A Microporous Heterovalent Copper-Organic Framework Based on

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A Microporous Heterovalent Copper-Organic Framework Based on [Cu2I]n and Cu2(CO2)4 SBUs: High Performance for CO2 Adsorption and Separation, Iodine Sorption and Release Yuan Jiaqi, Jiantang Li, Liang Kan, Lifei Zou, Jun Zhao, Dongsheng Li, Guanghua Li, Li-Rong Zhang, and Yunling Liu Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00820 • Publication Date (Web): 11 Jul 2018 Downloaded from http://pubs.acs.org on July 19, 2018

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Crystal Growth & Design

A Microporous Heterovalent Copper-Organic Framework Based on [Cu2I]n and Cu2(CO2)4 SBUs: High Performance for CO2 Adsorption and Separation, Iodine Sorption and Release Jiaqi Yuan,a Jiantang Li,a Liang Kan,a Lifei Zou,a Jun Zhao,b Dong-Sheng Li,b Guanghua Li,a Lirong Zhang*, a and Yunling Liu*, a a

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of

Chemistry, Jilin University, Changchun 130012, P. R. China b

College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002, China

*To whom correspondence should be addressed. Professor Lirong Zhang, E-mail: [email protected] Professor Yunling Liu, E-mail: [email protected]

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ABSTRACT

A microporous heterovalent Cu-MOF, [(Cu2I)Cu2L2(H2O)2]22+·2NO3-·5DMF (1) (L = 5-(4H-1, 2, 4-triazol-4-yl) benzene-1, 3-dicarboxylic acid, DMF = N, N-dimethylformamide), has been successfully synthesized by using the mixed secondary building unit (SBU) strategy. Compound 1 was constructed by [Cu2I]n chain and Cu2(CO2)4 paddlewheel SBUs which exhibited a new (3, 4, 4)-connected topology. Although compound 1 possesses moderate surface area, it exhibits better CO2 capture (91.9 cm3 g-1 at 273 K) and separation ability (selectivity for CO2 over CH4: 8.2 under 1 bar at 298 K) than most of the reported CuxIy based MOFs. Moreover, compound 1 is also a good candidate for the capture and release of iodine.

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INTRODUCTION

Currently, environment pollution and energy shortage problems seems to be one of the most intractable issues that scientists concerning.1-3 CO2, as one of the main gases that can cause greenhouse effect, whose emission reduction has been attracted more and more attention from scientists all over the world.4-9 In addition, CO2 is also a main impurity of natural gas, which would reduce the energy conversion efficiency.10-13 Therefore, it is necessary to develop such new materials that not only effectively capture CO2, but also separate CO2 from the natural gas to improve the energy conversion rate.

In the last two decades, metal-organic frameworks (MOFs), as a burgeoning category of porous materials, which were constructed of organic ligands and metal ions or clusters through coordination bonds,14-17 have the features of high surface area and structural or functional tunability.18-19 MOFs constructed by metal halides as inorganic parts are a significant class of functional porous materials (particularly hybrid sliver(I) and copper(I) halides).20 Cu(I)-halide MOFs have gained considerable interest due to their diverse structural and photophysical properties and potential applications as low-cost,25-28 plentiful materials in gas adsorption and separation,29-31 organic molecule adsorption and catalysis,32-37 etc.

Secondary building units (SBUs) design is an effective synthetic strategy to construct diverse MOFs with robust and multifunctional properties.38-41 The Cu(I)-iodide based SBUs affords us a series of geometrical diverse units, such as the tetrameric 3



cubane-like [Cu4I4], the dimeric rhomboid [Cu2I2], the hexagonal prism-shaped [Cu6I6] and zigzag [CuxIy]n chain, etc.42-45 However, among most of the reported Cu(I)-iodide based MOFs, only a few is robust enough to exhibit gas adsorption property.46-47 CuI was used as the metal source since it can form various CuxIy clusters and Cu+ ions are also easy to partly convert into Cu2+ ions in the air to enrich the diversity of SBUs.48-50 Cu2+ ions are more likely to form the classic Cu2(CO2)4 paddlewheel SBU by coordinating with the O-donors, which is helpful to improve the structural stability of the MOFs based on CuxIy SBUs to develop the gas adsorption ability.50 In addition, it is known that azolate ligands with N-donors have the advantage of strong and directional coordination ability in connecting metal ions to construct stable frameworks, such as zeolitic imidazolate frameworks (ZIFs).51-53 Accordingly, Cu+ and I- ions can be coordinated with N-donors to form a much more stable [CuxIy]n chain than other CuxIy based SBUs such as Cu4I4 clusters.

