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Zr(IV)-Based Metal-Organic Framework with T‑Shaped Ligand: Unique Structure, High Stability, Selective Detection, and Rapid Adsorption of Cr2O72− in Water Tao He,† Yong-Zheng Zhang,† Xiang-Jing Kong,† Jiamei Yu,*,‡ Xiu-Liang Lv,† Yufeng Wu,‡ Zhen-Ji Guo,‡ and Jian-Rong Li*,† †
Beijing Key Laboratory for Green Catalysis and Separation, Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering and ‡Institute of Circular Economy, Beijing University of Technology, Beijing 100124, P. R. China S Supporting Information *
ABSTRACT: Dichromate is known for severe health impairments to organisms. New and valid strategies have been developed to rapidly detect and efficiently remove this pollutant. Constructing stable luminescent metal-organic frameworks (MOFs) for dichromate recognition and removal from aqueous solution could provide a feasible resolution to this problem. Herein, a new luminescent Zr(IV)MOF, Zr6O4(OH)7(H2O)3(BTBA)3 (BUT-39, BUT = Beijing University of Technology) was constructed through the reaction of a newly designed functionalized T-shaped ligand 4,4′,4″-(1Hbenzo[d]imidazole-2,4,7-triyl)tribenzoic acid (H3BTBA) with zirconium salt. BUT-39 has a unique porous framework structure, in which Zr6 cluster acts as a rare low-symmetric 9-connected node and BTBA3− as a T-shaped 3-connected linker. As far as we know, this represents the first case of a (3,9)-connected Zr(IV)-MOF. BUT-39 could retain its framework integrity in boiling water, 2 M HCl aqueous solution, and pH 12 NaOH aqueous solution. Due to its good water stability and strong fluorescent emission, BUT-39 is then employed in fluorescence sensing for various ions in aqueous solution and shows good performance toward Cr2O72− selectively, at a low concentration and a short response time (0.9999 was obtained (Figure S21b, Supporting Information), suggesting that the model is suitable for describing the adsorption kinetics of this system. Given these observations, it is reasonably inferred that both physisorption and chemisorption should be involved in the Cr2O72− adsorption process in BUT-39.73,74 The chemisorptions might be partially attributed to the coordination between Zr6 cluster and Cr2O72−.34 Meanwhile, the imidazole N atoms in the benzimidazole moieties are basic, which can form a protonated salt in acid solution, being also favorable to enrich negativecharged Cr2O72− as well. Selective adsorption of BUT-39 toward Cr2O72− was also explored in a mixed aqueous solution containing Cl−, Br−, CO32−, AcO−, PO43−, NO3−, SO42−, and Cr2O72− anions with the concentration of 100 ppm each. As shown in Figure S22, the adsorption ability of Cr2O72− in the mixture was almost not affected by these interfering ions compared to that in the pure Cr2O72− solution. This selectivity could be attributed to not only the higher charge density of Cr2O72− (compared to Cl−, F
DOI: 10.1021/acsami.8b03987 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Research Article
ACS Applied Materials & Interfaces
realized by adding either 0.1 M HCl or 0.1 M NaOH, while the initial concentration of Cr2O72− was kept at 50 ppm for all samples. The BUT-39 sample (10 mg) was dispersed in 10 mL of Cr2O72− solutions with different pH values. After 12 h, these solutions were separated from the adsorbent with a syringe filter and UV−vis spectroscopy (at λ = 350 nm) was used to analyze the residual concentrations of Cr2O72−. The Cr2O72− adsorption efficiency (% adsorption) was obtained by the equation
oven for 5 days. Afterward, the system was cooled to room temperature. The colorless hexagonal crystals of BUT-39 were collected by filtration, washed with fresh DMF and acetone, and then dried in air (5.3 mg, 68% based on H3BTBA). X-ray Crystallographic Analysis. The diffraction data of BUT-39 were collected in an Agilent SuperNova charge-coupled device diffractometer with a mirror-monochromated enhanced Cu Kα radiation (λ = 1.54184 Å) at 173 K. The data sets were corrected by empirical absorption correction using spherical harmonics implemented in the SCALE3 ABSPACK scaling algorithm. The structure was solved by direct methods and refined by full-matrix leastsquares method on F2 with anisotropic displacement using the SHELXTL software package. Hydrogen atoms of ligands (except those on imidazole N) were calculated in ideal positions with isotropic displacement parameters. Those in the imidazole N atoms and coordinated water and hydroxyl groups were not added but were calculated into molecular formula of the crystal data. For this MOF, the volume fractions of disordered solvents in pores could not be modeled in terms of atomic sites, but were treated by using the MASK routine in the Olex2 software package. Crystal parameters and structure refinement are listed in Table S1 (for details, see CCDC 1820512). Sample Activation. As-synthesized BUT-39 (100 mg) was immersed in 15 mL of DMF in a 20 mL vial and then heated at 80 °C for 24 h. Then, the supernatant DMF was removed as soon as possible and the crystals were soaked in acetone (10 mL) for 2 days at room temperature, when fresh solvents were exchanged every 12 h. The sample was collected by filtration and dried in air. Prior to the gas adsorption tests, the dry sample was loaded in a sample tube and further degassed under high vacuum at an optimal temperature of 80 °C for 6 h. Stability Test. The as-synthesized BUT-39 samples (20 mg) were soaked in water, 2 M