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Water-Stable Metal−Organic Framework for Effective and Selective Cr2O72− Capture through Single-Crystal to Single-Crystal Anion Exchange Li Ma,† Jin Yang,*,† Bing-Bing Lu,† Cheng-Peng Li,*,‡ and Jian-Fang Ma*,† †

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Key Lab for Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, People’s Republic of China ‡ College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, MOE Key Laboratory of Inorganic−Organic Hybrid Functional Material Chemistry, Tianjin Normal University, Tianjin 300387, People’s Republic of China S Supporting Information *

ABSTRACT: Effective and selective capture of environmentally toxic Cr2O72− from water is desirable for both environment protection and human health, but it still remains a significant challenge. We present a water-stable cationic metal−organic framework (MOF) with large nanotubular channels (ca. 1.4 × 1.4 nm2), (1-Cl). Remarkably, the resulting porous material exhibits rapid aqueous-phase removal of Cr2O72− via an anionexchange manner. Meaningfully, the capture and separation of aqueous Cr2O72− are highly selective even in the presence of other disturbing anions. More importantly, the crystal structure of 1-Cl after anion exchange (1-Cr2O7) could be determined by single crystal X-ray diffraction, elaborating the single-crystal-to-singlecrystal (SC-SC) transformation. The Cr2O72− removal process by 1-Cl thus was directly uncovered by the crystal structure of Cr2O72−-incorporated 1-Cr2O7.

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INTRODUCTION

Metal−organic frameworks (MOFs), as an important family of porous materials,19−24 possess tunable pore sizes and surfaces, making them suitable for selective separation and sorption applications.25−34 In this regard, cationic MOFs have received considerable attention as anion exchange hosts owing to confinement of substitutable anions.35−37 In terms of selectivity and loading capacity, however, the development of MOFs as anion-exchanged adsorbents for trapping of toxic oxoanion is still at the early stages.38 Thus far, only a limited number of cationic MOFs were employed to capture dichromate via the anion exchange manner with improved uptake capacity and selectivity.39−41 In particular, the dichromate trapping processes by the cationic MOFs are rarely observed through the single-crystal to single-crystal (SCSC) anion exchange.42−44 In this work, a water-stable cationic MOF with large nanotubular channels, {Cu2[CuCl(TTCA)(H2O)2]}·NO3· 4DMA·6H2O (1-Cl), was synthesized (H4TTCA = 1,4,7,10tetrazazcyclododecane-N,N′,N′′,N′′′-tetramethylenecinnamic acid and DMA = N,N-dimethylacetamide, Scheme 1). Most strikingly, 1-Cl represents an exceedingly rare example that shows fast and selective dichromate trapping from aqueous solution through the SC-SC anion exchange process.

Currently, water pollution has become a pressing environmental issue. Therefore, significant research attention was devoted to removing pollutants of wastewater.1−3 In particular, heavy-metal contaminations from industrial effluents have already resulted in severe water pollution with the widespread growth of modern industry.4,5 Among the common heavymetal pollutants, dichromate (Cr2O72−) has been a focus of concern owing to its serious damage to the environment.6 To date, several techniques, such as adsorption, degradation, ion exchange, or photocatalytic reduction, have been trialed for removal of heavy-metal contaminations.7−9 In these techniques, the ion-exchange pathway is always applied as a preferred route due to its several advantages in selectivity, sensitivity, as well as simplicity of operation.10−13 Very recently, the typical anionic contaminants such as radioactive 99TcO4−, toxic SeO32−, SeO42−, CrO42−, and Cr2O72− have been removed through the ion exchanges by using the designed ion exchangers.14−17 Commonly, the currently used ion exchangers, including layered double hydroxides and zeolites, usually exhibit poor selectivity, limited adsorption capacity, and slow process kinetics because of their small pore sizes.18 Thus, the development of new materials for higher-performance ion exchange capacity from wastewater still remains a significant challenge but is of great importance. © XXXX American Chemical Society

Received: July 6, 2018

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DOI: 10.1021/acs.inorgchem.8b01879 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Scheme 1. Synthetic Route for H4TTCA·HCl Ligand

