Assembly of Zeolite-like Metal–Organic Framework: An Indium-ZMOF

Aug 23, 2018 - A zeolite-like metal−organic framework JLU-MOF52 has been constructed based on 4-connected tetrahedral [In(O2C)4]− SBUs and organic...
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Article Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

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Assembly of Zeolite-like Metal−Organic Framework: An IndiumZMOF Possessing GIS Topology and High CO2 Capture Lifei Zou,†,‡ Xiaodong Sun,† Jiaqi Yuan,† Guanghua Li,† and Yunling Liu*,† †

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State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, P. R. China ‡ Inner Mongolia Key Laboratory of Photoelectric Functional Materials, College of Chemistry and Chemical Engineering, Chifeng University, Chifeng 024000, P. R. China S Supporting Information *

ABSTRACT: An In-ZMOF material, [(CH3)2NH2][In(ABTC)]·3DMF (JLU-MOF52), has been synthesized by using 2,2′,5,5′-azobenzenetetracarboxylic acid (H4ABTC) as a linker, which coordinated to four [In(O2C)4]− secondary building units (SBUs) to generate a 3D framework. JLUMOF52 is constructed by a rare 4 + 4 strategy from 4connected tetrahedral [In(O2C)4]− SBUs and tetrahedral ligands, which can be described as a (4, 4)-connected and forbidden interpenetrated zeolite-like MOF with GIS topology. The framework exhibits significant advantages in terms of chemical stability. N2 adsorption study of the activated JLU-MOF52 material reveals a Langmuir and a BET surface area is 1302 and 966 m2 g−1, respectively. Furthermore, the adsorption amount of CO2 for JLU-MOF52 is studied under 1 atm, which exhibits the highest CO2 capture ability at 273 K among the ZMOFs materials with GIS topology. These characteristics make JLU-MOF52 promising candidate materials for application in moderating increasing atmospheric CO2 levels.



INTRODUCTION Burning of oil, coal, and natural gas are the main sources of carbon dioxide emissions, which is primarily responsible for greenhouse gas and caused global warming in recent decades.1−4 Therefore, it has become a burning issue to effectively capture CO2 and sequester it from industrial flue gases. As one of the most promising materials, metal−organic frameworks (MOFs) have received increasing interests for applied prospect in gas capture and/or selectivity,5−7 catalysis,8,9 sensing,10,11 magnetism,12,13 luminescence,14 and so on. In recent years, MOFs have been applied diffusely in terms of CO2 adsorption and separation due to their tunable and controllable pore characteristics.15−17 Although gas storage and separation capacity of MOFs materials have great progress and development, most MOFs are sensitive in moisture/water, acidic, or basic media. Hence, it is a problem and challenge to synthesize MOFs with sufficient stability under chemical conditions that permits further potential applications. Zeolite-like metal−organic frameworks (ZMOFs) can be defined as a unique branch of MOFs that not only present zeolitic topologies but also exhibit distinctive properties: (1) prevent self-interpenetration of a three-dimensional networks and permit the construction of available larger pore space; (2) exhibit excellent chemical stability in aqueous media; and (3) show interesting ion exchange capability.18−22 Therefore, many researchers have been devoted to the design and construction of stable zeolite-like MOFs with desired framework structures. © XXXX American Chemical Society

The synthetic strategy of functional ZMOFs mostly adopted by mimic the Si−O−Si linker at T−L−T angles of average 145° with judicious choice of metal and ligand geometry.23,24 Until now, there are four different kinds of synthetic strategies toward the construction of ZMOFs:22 (1) based on the “‘edgeexpansion”’ of traditional zeolites;25−29 (2) assembled from supermolecular building blocks (SBBs), such as metal−organic cubes or squares (MOCs or MOSs);30−35 (3) derived from super tetrahedral building blocks;36,37 and (4) built via organic tetrahedral nodes.38,39 Among these approaches, the 4 + 2 synthetic strategy is especially popular and widely used up to now, which is formed by 2-connected ligands bridging 4connected tetrahedral nodes (T-nodes).40−42 Compared to 4 + 2 strategy, ZMOFs by a 4 + 4 strategy (a tetrahedral node linked to another tetrahedral node) have been rarely reported.39,43−45 Among all metal ions, In(III) ion possesses a high coordination number that generally forms structurally stable indium-organic frameworks (InOFs). In(III) ion is known to form three kinds of secondary building units (SBUs) in InOFs, including linear neutral [In(μ−OH)(O 2C−) 2], charged trimeric [In3(μ3-O)(O2C−)6] and tetrahedral [In(O2C−)4]/ [InN4(O2C−)4].46−53 In this work, we selected In(III) ion as metal center and adopted a 4 + 4 synthetic strategy for the Received: May 15, 2018

