A Highly Symmetric Bimetallic-Tetracarboxylate Framework: Two-Step

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Article Cite This: Inorg. Chem. 2019, 58, 9425−9431

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A Highly Symmetric Bimetallic-Tetracarboxylate Framework: TwoStep Crystallization and Gas Separation Properties Lianyan Jiang, Junying Zhao, Sheng Chen, Jia Li,* Dapeng Wu, and Yanshuo Li Advanced Separation Material (NBU-ASM) Laboratory, School of Materials Science and Chemical Engineering, Ningbo University, Ningbo, 315211, People’s Republic of China

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S Supporting Information *

ABSTRACT: A novel noninterpenetrated MOF (NbU-2, NbU denotes Ningbo University) based on an enneanuclear bimetallic cluster was synthesized by postsynthetic uptake of Ni(II) ions of a sodium-based framework via two-step crystallization. This result demonstrated that the hydrolysis of metal ions in the step-by-step synthesis process is controllable and provided a new method for synthesizing high-nuclear metal cluster-based MOF materials. Note that the activated NbU-2 displays relatively high CO2/N2 selectivity, which was proved by breakthrough experiments of CO2/N2 mixtures.

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INTRODUCTION Metal−organic frameworks (MOFs) are renowned for their designable structure over the past few decades.1−3 Intrigued by their unique characteristics, the prospective applications involving the storage of gaseous energy,4 separation of light hydrocarbons,5 catalysis,6 capture of volatile organic compounds,7 chemical sensing,8 and biomedical delivery,9 as well as other applications, are widely explored. In general, the rational selection of secondary building units (SBUs), polydentate ligands, and even reaction conditions during synthesis is a key factor in the successful construction of MOF materials. Although an MOF structure can be in principle controlled through judicious selection of SBUs and linkers, the direct synthesis of stable MOFs with high porosity is still very difficult considering the hydrolysis of metal ions and/or interactions between organic ligands. Very recently, there are overwhelming demands for CO2 capture-based materials owing to the concern of global warming, economic developments, and human life. Much work has been devoted to improve the selective performances of CO2 by effectively adjusting the pore size and inner environment of MOF materials. Moreover, the trade-off between gas selectivity and adsorption capacity of MOF materials is still a key issue that must be addressed to obtain efficient gas separation materials. Therefore, a new strategy has been attempted to use MOFs with expected large pores to enhance the gas separation performance. One of the methods is to use larger organic linkers and/or polynuclear metal © 2019 American Chemical Society

clusters as a building block. Polynuclear metal clusters can not only avoid structural interpenetration but also endow MOF materials with new possibilities in terms of topology and excellent functionalities.10 However, the use of polynuclear metal clusters for the syntheses of MOFs with large pores still poses a great challenge, partly because the coordination of reported metal nodes with large linkers is less predictable and controllable, and/or the interactions between large linkers leads to interspersed structures or close-packed structures. As an effective postsynthesis method, step-by-step synthesis exhibits a further level of superiority in producing interesting structures.11−13 Up to now, the stepwise synthesis strategies involve altering either SBU and/or organic linkers after the initial crystallization. Various factors including temperature,14 light,15 solvent exchange,16,36,37 ligands exchange34/insertion,17 sorption of metal ions/metal clusters,18,38,39 and pressure effect30 have been widely studied. Due to the existence of the cleavage and formation of metal−ligand bonds simultaneously in the solid state structure, the stepwise synthesis process is generally accompanied by the appearance of recrystallization,29 single-crystal-to-single-crystal (SCSC),14−16 and even crystalto-amorphous-to-crystal (CAC)35 transitions. At the same time, the crystal structure before and after the initial crystallization shows not only 0D-to-2D,19 1D-to-2D,20 and 2D-to-3D17,21 but also 3D-to-3D18 conversions. It is obvious Received: April 30, 2019 Published: June 24, 2019 9425

DOI: 10.1021/acs.inorgchem.9b01258 Inorg. Chem. 2019, 58, 9425−9431

Article

Inorganic Chemistry

Figure 1. Optical images show the stepwise synthesis process through uptake of nickel ions at room temperature.