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RESULTS AND DISCUSSION Structural Description of 1-Cl. Self-assembly of H4TTCA·HCl with Cu(NO3)·2.5H2O under solvothermal conditions gave blue block-shaped crystals of {Cu2[CuCl(TTCA)(H2O)2]}·NO3·4DMA·6H2O (1-Cl) in a ca. 85% yield. Crystallographic analysis shows that 1-Cl crystallizes in the hexagonal P63/mcm space group. During the refinement, the disordered solvents were removed by utilizing the SQUEEZE routine in PLATON with a solvent accessible volume of ca. 56.7%,45 which is lower than the known value (ca. 69%) of the related MOF MMCF-2.24 The formula of 1Cl thus was established by electron diffraction density, thermogravimentric analysis (TGA), and elemental analysis (Figure S1). Cu1 is surrounded by four chelating azamacrocycle nitrogen atoms and one chlorine anion to give a Cu(II)metalated [CuCl(TTCA)]3− unit (Figure S2a). Cu2 and its symmetry-related species are bridged by four carboxylates from four different Cu(II)-metalated [CuCl(TTCA)]3− units to yield [Cu2(COO)4] secondary building units (SBUs). The backbone of each [CuCl(TTCA)]3− unit bridges four paddlewheel-like SBUs, and each SBU is linked by four distinct [CuCl(TTCA)]3− units (Figure S2b and S2c), then resulting in a highly porous 3D framework with a nanotubelike triangular channel (ca. 1.4 × 1.4 nm2) and hexagonal channel (ca. 2.0 × 2.0 nm2) along the c axis (Figures 1 and S2d). The NO3− anions are located in the hexagonal channels and served as a negative template to balance the positive charges of the framework. Noticeably, such large cavities induced 3-fold interpenetration of the framework along the c direction, which still possesses a large channel with an exterior and interior wall diameter of ca. 2.3 nm and ca. 1.4 nm, respectively (Figures 1c and 1d). Apparently, the free spaces in 1-Cl are occupied by structurally disordered solvents. Further topological analysis demonstrates that the Cu(II)-metalated TTCA4− anions act as one type of 4-connected nodes, and the [Cu2(COO)4] SBUs can be regarded as another type of 4-connected nodes, thus yielding a (4,4)-connected (42·84)(42·64) net (Figure 2). Fast and Selective Dichromate Trapping via SC-SC Ion Exchange. Crystalline samples of 1-Cl are highly stable in water. Particularly, the PXRD patterns demonstrate that 1-Cl still retains crystallinity and structural integrity after it is soaked in aqueous solution for several months (Figure 3). Given the high aqueous stability of 1-Cl and the anions (Cl− and NO3−) in the nanotubular access channels, thus anion exchanges were conducted with harmful aqueous solution of Cr2O72−. The anion exchange experiment was performed by simply placing crystal samples of 1-Cl (40 mg) into a 3 mL Cr2O72− aqueous solution (2 mM). The resulting anion exchange solution was

Figure 1. (a) View of the 3D framework of 1-Cl along the c axis. (b) View of the nanotubular hexagonal channel with a diameter of ca. 2.0 nm. (c) The 3-fold interpenetrated framework of 1-Cl along the c axis. (d) The 3-fold interpenetrated nanotubular subunit of 1-Cl along the c axis.

Figure 2. (a) Schematic representation of the (4,4)-connected (42· 84)(42·64) net of 1-Cl. (b) Schematic representation of the 3-fold interpenetrated (4,4)-connected net of 1-Cl.

Figure 3. Simulated (black), as-synthesized (green), and resolvated (red) PXRD patterns of 1-Cl.

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DOI: 10.1021/acs.inorgchem.8b01879 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Meanwhile, similar anion exchange experiments were further performed in 4 mM and 6 mM solutions of Cr2O72−, respectively. The Cr2O72− concentrations significantly decreased by ca. 63.5% and 47.2% within 5 min, respectively (Figure S3b and S3c). Subsequently, the concentrations of Cr2O72− decrease slowly with anion exchanges. The UV/vis spectroscopy demonstrated that the Cr2O72− adsorption nearly reached to the anion-exchanged sorption equilibrium after 180 min, where ca. 53.0 mg/g and 65.8 mg/g of the dichromate in aqueous solutions were trapped into the channels of 1-Cl, respectively (Figure 4a). That is to say, the total anion exchange capacity of 1-Cl for Cr2O72− reaches up to ca. 65.8 mg/g. The theoretically maximum dichromate capture capacity is 67.9 mg/g calculated by the crystallographic data, which is comparable to the experimental value. In contrast to the amorphous anionic exchange resins with random pores, the crystalline samples of 1-Cl exhibit very high anion exchange efficiency.46,47 Moreover, the Langmuir model can be applied to describe the anion-exchanged equilibrium occurring on samples of 1-Cl. Based on the Langmuir fitting, the maximum Cr2 O72− adsorption capacity reaches up to 65.16 mg/g, which is very near to the experimental value of 65.8 mg/g (Figure S4). It is noteworthy that only limited examples have been documented for the Cr2O72− exchange by cationic crystalline MOF materials thus far.38 In contrast to conventional adsorption materials, such as natural zeolites (adsorption capacity for Cr2O72− is 14.3 mg/g within 48 h), 1-Cl exhibits high adsorption capacity and efficient Cr2O72− capture.48 In addition, the adsorption behavior of 1-Cl toward a trace of dichromate in aqueous solution was studied as well. 1-Cl (32 mg) was put into 5 mL of aqueous solution containing 0.5 mM (108 ppm) of Cr2O72−. As illustrated in Figure 5, the intensity of the characteristic adsorption peak of dichromate decreases drastically at the beginning time. The removal of Cr2O72− reaches up to ca. 90.6% after 5 min and ca. 93% at 10 min (Figure 5). It takes ca. 30 min to attain the sorption equilibrium. The result implied that 1-Cl can rapidly remove the aqueous Cr2O72− with the ppm scales and may have some potential applications for purification of wastewater. In removing pollutant anions, the selective adsorption capacity is highly critical for anion trapping use of the materials.49,50 Thus, the selective adsorption behavior of 1-Cl toward Cr2O72− was studied in the presence of several disturbing anions, such as ClO4−, BF4−, and CF3SO3−. When the molar concentration ratio of the disturbing anion and