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DOI: 10.1021/acs.inorgchem.8b01330 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Figure 1. Structure description of JLU-MOF52: (a) ABTC4− ligand can be viewed as a 4-connected tetrahedral node, In(III) ion coordinated to four carboxylate groups to form a 4-connected tetrahedral node; (b) ball-and-stick view of the structure; (c) polyhedral view of the topology; (d) (4, 4)-connected GIS topology; (e) natural tiling representation. Color code: In, green; C, gray; O, red. Guest molecules and hydrogen atoms are omitted for clarity. achieved on the Germany Elementar vario MICRO instrument. Micromeritics ASAP 2420 was performed to measure nitrogen adsorption isotherms at 77 K, and Micromeritics ASAP 2020 instrument was carried out to measure carbon dioxide, methane, ethane and propane gas adsorption isotherms at 273 and 298 K. Before testing the gas adsorption performance, all the samples were prepared by exchanging guest molecules with dry ethanol 25 times for 5 days and evacuated under vacuum to remove the ethanol molecules at 85 °C for 10 h. Synthesis of [(CH3)2NH2][In(ABTC)]·3DMF (JLU-MOF52). Eight mg (0.02 mmol) of In(NO3)3·4H2O, 3.5 mg (0.01 mmol) of H4ABTC and 0.6 mL HNO3 solution (2.7 M in DMF) were added to 1.5 mL of DMF/H2O (1:0.5 v/v) mixed solvent in a 20 mL glass vial, and sonicated for 5 min to generate a clear solution, then the vial was heated at 115 °C for 16 h. The obtained yellow polyhedral samples were collected (yield: 70 wt %). Anal. Calcd (wt %) for C27H35O11N6In: C, 44.1; H, 4.80; N, 11.4. Found (wt %): C, 41.2; H, 4.70; N, 11.0. Crystallographic Data. Single-crystal diffraction data of JLUMOF52 was collected using a Bruker Apex II CCD diffractometer (Mo−Kα, 0.71073 Å) at 296 K. Its structure was solved with direct methods by SHELXS program of SHELXTL package. The positions of In, O, N and C atoms for this structure were successively obtained

assembly of In-ZMOF by 4-connected tetrahedral [In(O2C)4]− and tetrahedral organic ligand. It is worth mentioning that the tetrahedral organic ligand node is attributed to the distorted 2,2′,5,5′-azobenzenetetracarboxylic acid ligand (H4ABTC), in which two benzene rings are almost perpendicular to each other. Herein, we successfully synthesized a new In-ZMOF, [(CH3)2NH2][In(ABTC)]· 3DMF (JLU-MOF52), which is a forbidden self-interpenetrating ZMOF with GIS topology and exhibits good chemical stability as well as high CO2 capture ability.



EXPERIMENTAL SECTION

Materials and Measurements. Reagents and solvents were obtained through purchase and used without further purification, such as 2,2′,5,5′-azobenzenetetracarboxylic acid (H4ABTC), In(NO3)3· 4H2O, N,N-Dimethylformamide (DMF), HNO3 and dry ethanol. A Rigaku D/max-2550 diffractometer (Cu−Kα, 1.5418 Å) was carried out to collect the powder X-ray diffraction (PXRD) patterns from 4 to 40°. TGA Q500 thermogravimetric analyzer was performed for thermal gravimetric analyses (TGA), as-synthesized and activated samples were heated in a range from 28 to 800 °C with an increasing rate of 10 °C min−1 under air. Elemental analyses (EA) data were B

DOI: 10.1021/acs.inorgchem.8b01330 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry in difference Fourier maps and all non-H atoms were refined anisotropically by full-matrix least-squares refinements based on F.254 Because [(CH3)2NH2]+ cation and DMF molecules in the channels of JLU-MOF52 are highly disordered and impossible to be modeled properly, SQUEEZE method in the PLATON program was used to eliminate diffraction contribution and the results were appended in the CIF file. Single-crystal structure data, combine with TGA and EA results determined the final formula of JLU-MOF52. CCDC 1839697 for JLU-MOF52. TOPOS 4.0 was adopted to calculate the topology information on JLU-MOF52.55 Selected information on single-crystal X-ray data and structural refinement are listed in Table S1.



