Reversing the Dye Adsorption and Separation Performance of Metal

Apr 3, 2017 - In this work, two hydrostable Cr-based metal–organic frameworks (MOFs), MIL-101(Cr) and MIL-101(Cr)-SO3H, were successfully synthesize...
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Reversing the dyes adsorption and separation performance of metal-organic frameworks via introduction of –SO3H groups Xudong Zhao, Keke Wang, Zhuqing Gao, Huihui Gao, Zhixia Xie, Xiaoyu Du, and Hongliang Huang Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b00128 • Publication Date (Web): 03 Apr 2017 Downloaded from http://pubs.acs.org on April 4, 2017

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Reversing the Dyes Adsorption and Separation Performance of Metal-Organic Frameworks via Introduction of –SO3H Groups Xudong Zhao,† Keke Wang,‡ Zhuqing Gao,*,† Huihui Gao,† Zhixia Xie,† Xiaoyu Du† and Hongliang Huang*,‡ †

College of Chemical and Biological Engineering, Taiyuan University of Science and

Technology, Taiyuan 030012, China ‡

State Key Laboratory of Organic-Inorganic Composites, Beijing Advanced Innovation Center

for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China

KEYWORDS: metal-organic frameworks; adsorption and separation; dyes; -SO3H groups; reversion ABSTRACT: In this work, two hydrostable Cr-based MOFs, MIL-101(Cr) and MIL-101(Cr)SO3H were successfully synthesized and applied in the adsorption and separation of ionic dye Fluorescein sodium (FS) and cationic dye Safranine T (ST). Interestingly, MIL-101(Cr) can efficiently adsorb FS dye but hardly adsorb ST dye and MIL-101(Cr)-SO3H exhibits thoroughly opposite phenomenon. More importantly, the reversed adsorption with high selectivity on the two MOFs can also be attained in the mixed solutions of the dyes. At last, mechanism analysis indicates that this significant reversion in performance for the dyes is mainly attributed to the opposite surface charges of the two MOFs caused by -SO3H groups.

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1. INTRODUCTION Dyes have been widely applied in the paper, pharmaceutical, food and textile industries.1 In the production process of dyes, the nitration, sulfonation, diazotization and salting-out units can produce large amounts of dye-containing wastewater, which is difficult to clear up for various reasons.2 More seriously, some carcinogenic and mutagenic structures such as benzene, naphthalene and benzoquinone are widely existed in the dyes.3-4 Therefore, the removal of dyes from wastewater is significantly necessary to improve human health and environmental sustainable development. Among the removal methods reported so far, adsorptive removal was paid large attentions due to its advantages such as low operation cost, easy regeneration and low secondary products.5 Metal-organic frameworks (MOFs), consisting of metal ions and organic ligands, have shown great potentials in many applications.6-11 In particular, thanks to their advantages including large specific surface areas and abundant adsorption sites, MOFs have been widely applied in liquid adsorption and separation.12-17 In recent years, various MOFs were selected in purification of dye-containing water and many methods were explored to improve the adsorption or separation performance for dyes.2,18-22 However, the attempts to reverse the performance were rarely reported.23 In this work, reversion of the performance for FS and ST dyes was tried by introducing -SO3H groups into MOF framework. Due to excellent water stability, large specific surface area and pore size,24-26 MIL-101(Cr) and MIL-101(Cr)-SO3H were selected as adsorbents to study the effect of -SO3H groups. From both the adsorption and separation experiments, MIL-101(Cr) can exhibit competitive adsorption ability for FS rather than ST and interestingly, MIL-101(Cr)SO3H has thoroughly opposite adsorption ability. Mechanism analysis indicates that the opposite