HCl, and pH 12 NaOH aqueous solutions at room temperature and in boiling water for 24 h separately. Then, the samples were collected by filtration, washed with water, and soaked in acetone for further PXRD and N2 adsorption investigations. Fluorescence Measurements. BUT-39 was finely ground before the measurement. The homogeneous powder sample of BUT-39 (20 mg) was soaked in 40 mL of deionized water and ultrasonicated for 30 min to form a uniform turbid suspension. The suspension (1.8 mL) was added to a quartz cuvette container, and then aqueous solutions (5 mM, 0.2 mL) of NanX or KnX (X = F−, Cl−, Br−, I−, NO2−, NO3−, ClO4−, IO3−, AcO−, CO32−, SO42−, MoO42−, WO42−, PO43−, and Cr2O72−; n = 1−3), MCln, or M(NO3)n (Mn+ = Na+, Mg2+, K+, Ca2+, Ni2+, Cu2+, Zn2+, Cd2+, Cr3+, Co2+, Hg2+, and Fe3+; n = 1−3) were separately injected into the suspensions by a pipette and uniformly mixed at room temperature to afford a series of mixtures containing different cations and anions with the same concentration of 0.5 mM. The fluorescence intensities of these mixtures were then recorded on a fluorescence spectrophotometer. The fluorescence intensities were measured at different intervals, and the obtained fluorescence intensities stayed almost the same without obvious variation after the quenching time reaching 1 min. To 1.8 mL of the MOF aqueous suspension, 0.2 mL of Cr2O72− aqueous solution with different concentrations was added to prepare the mixtures containing Cr2O72− with the controlled concentration of 10−500 μM. Concentration-dependent luminescence quenching of BUT-39 suspension by Cr2O72− was evaluated via measuring the fluorescence of the mixtures. For checking the influence of competing ions, 0.2 mL of aqueous solution containing all species of NanX or KnX (X = F−, Cl−, Br−, I−, NO2−, NO3−, ClO4−, IO3−, AcO−, CO32−, SO42−, MoO42−, WO42−, and PO43−; n = 1−3, with a concentration of 5 mM for each anion) was added into 1.8 mL of BUT-39 suspension. The fluorescence intensity of the mixture was measured. Then, 0.2 mL of Cr2O72− aqueous solution (5 mM) was added to the cuvette containing 1.8 mL of the mixture solution and the fluorescence intensity of the final mixture was measured. Cr2O72− Adsorption. The effect of pH on Cr2O72− adsorption was recorded in a pH range of 1−10. The variation of pH values was
adsorption efficiency (%) =
(C0 − Ce) × 100% C0
where C0 and Ce are the initial and equilibrium Cr2O72− concentrations (mg L−1), respectively. To evaluate the adsorption capacity, BUT-39 (10 mg) was separately dispersed in 10 mL of Cr2O72− solutions with different concentrations between 50 and 1000 ppm at pH = 3. After 12 h, the solution was separated from the adsorbent with a syringe filter and UV−vis spectroscopy (at λ = 350 nm) was used to analyze the residual concentrations of Cr2O72−. The equilibrium adsorption capacity (Qe) was calculated by the equation
Qe =
⎛ C0 − Ce ⎞ ⎜ ⎟V ⎝ m ⎠
where C0 and Ce (mg L−1) are the initial and equilibrium concentrations of Cr2O72−, respectively, V (L) represents the volume of the solution, and m (g) is the mass of sorbent. To describe the adsorption isotherm, the Langmuir adsorption model was exploited, which is applicable for monolayer adsorption with all adsorption sites identical and energetically equivalent. By fitting the equilibrium adsorption data with the Langmuir adsorption model, the adsorption capacity of BUT-39 could be calculated by the following equation
Ce C 1 = + e Qe Q mKL Qm where Ce is the equilibrium concentration of remaining Cr2O72− in the solution (mg L−1), Qe is the amount of Cr2O72− adsorbed on the adsorbent at equilibrium (mg g−1), Qm is the monolayer adsorption capacity (mg g−1), and KL is the Langmuir constant (L mg−1). For the adsorption kinetics experiment, BUT-39 (10 mg) was dispersed in 20 mL of Cr2O72− solution with the concentration of 100 ppm at pH = 3, which was then stirred for certain times at room temperature. The solution was filtered with a syringe filter for calculating Cr2O72− concentration by comparing the UV−vis absorbance (at λ = 350 nm) with the standard curve. The adsorption capacities (Qt) were calculated by the equation
Qt =
⎛ C0 − C t ⎞ ⎜ ⎟V ⎝ m ⎠
where C0 is the initial concentration of Cr2O72−, Ct (mg L−1) is the concentration of Cr2O72− at time t (min), V (L) is the volume of the solution, and m (g) is the mass of sorbent.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.8b03987. Detailed synthesis of ligand; 1H NMR, FT-IR, UV−vis, and luminescence spectra; TGA; and scanning electron microscopy images (PDF) Crystallographic data (CIF)
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AUTHOR INFORMATION
Corresponding Authors
*E-mail:
[email protected] (J.Y.). *E-mail:
[email protected] (J.-R.L.). G
DOI: 10.1021/acsami.8b03987 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
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Yufeng Wu: 0000-0003-2164-4465 Jian-Rong Li: 0000-0002-8101-8493 Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS The authors acknowledge financial support from the National Natural Science Foundation (21506003 and 21576006) and the National Natural Science Fund for Innovative Research Groups (51621003).
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DOI: 10.1021/acsami.8b03987 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
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DOI: 10.1021/acsami.8b03987 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