detected with UV/vis spectra at different time intervals. The characteristic adsorption peak intensity of dichromate (λmax = 352 nm) sharply reduced at the beginning 10 min, demonstrating that the Cr2O72− rapidly entered the channels of 1-Cl via anion exchange (Figure S3a). The fast adsorption may be partially ascribed to the ordered and regular nanotubular channels in samples of 1-Cl which allow for efficient delivery and transport of Cr2O72−. Accordingly, the concentration of Cr2O72− in aqueous solution decreased by ca. 68.6% within 5 min, as shown in Figure 4. It takes ca. 60 min to

Figure 4. (a) Adsorption kinetics of Cr 2O 7 2− at different concentrations (2 mM, 4 mM, and 6 mM) for 1-Cl. (b) Color changes of 1-Cl crystals before and after anion exchanges.

attain the anion-exchanged sorption equilibrium with the Cr2O72− adsorption capacity of 28.7 mg/g (Figure 4). The colors of the solution changed from yellow to pale yellow, while the colors of the samples varied from deep blue to green (Figure 4b).

Figure 5. (a) UV/vis absorption spectra of the aqueous solutions of Cr2O72− with removal of dichromate by 1-Cl at different time intervals. (b) Sorption kinetics of Cr2O72− (108 ppm) during the anion exchange with 1-Cl.. C

DOI: 10.1021/acs.inorgchem.8b01879 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Cr2O72− is 1:1, 1-Cl still exhibits highly selective adsorption behaviors for Cr2O72− with removal percentages of 74.2%, 75.6%, and 80.9% in the presence of the ClO4−, BF4−, and CF3SO3−, respectively (Figure 6). These removal percentages

exchange, the resultant green crystals of 1-Cr2O7 were collected for ICP analysis. The ICP result revealed that the molar ratio of Cu and Cr is 3:1 for the anion-exchanged samples of 1-Cr2O7, suggesting that the Cl− anions were fully exchanged by the Cr2O72− anions. Further, the energydispersive X-ray (EDX) spectra also verified the complete removal of the chloride anions and the inclusion of loaded dichromate anions after ion exchange, as illustrated in Figures 8 and S6. The crystallographic data and structure refinement for 1-Cl and 1-Cr2O7 are summarized in Table 1.

Figure 6. Effects of the competing anions on the removal of Cr2O72− by 1-Cl. The initial concentration of Cr2O72− is 0.2 mM.

of Cr2O72− are almost comparable to the value of 81.6% without any disturbing anions. Even though a mixture of 10fold disturbing anion was applied, the capability of the Cr2O72− exchange is still at a high efficiency with the removal percentages of 62.5%, 73.4%, and 77.5% in the presence of the ClO4−, BF4−, and CF3SO3−, respectively. The result suggests that 1-Cl reveals highly selective adsorption behaviors for aqueous Cr2O72− even in the presence of large excesses of competing anions. The selective capture of the Cr2O72− over the ClO4−, BF4−, and CF3SO3− anions may be attributed to the strong interactions of the Cr2O72− with the cationic framework. Remarkably, the PXRD patterns demonstrate that the structure of 1-Cl was identical with Cr2O72−-exchanged 1Cr2O7 (Figure S5). Fortunately, the block crystals were still well maintained after 24 h of the Cr2O72− exchange (5 mM) and were suitable for SC-XRD. In other words, the spontaneous SC-SC transformation from 1-Cl to 1-Cr2O7 could be achieved by anion exchange in the aqueous solution of Cr2O72− after 24 h. As shown in Figure 7, the SC-XRD of 1-

Figure 8. EDX mapping profiles for 1-Cl and 1-Cr2O7.