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surface charges of these two MOFs lead to this special phenomenon. In conclusion, this work provides an efficient method to regulate the adsorption and separation performance for dyes in MOFs. 2. MATERIALS AND METHODS 2.1. Synthesis of materials Synthesis of MIL-101(Cr). The MOF was synthesized according to the reported work.24 Synthesis of MIL-101(Cr)-SO3H. MIL-101(Cr)-SO3H was synthesized according to the literature with some modification.27 Chromium trioxide (1.25 g) and monosodium 2-sulfoterephthalic acid (3.35 g) were mixed in water (50 mL) and concentrated hydrochloric acid (0.772 mL) was added. After stirred for several minutes, the mixture was transferred to a Teflon-lined stainless steel autoclave and heated at 453 K for 6 days. The obtained product was washed with hot water (400 mL) and hot methanol (250 mL), respectively. At last, the solid was dried at 373 K overnight. 2.2. Characterization and measurements PXRD patterns of MIL-101(Cr) and MIL-101(Cr)-SO3H were measured on a D8 Advance X diffractometer with Cu Kα radiation (λ = 1.5406 Å) from 1°to 20°. The BET specific surface areas of MOF samples were characterized on an Auto-IQ-MP (Quantachrome Instruments) using N2 adsorption at 77 K. The infrared spectra data was collected with a Nicolet iS50 FT-IR spectrophotometer. The zeta potentials of samples at different pH values were determined on a Zetasizer Nano ZS Zeta potential analyzer (Malvern Instruments). 2.3. Adsorption experiment The dyes adsorption experiments were carried out in 15 mL dye-containing solution with different concentrations at 298 K. The dosages of MIL-101(Cr) and MIL-101(Cr)-SO3H were both 15 mg. After stirred for some time, the suspension was filtered by microfiltration membrane

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and the collected filter liquor was used in the measurement of the dye concentration by UV-vis spectroscopy (TU-1901). In the adsorption experiments for investigating the effect of non-polar molecules, the initial concentration ratio of the dye and the non-polar molecule was 1:1. It is noted that benzene and naphthalene were solved in the mixture of 1-butanol and water (1:100, v/v) due to their low water solubilities.28-29 2.4. Regeneration methods The regeneration methods for ST-loaded MOFs and FS-loaded MOFs are different. FS-loaded MOFs were regenerated by using 0.1 M HCl aqueous solution (eluent) under ultrasonic vibration. For ST-loaded MOFs, the eluent was 0.1 M NaNO3 aqueous solution. 2.5. Separation experiment MIL-101(Cr) or MIL-101(Cr)-SO3H (15 mg) was added into 15 mL mixed solutions of FS and ST. The initial concentration ratio of FS and ST in the mixture was set as 1:1. After stirred for 24 h at 298 K, the suspension was filtered by microfiltration membrane. The filter liquor was collected for the measurement of the dye concentration by UV-vis spectroscopy. The concentrations of FS and ST in two-component solutions were calculated via two equations (1) and (2):30

A488.0  ,ST  CST +  FS  CFS

(1)

A520.0   ,ST  CST +   FS  CFS

(2)

where A488.0 and A520.0 are the absorbance values at the wavelengths of 488.0 nm and 520.0 nm, respectively (488.0 nm and 520.0 nm are the UV maximum adsorption wavelengths of FS and ST respectively); CST and CFS are the initial concentrations of ST and FS in the two-component solutions, respectively; α1,ST, α1,FS, α2,ST and α2,FS are the constants to be fitted. The competitive

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adsorption ability for FS over ST and that for ST over FS can be characterized by the adsorption selectivity constants αFS/ST and αST/FS as shown in equations (3) and (4),30 where QFS and QST are adsorption capacities for the FS and ST respectively.

 QFS   CST     QST   CFS 

(3)

 QST   CFS    Q  FS   CST 

(4)

 FS ST  

ST FS  

3. RESULTS AND DISCCUSSION 3.1. Characterization of MOFs

Intensity (a.u.)

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MIL-101(Cr)-SO3H MIL-101(Cr) MIL-101(Cr) sim 2

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Figure 1. The PXRD patterns of as-synthesized materials and simulated XRD pattern of MIL-101(Cr).