Figure 2. (a) The enneanuclear metal cluster in NbU-2. (b) Molecular structures of H4ptptc ligand. (c) The three-dimensional structure without guest solvent molecules showing voids viewed along the c axis. All of the hydrogen atoms in the picture have been deleted for clarity. solid sodium perchlorate was added to the tube directly. After one night, columnar white crystal (NbU-2a) aggregates formed on the bottom of the tube. The columnar white crystals of NbU-2a were first washed with fresh DMSO, and then, the filtered samples were lyophilized in a lyophilizer (LABCONCO, FreeZone2.5L). The chemical composition of the activated NbU-2a can be presumed to be Ni3.5(C6H16N)0.5(ptptc)(DMSO)2 (C6H16N = protonated triethylamine). Elemental analysis for the activated NbU-2a: calcd.: C 50.00%, H 4.38%, N 1.01%, S 9.29%; found: C 50.09%, H 4.77%, N 1.10%, S 10.05%. According to the speculated elemental composition and the quality of the resulting crystal, the yield of the first step is about 80% based on the H4ptptc ligand. The synthesis for NbU-2 follows: After the formation of NbU-2a, the remaining solutions of the tube were carefully removed. Then 1 mL of fresh DMSO was added, above which layered 8 mL of DMSOMeOH (1:3 v/v), and 4 mL of methanol containing 0.3 mmol of Ni(NO3)2 was layered on the top. Columnar white crystals gradually turn yellow day by day (Figure 1). After 2 weeks, dark yellow crystals of [Ni3Na6(μ3-DMSO)(μ2-MeOH)3(MeOH)3(ptptc)3]·5DMSO· 3H2O (NbU-2·S) were obtained (the yield calculated based on H4ptptc is about 65%). Elemental analysis for the activated NbU-2: calcd.: C 45.10%, H 4.33%, N 0%, S 8.60%; found: C 44.49%, H 4.34%, N 0.11%, S 8.66%. The amounts of extra framework guest molecules were calculated by elemental analyses and TG analyses (Figure S2).

that a stepwise strategy can effectively overcome the hydrolysis of metal ions22,23 and the interaction between ligands18 and obtain novel structures that usually cannot be obtained by a one-step reaction.11−23,29,30,34−39 In addition, it should be noted that the stepwise synthesis process can give rise to more stable structures,23 which provides greater possibilities for the application of materials. Due to our extensive interest in metal cluster-based MOF materials, a series of polynuclear cluster-based MOFs showing excellent structural aesthetics and high selectivity of CO2/CH4 and/or C2HX/CH4 have been systematically designed. Herein, we report a bimetallic-tetracarboxylate framework, (NbU-2)·S, namely, [Ni3Na6(μ3-DMSO)(μ2-MeOH)3(MeOH)3 (ptptc)3]·5DMSO·3H2O (MeOH = CH3OH, DMSO = C2H6SO, H4ptptc = p-terphenyl-3,3″,5, 5″-tetracarboxylic acid), based on a novel enneanuclear [Ni3Na6(DMSO)(MeOH)6(COO)12] SBU, was obtained by a two-step crystal growth method through postsynthetic uptake of nickel ions. Impressively, this result demonstrated that the hydrolysis of metal ions in the step-by-step synthesis process is controllable and provided a new method for synthesizing high-nuclear metal cluster-based MOF materials. Simultaneously, the activated NbU-2 displays high CO2 uptake capacity and relatively high CO2/N2 selectivity, which was proved by breakthrough experiments.

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RESULTS AND DISCUSSION Crystal Structure of NbU-2. We cannot get the crystal structure of NbU-2a because of its polycrystalline state and instability. After leaving its mother liquor, NbU-2a quickly turns gray, which means the collapse of its structure. We performed elemental analysis on the crystals of both materials;

EXPERIMENTAL SECTION

Synthesis. The synthesis for NbU-2a follows: 0.1 mmol of H4ptptc and 80 μL of triethylamine were dissolved in 4 mL of DMSO. The resulting solution was placed in a test tube; then 0.3 mmol of 9426

DOI: 10.1021/acs.inorgchem.9b01258 Inorg. Chem. 2019, 58, 9425−9431

Article

Inorganic Chemistry

Figure 3. Images showing the 3-connected ptptc4− ligands connected three metal clusters (a), 9-connected enneanuclear [Ni3Na6(μ3-DMSO)(μ2MeOH)3(MeOH)3(COO)12] unit linked nine independent ligands (b), topological structure (c), and accessible surfaces of NbU-2 (d).