Moreover, the release experiment was also conducted via the anion exchange by soaking 1-Cr2O7 (30 mg) into an aqueous solution containing NaCl (1 M, 6 mL). Noticeably, ca. 70% of Cr2O72− was released from green crystals of 1-Cr2O7 after 5 min and ca. 92% of Cr2O72− was released finally (Figures 9 and S7). The color of the solution rapidly varied from colorless to yellow. Note that the fast adsorption and release kinetics of 1Cl made it a promising material for emergency removal of Cr2O72− from wastewater. The PXRD patterns demonstrate that the structural integrity almost remained after release of Cr2O72− (Figure S8).

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CONCLUSION In summary, we report an attractive cationic MOF sorbent material (1-Cl) consisting of nanotubular channels. The unusually large channels of the framework of 1-Cl present a very convenient route for the Cr2O72− trapping from contaminated water with high or low Cr2O72− concentrations. 1-Cl, as a remarkable example of a cation MOF adsorbent for removing the environmental pollutant Cr2O72−, exhibits fast and selective Cr2O72− removal with visual color changes. Particularly, the efficient capture and separation of the dichromate anions occurred with the anion-exchanged SC-

Figure 7. SC−SC structural transformation from 1-Cl to 1-Cr2O7 triggered by anion exchange.

Cr2O7 demonstrates that 1-Cl is isostructural with 1-Cr2O7, but the coordinated Cl− anions in 1-Cl were fully replaced by water molecules during the anion exchange process. It is worth mentioning that one type of NO3− anions are not exchangeable as a template and are still located in the triangular channels, which may be attributed to the sterical hindrance of the small channels toward the NO3− anions and the strong interactions of the NO3− anions with the framework. After the Cr2O72− D

DOI: 10.1021/acs.inorgchem.8b01879 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

Table 1. Crystallographic Data and Structural Refinements for 1-Cl and 1-Cr2O7 compound

1-Cl

1-Cr2O7

formula Mr crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z Dcalc (g cm−3) F(0 0 0) Rint GOF on F2 R1a [I > 2σ(I)] wR2b (all data)

C64H100ClCu3N9O23 1589.6 Hexagonal P63/mcm 20.7550(8) 20.7550(8) 36.9682(15) 90 90 120 13791.3(12) 6 1.148 5010 0.1171 1.014 0.0885 0.2831

C48H69CrCu3N5O25 1358.7 Hexagonal P63/mcm 20.7844(6) 20.7844(6) 36.9510(16) 90 90 120 13823.9(10) 6 0.979 4218 0.1568 0.937 0.0813 0.2561

a R 1 = ∑||F o| − |F c ||/∑|F o |. ∑w(Fo2)2]}1/2.

b

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Corresponding Authors

*E-mail: [email protected] (J. Yang). *E-mail: [email protected] (C.-P. Li). *E-mail: [email protected] (J.-F. Ma). Fax: +86-43185098620 (J.-F. Ma). ORCID

Jian-Fang Ma: 0000-0002-4059-8348 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (Grant no. 21771034 and 21471029).

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wR 2 = {∑[w(F o 2 − F c 2 ) 2 ]/

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Figure 9. Concentration dependent UV−vis absorption spectra for the release of Cr2O72− within 1-Cr2O7 crystals at various time intervals and the color change of an aqueous solution of Cr2O72−.

SC transformation, thus providing a direct evidence to elucidate the nature of such Cr2O72− removal process. Also, the highly effective and selective trapping of Cr2O72− makes 1Cl a promising prototype of the MOF-based ion-exchange material for water purification. This work afforded a feasible strategy to fabricate new porous crystalline MOF adsorbent materials for efficient removal of anionic pollutants in the future.

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AUTHOR INFORMATION

ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b01879. Experimental section, IR, TGA, PXRD patterns, figures and tables (PDF) Accession Codes

CCDC 1849301−1849302 contain the supplementary crystallographic data for this paper. These data can be obtained E

DOI: 10.1021/acs.inorgchem.8b01879 Inorg. Chem. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.inorgchem.8b01879 Inorg. Chem. XXXX, XXX, XXX−XXX