As shown in Figure 1, the PXRD patterns of as-synthesized MIL-101(Cr) and MIL-101(Cr)SO3H are basically consistent with the simulated XRD pattern of MIL-101(Cr), indicating these two MOFs are well synthesized and have similar topological structure. In Figure S1, the peaks at 1080 cm-1 and 1183 cm-1 in the spectrum of MIL-101(Cr)-SO3H are attributed to the –SO3 groups,31-32 demonstrating the successful introduction of –SO3H groups. Furthermore, to verify the permanent porosity of the MOFs, the N2 adsorption-desorption measurement at 77 K was performed, as shown in Figure S2. The BET specific surface areas of MIL-101(Cr) and MIL-

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101(Cr)-SO3H were calculated to be 3016 m2 g-1 and 1546 m2 g-1 respectively, which are consistent with those in the previous works.24,27 3.2. Dyes adsorption in MOFs MIL-101(Cr) and MIL-101(Cr)-SO3H have large surface areas and excellent water stability, which makes these MOFs can serve as adsorbents for pollutants in aqueous solution. In this work, cationic dye ST and anionic dye FS were selected as target pollutants to study the capture ability of these MOFs. Their molecular structures are shown in Figure S3.

(b)

(a)

FS adsorption

ST adsorption

Figure 2. The photographs of FS solutions (a) and ST solutions (b) before and after contacted with the MOF samples.

The adsorption abilities of the two Cr-MOFs were firstly evaluated by adding 15 mg MOF sample into 15 mL dye-containing aqueous solution (initial concentrations are 50 mg L-1). After 24 h, changes with obvious differences in the color of the solutions were observed. As shown in Figure 2a, FS solution with MIL-101(Cr) turned from fluorescence green to colorless and the solution with MIL-101(Cr)-SO3H had little change; on the contrary, ST solution with MIL101(Cr)-SO3H turned from pink to colorless and the solution with MIL-101(Cr) kept almost unchanged as shown in Figure 2b. In addition, it was found that the adsorption capacities under nature light irradiation and dark environment were almost equal for both the two MOFs (Figure S4), indicating the dyes were adsorbed rather than degraded by the MOFs. These results indicate

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that not only MIL-101(Cr) and MIL-101(Cr)-SO3H have large potentials in adsorption for FS and ST respectively, but also -SO3H groups can induce the reversion of adsorption performance of the MOFs. In addition, compared to other MOFs-SO3H adsorbents such as UiO-66-SO3H33, larger pore size and specific surface area induce that MIL-101(Cr)-SO3H as well as MIL-101(Cr) can serve as adsorbent for larger organic molecules such as ST and FS. To systematically study the adsorption performance of the two MOFs for ST and FS, the kinetic data was first examined. As revealed from Figure 3, in the adsorption of FS, both MIL101(Cr) and MIL-101(Cr)-SO3H can reach adsorption equilibrium at about 100 min; with respect to ST dye, the adsorption in MIL-101(Cr) and MIL-101(Cr)-SO3H can reach equilibrium quickly at only 5 min. Based on the results, 24 h was selected as adsorption time in the experiments below. 500

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Figure 3. The adsorption capacities of MIL-101(Cr) and MIL-101(Cr)-SO3H towards contact time at the initial concentrations of 100 mg L-1 and 500 mg L-1.

Furthermore, the capture abilities for the dyes of MIL-101(Cr) and MIL-101(Cr)-SO3H were studied via adsorption isothermals. From Figure 4a, the saturated adsorption capacity for FS of MIL-101(Cr) can reach 297.5 mg g-1 and the data of MIL-101(Cr)-SO3H is only 70.8 mg g-1. On the contrary, in the adsorption for ST (Figure 4b), the saturated adsorption capacity of MIL-

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101(Cr)-SO3H can reach 425.5 mg g-1; however, the largest adsorption capacity of MIL-101(Cr) can reach only 113.8 mg g-1 under the same condition. From these results, it can be directly seen that the adsorption performance for the dyes can be reversed via the introduction –SO3H groups.

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MIL-101 MIL-101-SO3H

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(b) 400 300

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Figure 4. The adsorption isothermals of MIL-101(Cr) and MIL-101(Cr)-SO3H for FS (a) and ST (b).