three-dimensional structure (Figure 3a,b). To give a simplified mode of the structure (Figure 3c), the enneanuclear cluster and ptptc4− ligand have been seen as 9- and 3-connected nodes, giving a (3,9)-connected network with a point symbol of {4·62}3{46·621·89}, as calculated by the TOPOS software.24 Apparently, larger bridged ligands connect large-sized and high-nuclear SBUs, which can effectively avoid interpenetration. Regardless of the coordinated MeOH molecules and DMSO guests, the guest accessible volume of NbU-2 is about 55.7% per unit cell estimated by PLATON. The 3D structure of NbU-2 features intersecting 3-D channels and a trigonal window with a side length of about 10.3 Å (Figure 2c) (ignore the van der Waals radii). Additionally, there are many kinds of irregular cavities calculated by PLATON with the radius between 2.3 and 4.2 Å (Figure S1, Supporting Information (SI)), indicating that NbU-2 may exhibit excellent adsorption properties. Purity and Stability. Powder X-ray diffraction (PXRD) studies were carried out on both of the as-synthesized NbU-2a and NbU-2 to verify the phase purity of the two compounds. After leaving its mother liquor, NbU-2a quickly turns gray, which means the collapse of its structure, and powder X-ray diffraction gave very few weak diffraction peaks even in the presence of DMSO. At 100 K, diffraction peaks are given by an Agilent Technologies SuperNova X-ray single-crystal diffractometer to prove that NbU-2a is still in a crystalline phase (Figure 4). In addition, the crystalline samples of NbU-2a were also soaked in methanol and DMSO at 298 K for 1 week. During this time, NbU-2a did not dissolve in these two organic solvents, and even no significant changes were observed on the crystal surface. TGA study of the as-synthesized NbU-2 revealed a first-step weight loss before 100 °C is about 11.17% (Figure S2 in the SI), which could be attributed to the release of solvent water and ethanol molecules. After that, a small platform appeared at 100−300 °C, and then, with the loss of high boiling DMSO, the structure gradually decomposed after 300 °C. Considering that DMSO is difficult to remove at low temperatures, TGA

obviously, the content of nitrogen in NbU-2a exceeds that of NbU-2, which means that NbU-2a may also be an anionic framework and protonated triethylamine was filled in the channels as cations to balance the charge of the framework. From the result of single-crystal X-ray diffraction study, NbU-2 crystallized in trigonal R3c space group and consists of novel enneanuclear [Ni 3 Na 6 (μ 3 -DMSO)(μ 2 -MeOH) 3 (MeOH)3(COO)12] SBUs. The asymmetric unit is composed of one independent Ni2+ ion, two Na+ ions, one ptptc4− ligand, one μ2-MeOH molecule, one terminal methanol molecule, and one-third μ3-DMSO groups. As shown in Figure 2a, the Ni1 ion locates in a distorted octahedral geometry, which combined six O atoms from four carboxyl groups. Na1 and Na2 ions adopt the common 5-coordinate and 4-coordinate modes, respectively.32,33 Na2 is linked to three O atoms from ptptc4− ligands (O2, O6, and O7) and one methanol molecule (O11). Carboxyl oxygen atoms O2 and O7 further μ2-bridge Ni1 and Na2, forming anionic binuclear [NiNa(CH3OH)(COO)4]−. Na1 is combined by five O atoms from two carboxylate groups and two MeOH and one DMSO molecules. The MeOH molecules further μ2-bridge two Na1 centers, while the DMSO molecule is μ3-capping three Na1 centers, forming cationic trinuclear [Na3(μ2-MeOH)3(μ3-DMSO)]3+. The structure of enneanuclear [Ni3Na6(μ3-DMSO)(μ2MeOH)3(CH3OH)3(COO)12] SBUs can be viewed as the assembly of two ionic moieties, the trinuclear [Na3(μ2MeOH)3(μ3-DMSO)]3+ and three binuclear [NiNa(CH3OH)(COO)4]− units, held together by carboxyl oxygen (μ2-O4, μ2O7, and O8). The [Ni 3 Na 6 (μ 3 -DMSO)(μ 2 -MeOH) 3 (MeOH)3(COO)12] clusters are finally bound to three ptptc4− ligands with Ni−O = 1.985(6)−2.106(11) Å and Na−O = 2.269(11)−2.586(10) Å, two μ2-MeOH groups with Na−O = 2.363(1) Å, one μ3-DMSO group with Na−O = 2.521(8)Å, and three terminal methanol molecules with Na− O11 = 2.273(13) Å, respectively. The resulting enneanuclear clusters are connected to nine neighbors, and each ptptc4−, conversely, connected three enneanuclear clusters, thereby establishing a 3,9-connected 9427

