes: Methylene Blue (MB, 17 mg L-1), Basic Red 2 (BR2, 16 mg L-1), and Crystal Violet (CV, 19 mg L-1); neutral dye: Methyl Red (MR, 12 mg L-1); anionic dyes: Methyl Orange (MO, 15 mg L-1), Orange G (21 mg L-1), and Orange II (16 mg L-1)

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