To explain this interesting phenomenon, PXRD patterns of the MOFs after adsorption were first measured. From Figure S5, the frameworks of MIL-101(Cr) and MIL-101(Cr)-SO3H can keep almost intact in the presence of the dyes. Figure S6 shows the zeta potentials of MIL101(Cr) and MIL-101(Cr)-SO3H at different pH values. It can be seen that the surfaces of MIL101(Cr) and MIL-101(Cr)-SO3H are positively and negatively charged at natural pH (pH = 6.20), respectively. Furthermore, adsorption sites in the MOFs were investigated as shown in Scheme 1. In MIL-101(Cr), the O sites in C=O groups at the pH of 6.20 turn to OH+, which can adsorb FS2(FS→FS2- + 2Na+) via electrostatic interaction;34 on the other hand, although the open metal sites can be first occupied by water molecules in aqueous solution, these coordinated water molecules may be replaced by FS2-.35 Therefore, we suggest that both the OH+ site in the ligand and the open metal site may play important roles in the adsorption for anionic dye FS. In MIL-101(Cr)SO3H, large amounts of –SO3- groups from the synthesis process of the MOF27 and the ionization process of –SO3H groups in aqueous solution can act the adsorption sites for cationic dye ST.

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FS

electrostatic interaction

ST

Scheme 1. The possible mechanism of the adsorption for cationic dye ST and ionic dye FS in MIL-101(Cr) and MIL-101(Cr)-SO3H.

In addition, the effect of co-existed non-polar molecules on the adsorption performance was investigated. As shown in Figure S7, the adsorption capacities of both MIL-101(Cr) and MIL101(Cr)-SO3H keep almost unchanged with the existence of non-polar benzene and naphthalene, further demonstrating the excellent selective adsorption abilities of the two MOFs. Meanwhile, the reusability of the MOFs was investigated as shown in Figure S8. It was found that FS-loaded MOFs can be well regenerated; however, for ST-loaded MOFs, the adsorption abilities first decreased and finally tend to be almost stable along with the regeneration processes, which is similar to the cases of some other adsorbents.36-37 3.4. Dyes separation in MOFs

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=

+ ST

FS

Figure 5. The separation process of ST-FS mixture in MIL-101(Cr) and MIL-101(Cr)-SO3H.

On the basis of data analysis for single component mentioned above, MIL-101(Cr) and MIL101(Cr)-SO3H were further applied in dyes separation. First, 15 mg MOF sample was added into 15 mL mixed aqueous solution of FS and ST (1:1, 50 mg L-1). After 24 h, an interesting phenomenon was observed as shown in Figure 5. It is obvious that the orange mixtures with MIL-101(Cr) and MIL-101(Cr)-SO3H return to be pink and fluorescence green respectively, indicating that MIL-101(Cr) and MIL-101(Cr)-SO3H are a couple of efficient materials for FS and ST separation. Therefore, the introduction of –SO3H groups can induce the reversion of the dyes separation performance, which is much different from most of previous works about dyes

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Figure 6. The adsorption isothermals for ST (a) and FS (b) of MIL-101(Cr) and MIL-101(Cr)-SO3H in twocomponent solutions.

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Next, the separation abilities of these two MOFs were investigated in details. As shown in Figure 6, in the two-component solutions, MIL-101(Cr) and MIL-101(Cr)-SO3H exhibit competitive adsorption ability for FS and ST respectively, similar to the situation in single component solutions. Furthermore, the adsorption selectivity was calculated to quantitatively evaluate the separation performance. As shown in Figure 7a, the selectivity αFS/ST of MIL-101(Cr) decreases gradually with the increase of the initial concentration and tends to be 36.1; while the selectivity αST/FS of MIL-101(Cr) keeps a very low value (less than 0.05) under the same condition. On the other hand, as expected, MIL-101(Cr)-SO3H exhibits thoroughly opposite selectivity as shown in Figure 7b. The αFS/ST in MIL-101(Cr)-SO3H keeps less than 0.1 but the αST/FS can reach up to 10.14 at the initial concentration of 50 mg L-1. These results demonstrate that MIL-101(Cr) and MIL-101(Cr)-SO3H are of great potential for the separation of dyes mixtures.

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Figure 7. The adsorption selectivity of MIL-101(Cr) (a) and MIL-101(Cr)-SO3H (b) towards different initial concentrations.

4. CONCLUSIONS In this work, two water stable MOFs, MIL-101(Cr) and MIL-101(Cr)-SO3H were applied in the adsorption and separation for cationic dye ST and ionic dye FS. It is found that MIL-101(Cr) and

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MIL-101(Cr)-SO3H can exhibit thoroughly opposite adsorption and separation performance for the dyes, which is mainly attributed to the opposite surface charges of the two MOFs due to introduction of –SO3H groups. Therefore, this work provides a significantly efficient approach to modify and even reverse adsorption or separation performance of MOFs.