DOI: 10.1021/acs.inorgchem.9b01258 Inorg. Chem. 2019, 58, 9425−9431

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activated at various temperatures under dynamic vacuum for 24 h. As shown in Figure 4, the PXRD patterns reveal that the framework of NbU-2 remains intact until 80 °C, and when heated to 100 °C under dynamic vacuum, the structure completely collapsed. Gas Adsorption Properties of NbU-2. N2 gas adsorption at 77 K was performed using a Micromeritics Trist 3020 aparatus to check the permanent porosity of activated NbU-2. Before the gas adsorption test, the methanol-exchanged NbU-2 was activated at 80 °C under dynamic vacuum for 24 h to give fully activated samples. As shown in Figure 4, powder X-ray diffraction study has verified the stability of the activated NbU2. It should be noted that both of the adsorption and desorption isotherms of activated NbU-2 exhibit a typical typeIV adsorption behavior25 with the maximum nitrogen adsorption capacity of ∼160.7 cm3(STP)·g−1 at 1 bar (Figure 5a). The corresponding Langmuir surface area was estimated to be 421.3 m2 g−1 (BET surface area about 200.7 m2 g−1), and the pore size distribution curves (Figure S10) obtained by the Horvath−Kawazoe method show a pore distribution of about 5−7 Å, which is consistent with the crystal structure. Obviously, the actual amount of adsorption before P/P0 = 0.9 was significantly lower for the calculated solvent accessible volume, which is probably due to the incomplete activation. The DMSO guest molecules are hard to be exchanged with methanol and activated at relatively low temperature, which occupied the cages and/or the channels in the structure. Simultaneously, the completely reversible sorption−desorption behavior before P/P0 = 0.9 is probably owing to the suitable triangle channels. The substantial interparticle adsorption and/ or the capillary condensation effect causes a rapid increase of N2 uptake in the high-pressure region (close to P/P0 = 1),

Figure 4. PXRD patterns of samples.

study of the methanol-exchanged NbU-2 was also performed under the same condition. The first-step weight losses of the methanol-exchanged samples between 30 and 100 °C are increased to 25.05%, which means that 3.5 DMSO molecules are replaced by MeOH molecules. Then, similar thermogravimetric platforms and decomposition temperatures were measured. Overall, the TGA study reveals that NbU-2 can remain stable at about 150 °C under the protection of nitrogen. Powder X-ray diffraction studies were performed to further check the thermal stability of NbU-2; the samples were

Figure 5. (a) N2 adsorption isotherm for NbU-2 at 77 K and 1 bar. (b) Adsorption isotherms of NbU-2 for CH4, CO2, and N2 at 273 and 298 K. (c) CO2 and CH4 adsorption enthalpies for NbU-2. (d) Adsorption selectivity of CO2/CH4 using different mole ratios calculated by IAST. 9428

DOI: 10.1021/acs.inorgchem.9b01258 Inorg. Chem. 2019, 58, 9425−9431

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Inorganic Chemistry Table 1. Summary of the Adsorption Uptakes, Adsorption Enthalpies, and Selectivity Data in Various MOFsa 31

SNNU-95 JLU-Liu3041 SIFSIX-2-Cu42 IISERP-MOF2040 MAF-2343 NJU-Bai742 NJU-Bai3544 13X42 SIFSIX-3-Zn42 Cs@RWY46 NbU-2

SBET (m2 g−1)

pore size (N2, Å)

206.6 2409 1881 945 622 1155 862.8

4.2 11.2 13.05 5.85

250 526 216

pore volume (cm3 g−1) 0.81

0.21 0.439 10 3.84 8.4

CO2 uptake (cm3 g−1)

Qst CO2 (kJ mol−1)

27.9 49 41.4 78.4 74.2 66.2 71.3 112 57.0 71.9 58.2

34.2 24 22 22 47.4 40.5 33.37 44 45 30.2 22.4

selectivity for CO2/N2 5.8 13.7 220 163 97 275.8 420 1700 180 464

a

CO2 uptake data: at 273 K and 1.0 bar. The selectivity data for SIFSIX-2-Cu, NJU-Bai35, and 13X are at a temperature of 298 K.