RESULTS AND DISCUSSION Structure Descriptions. JLU-MOF52 crystallizes in the Orthorhombic space group Fddd. It contains one In(III) ion, one ABTC4− ligand, three DMF and one [(CH3)2NH2]+ cation for charge balance in the asymmetric unit of JLUMOF52. Two benzene rings in ABTC4− are almost perpendicular to each other and form a dihedral angle of 89° due to the distorted ABTC4− ligand. All carboxylate oxygen atoms in ABTC4− connect to four independent In(III) centers to form a tetrahedral node, in which the T−L−T angles are 125, 94, and 89°, respectively (Figure S1). Each In(III) center adopts 8-coordinated geometry from four carboxylate groups of four fully deprotonated ABTC4− ligands to make up a typical [In(CO2)4]− SBU. Topologically, 4-connected [In(COO)4]− unit can be simplified as a tetrahedral node, and one ABTC4− coordinated to four In(III) ions to also form a tetrahedral node. Accordingly, the two kinds of tetrahedral nodes linked each other to generate a zeolite GIS topology with Schläfli symbol of {43.62.8} (Figure 1). The anionic framework possesses two kinds of channels from the directions of [100] and [110], with approximate dimensions of 3.7 × 3.7 Å2 and 9.7 × 3.3 Å2 regardless of the van der Waals radii (Figure S2). Moreover, ten [In(COO)4]− units are connected to ten ABTC4− to generate a GIS cage with the size of 9.9 Å, and the structural features encourage us to study its adsorption properties. Stability Study of JLU-MOF52. To assess the thermal stability of JLU-MOF52, we performed TGA in atmosphere. As seen from Figure S3, 82% weight loss is observed over the temperature range of 28−530 °C because of the elimination of [(CH3)2NH2]+ counterions and DMF molecules, accompanied by collapse of structural framework. It is further proved from variable-temperature PXRD experiments on the as-synthesized samples, and the diffraction peaks show no obvious change and indicate that the structure of the samples can be stable up to 250 °C (Figure S5a). Meanwhile, the as-synthesized samples were immersed in aqueous solutions of various pH to evaluate the chemically stability for JLU-MOF52. PXRD data obviously demonstrated that the crystallinity and structural framework of JLU-MOF52 can be well retained in pH 5 to pH 9 for 2 days (Figure S5b). Gas Adsorption Properties. To assess the permanent porosity of desolvated JLU-MOF52, we explored the N2 adsorption isotherm at 77 K. JLU-MOF52 exhibited the typical type-I adsorption isotherm as shown in Figure 2, which indicated the presence of permanent micropores. Additionally, the calculated total micropore volume of 0.46 cm3 g−1 is smaller than the theoretical value. It can be described that the cavity was occupied by the disordered [(CH 3 ) 2 NH 2 ] + counterions, which decreased the space of the pores.56 On the basis of the N2 adsorption data, a Langmuir and a Brunauer−Emmett−Teller (BET) surface area is 1302 and 966

Figure 2. N2 gas sorption isotherms for JLU-MOF52 at 77 K (inset: pore size distribution calculated by NLDFT method).

m2 g−1, respectively. Pore size distribution curve through nonlocal density functional theory (NLDFT) method exhibits a sharp micropore distribution, which is corresponding to the channel diameters in the crystal structure. To confirm the accessibility of the porosity for JLU-MOF52, CO2 adsorption ability was studied under 1 atm. From the measurement results, the adsorption amount of CO2 for JLUMOF52 is 129 cm3 g−1 at 273 K and 82 cm3 g−1 at 298 K as shown in Figure 3. A large quantity structures of MOFs have been reported, but it remains an important challenge to attain high CO2 capture performance at 273 K for MOFs exhibiting a CO2 adsorption >100 cm3 g−1. Notably, JLU-MOF52 exhibits the highest capture ability for CO2 among the ZMOFs with GIS topology at 273 K and 1 atm (Table S2). Interestingly, although the BET value for JLU-MOF52 is lower than that of ZSA-3 (1426 m2 g−1), ZSA-1 (1382 m2 g−1) and ZSA-4 (1158 m2 g−1), its CO2 capture capacity is significantly higher than that of them.33−35 The results indicated that high BET and large pore volume are not necessary in terms of increasing CO2 capture, and matching size is desirable between the suitable pore and a gas molecule for enhancing capture capacity of small gas molecules.57 Moreover, the CO2 adsorption amount of JLU-MOF52 at 273 K is superior to other In-MOFs with large porosity except InOF-1 (Table S3), but lower than that of Mg-MOF-74,58 Cu-TDPAT59 and CPM-200-Fe/Mg.60 According to all mentioned above, the high CO2 capture ability of JLU-MOF52 can be attributed to the integrated structural features, which possess suitable pore sizes matched with the size of CO2 molecule, the big cavity of GIS cage, and large BET surface area. To estimate the affinity between CO2 molecules and the host framework of JLU-MOF52, we calculated the isosteric enthalpy (Qst) according to the obtained adsorption data at 273 and 298 K. The initial Qst of JLU-MOF52 exhibits 30.4 kJ mol−1, which suggests the host framework and adsorbed CO2 molecules strongly interact with each other (Figure S6). Such a Qst value for CO2 capture can be compared to those of many InOFs materials, for example, InOF-13 (20.4 kJ mol−1), FJI-C1 (20.7 kJ mol−1), as well as InOF-1 (29.4 kJ mol−1).46,61,62 JLU-MOF52 is appraised its potential application in adsorption and selective separation of small hydrocarbons, which are mainly derived from natural gas and petroleum. For CH4, C2H6 and C3H8, single-component gas adsorption isotherms for JLU-MOF52 are tested at 1 atm. Figure 3b shows the uptake capacity for CH4 reaches 40.9 at 273 K and 23.2 cm3 g−1 at 298 K. It is noteworthy that the value at 273 K is much larger than many reported InOFs including (In2X)(Me2NH2)2(DMF)9(H2O)5 (22.5 cm3 g−1),56 FJI-C1 (15.1 C