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ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on ACS Publications website. FTIR spectra, N2 adsorption-desorption isothermals and zeta potentials of MIL-101(Cr) and MIL-101(Cr)-SO3H; molecular structures of ST and FS; the effect of light and co-existed nonpolar molecules on the adsorption; stability investigation of the MOFs in dyes-containing solutions; and regeneration of the dyes-loaded MOFs. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]; [email protected] Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was supported by Doctoral Scientific Research Foundation of Taiyuan University of Science and Technology (No. 20162012) and Natural Science Foundation of China (No. 21606007). REFERENCES (1) Wang, T.; Zhao, P.; Lu, N.; Chen, H.; Zhang, C.; Hou, Z. Facile Fabrication of Fe3O4/MIL101(Cr) for Effective Removal of Acid Red 1 and Orange G from Aqueous Solution. Chem. Eng. J. 2016, 295, 403. (2) Haque, E.; Lee, J. E.; Jang, I. T.; Hwang, Y. K.; Chang, J. S.; Jegal, J.; Jhung, S. H. Adsorptive Removal of Methyl Orange from Aqueous Solution with Metal-Organic Frameworks, Porous Chromium-Benzenedicarboxylates. J. Hazard. Mater. 2010, 181, 535.

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(3) Zhang, C.; Li, P.; Huang, W.; Cao, B. Selective Adsorption and Separation of Organic Dyes in Aqueous Solutions by Hydrolyzed PIM-1 Microfibers. Chem. Eng. Res. Des. 2016, 109, 76. (4) Guo, H.; Lin, F.; Chen, J.; Li, F.; Weng, W. Metal-Organic Framework MIL-125(Ti) for Efficient Adsorptive Removal of Rhodamine B from Aqueous Solution. Appl. Organometal. Chem. 2015, 29, 12. (5) Khan, N. A.; Hasan, Z.; Jhung, S. H. Adsorptive Removal of Hazardous Materials Using Metal-Organic Frameworks (MOFs): A Review. J. Hazard. Mater. 2013, 244-245, 444. (6) Wang, B.; Lv, X.-L.; Feng, D.; Xie, L.-H.; Zhang, J.; Li, M.; Xie, Y.; Li, J.-R.; Zhou, H.-C. Highly Stable Zr(IV)-Based Metal-Organic Frameworks for the Detection and Removal of Antibiotics and Organic Explosives in Water. J. Am. Chem. Soc. 2016, 138, 6204. (7) Wang, N.; Zhang, R.; Liu, T.; Shen, H.; Ji, S.; Li, J.-R. Ceramic Tubular MOFs Hybrid Membranes Fabricated Through in situ Layer-by-Layer Self-Assembly for Nanofiltration. AIChE. 2016, 62, 538. (8) Chang, G.; Huang, M.; Su, Y.; Xing, H.; Su, B.; Zhang, Z.; Yang, Q.; Yang, Y.; Ren, Q.; Bao, Z.; Chen, B. Immobilization of Ag(I) into a Metal-Organic Framework with -SO3H Sites for Highly Selective Olefin-Paraffin Separation at Room Temperature. Chem. Commun. 2015, 51, 2859. (9) Lv, X.-L.; Wang, K.; Wang, B.; Su, J.; Zou, X.; Xie, Y.; Li, J.-R.; Zhou, H.-C. BaseResistant Metalloporphyrinic MOFs for C-H Bond Halogenation. J. Am. Chem. Soc. 2017, 139, 211. (10)

Ahmed,

I.;

Jhung,

S.

H.

Applications

of

Metal-Organic

Frameworks

in

Adsorption/Separation Processes via Hydrogen Bonding Interactions. Chem. Eng. J. 2017, 310, 197.

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Table of Contents MIL-101(Cr)

FS

+ = ST FS

ST

MIL-101(Cr)-SO3H

Introduction of –SO3H groups into MIL-101 framework induces the reversion of separation performance for dyes.

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