while a hysteresis close to P/P0 = 1 may be attributed to the agglomeration of the samples. The adsorption capacity of NbU-2 for the uptake of CH4, CO2, and N2 was performed at 273 and 298 K (Figure 5b). The pure component adsorption values of CO2 at 1 atm are 58.2 and 29.8 cm3(STP)·g−1, respectively, which are larger than that of SNNU-95 and other compounds with larger cages or channels (Table 1).41−44 The adsorption enthalpy of CO2 at zero loading calculated by the virial equation using the adsorption isotherms of 273 and 298 K is 22.4 kJ·mol−1 (Figure 5c and Figure S5 in the SI). The adsorption of N2 was not observed at 273 K, suggesting that NbU-2 may become a promising candidate material for CO2/N2 separation.45 For methane adsorption under the same conditions, NbU-2 adsorbs only 12.5 and 7.9 cm3(STP)·g−1 at 1 atm, respectively. Herein, the CO2 uptakes are nearly 5 times greater than that of CH4 at 273 K (Figure 5b). Gas Separation Performance of NbU-2. The IAST (ideal adsorbed solution theory) calculations were first used to evaluate the adsorption selectivity of CO2/CH4 and CO2/N2. As shown in Figure 5d, CO2/CH4 with three different mole ratios of 8:2, 5:5, and 2:8 were done, giving the calculated selectivities for CO2 over CH4 under 100 kPa as 6.6, 6.4, and 6.3 at different mole ratios, indicating a moderate CO2/CH4 selectivity. More interestingly, the selectivity value for the 25− 75 CO2/N2 binary mixtures is 464.0 under 1 kPa and 273 K (Figure 6 inset), which is larger than that of many porous materials only functionalized with the open metal sites or Lewis basic sites.26,27 We further examined the activated NbU-2 in the actual adsorption process for CO2/N2 mixtures through experimental breakthrough study. The test was conducted with a stainless steel column filled with activated NbU-2 (0.467 g), and a mixed binary gas (25−75 CO2/N2, v/v) flow was then introduced at 273 K and 1 atm. As shown in Figure 6, the breakthrough curve shows that CO2 is completely separated from N2. After the gas mixture passed, the nitrogen gas was first detected and the breakthrough time of CO2 takes place at approximately 5 min, which represents about 16.1 cm3 of CO2 was captured per gram of NbU-2 under these dynamic conditions. Although this value is much less than the amount of CO2 adsorption observed in volumetric measurement, the experimental result is consistent with the IAST theoretical calculations and is comparable to the reported materials such as ZIF-93.28 Therefore, the overall results demonstrate that NbU-2 has potential application for CO2 capture.

Figure 6. Breakthrough curves of a CO2/N2 gas mixture (25:75) at 273 K, gas flow: 6 mL/min; sample mass: 0.467 g of activated NbU-2. Inset: IAST adsorption selectivity of CO2/N2 at 273 K.

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CONCLUSIONS In conclusion, a novel enneanuclear bimetallic-based MOF (NbU-2) with a noninterpenetrated structure has been obtained through a step-by-step synthesis method. Notably, NbU-2 shows preferential gas selectivity of CO2/N2, which was proved by breakthrough experiments of CO2/N2 mixtures. In addition, this result demonstrated that the hydrolysis of metal ions in the stepwise synthesis process is controllable under alkaline conditions, and this method could be a powerful way to design and explore multifunctional cluster-based MOFs.

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ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.9b01258. Experimental materials, calculation methods, and additional figures (PDF) Accession Codes

CCDC 1870993 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. 9429

DOI: 10.1021/acs.inorgchem.9b01258 Inorg. Chem. 2019, 58, 9425−9431

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Inorganic Chemistry

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Jia Li: 0000-0002-8392-1125 Yanshuo Li: 0000-0002-7722-7962 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We gratefully acknowledge the National Natural Science Foundation of China (21701091), the Open Project of the State Key Laboratory of Physical Chemistry of the Solid Surface (Xiamen University) (201707), and the K. C. Wong Magna Fund in Ningbo University. The authors also thank Prof. Jun Tao and Zi-Shuo Yao from Beijing Institute of Technology for their help in single-crystal testing and analysis.

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