DOI: 10.1021/acs.inorgchem.8b01330 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 3. (a) CO2, (b) CH4, (c) C2H6, and (d) C3H8 gas sorption isotherms for JLU-MOF52 at 273 and 298 K under 1 atm.

cm3 g−1),62 InOF-15 (24 cm3 g−1)63 and InOF-8 (16.6 cm3 g−1).64 The sorption amount of C2H6 and C3H8 at 273 K for JLU-MOF52 are 119.5 and 110.6 cm3 g−1, whereas that of C2H6 and C3H8 at 298 K are 100.9 and 98.7 cm3 g−1. At initial coverage, Qst for CH4, C2H6, and C3H8 reaches 18.8, 26.1, and 23.3 kJ mol−1, respectively (Figures S7−S9). On the basis of the above data, the sorption amount for CO2, C2H6 and C3H8 are obviously higher than the values for CH4 under the same conditions. Therefore, we need to investigate the CO2/CH4 and C2H6, C3H8/CH4 gas separation based on a popular method, which is the ideal adsorbed solution theory (IAST) to forecast the adsorption selectivity between two components through single component adsorption isotherms at room temperature. The data were fitted based on the dual-site Langmuir−Freundlich equation and this result prompted us to serve JLU-MOF52 as a gas separator in industrial applications. The selectivity of CO2/CH4 (0.5/0.5, 0.05/0.95) for JLU-MOF52 is 5.5 and 5.6 at 298 K (Figure S10). Furthermore, the calculated selectivity of C2H6/CH4 is 17.6 and C3H8/CH4 is 56.6, which is comparable to the reported GIS-type ZMOF JUC-160 under the same conditions.65

Single-crystal X-ray data in CIF, PXRD patterns for simulated and as-synthesized samples, thermogravimetric analysis and gases adsorption properties for JLUMOF52 (PDF) Accession Codes

CCDC 1839697 contains the supplementary crystallographic data for this paper. These data can be obtained 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.



Corresponding Author

*E-mail: [email protected]. ORCID

Guanghua Li: 0000-0003-3029-8920 Yunling Liu: 0000-0001-5040-6816 Notes

The authors declare no competing financial interest.





ACKNOWLEDGMENTS This work was supported financially by the National Natural Science Foundation of China (21771078 and 21621001), the 111 Project (B17020), and the National Key Research and Development Program of China (2016YFB0701100).

CONCLUSION In conclusion, by utilizing a rare 4 + 4 strategy, a novel InZMOF (JLU-MOF52) with zeolite GIS topology has been constructed based on 4-connected tetrahedral [In(O2C)4]− and organic ligand SBUs. JLU-MOF52 not only possesses forbidden interpenetration and anionic framework character but also exhibits good chemical stability and excellent CO2 capture capability of 129 cm3 g−1 (273 K, 1 atm). Finally, these characteristics are important for industrial applications and this material can serve as a promising candidate for CO2 capture.



AUTHOR INFORMATION



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S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b01330. D

DOI: 10.1021/acs.inorgchem.8b01330 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

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DOI: 10.1021/acs.inorgchem.8b01330 Inorg. Chem. XXXX, XXX, XXX−XXX