Based on the above consideration, we choose the bifunctional organic ligand, 5-(4H-1, 2, 4-triazol-4-yl) benzene-1, 3-dicarboxylic acid (H2L), which contains two types of coordination groups (triazolate N- and carboxylate O-donor), as it has opportunities to combine two different SBUs into one framework. Consequently, a novel microporous heterovalent copper-organic framework, [(Cu2I)Cu2L2(H2O)2]22+·2NO3-·5DMF (1) has been successfully synthesized, which was constructed by two kinds of SBUs: [Cu2I]n chain SBUs and Cu2(CO2)4 paddlewheel SBUs.54-56 It exhibits a novel (3, 4, 4)-connected topology. Compared with most of the CuxIy based MOFs without adsorption ability, compound 1 possesses a moderate Brunauer-Emmett-Teller (BET) 4


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surface area (ca. 692 m2 g-1). Moreover, the result of ideal adsorbed solution theory (IAST) calculations illustrates that compound 1 may be a candidate material for CO2 capture and separation since it exhibits a good adsorption ability for CO2 and high selectivity for CO2 over CH4 (8.2 for CO2/CH4 = 0.05/0.95 and 7.4 for CO2/CH4 = 0.5/0.5 under 1 bar at 298 K). Meanwhile, the I2 sorption and release performance in organic solvents of the activated samples of compound 1 has been investigated, which indicates it is also a promising material for I2 capture.57-58

EXPERIMENTAL SECTION

Materials and methods

All of the related chemicals were purchased from commercial sources and used without further purification. Powder X-ray diffraction (PXRD) data were collected on a Rigaku D/max-2550 diffractometer with Cu-Kα radiation (λ = 1.5418 Å) over the 2θ range of 3-40o at room temperature. Elemental analyses (C, H, and N) were collected on a vario MICRO elemental analyzer (Elementar, Germany). The thermal gravimetric analyses (TGA) were carried out on the TGA Q500 thermogravimetric analyzer used in air with a heating rate of 10 oC min-1. The liquid state UV-vis spectra were recorded on a SHIMADZU UV-2450 UV-visible spectrophotometer within 200– 800 nm by using the same solvent as the blank. N2, CO2, CH4, C2H6 and C3H8 gas adsorption measurements were carried out on Micromeritics ASAP 2420 at 77 K and Micromeritics 3-Flex instruments at 273 and 298 K, respectively.

Synthesis of compound 1 5



A mixture of CuI (0.018 g, 0.09 mmol), H2L (0.009 g, 0.04 mmol), N, N-dimethylformamide (DMF) (1 mL), ethanol (0.5 mL), 1, 4-diazabicyclo [2.2.2]-octane (DABCO) (0.1 mL, 2 g DABCO in 10 mL DMF), HNO3 (0.3 mL, 2.2 mL HNO3 in 10 mL DMF) was sealed in a 20 mL vial and kept for 5 hours at room temperature until it became a transparent dark brown solution. The sealed vial was kept in an oven at 65 oC for 12 hours, and then cooled down to room temperature. The blue block crystals were collected, washed with DMF, and air dried (yield 76%, based on CuI). Elemental analysis (%) calc. for C55H63Cu8I2N19O31: C 29.35; H 2.8; N 11.83, found: C 30.25; H 2.5; N 12.36. The phase purity of compound 1 can be proved by comparing the experimental PXRD pattern of the as-synthesized samples with the simulated one from the single-crystal X-ray data (Fig. S1). Gas adsorption measurements

Before gas adsorption testing, the as-synthesized samples of compound 1 were exchanged in renewed ethanol for 3 days (6 times per day) in order to totally remove the DMF molecules, which can be confirmed by TG analysis (Fig. S2). The samples were activated by drying in vacuum oven at 90 oC for 20 minutes. Before the measurement, the activated samples were dehydrated again via the ‘outgas’ function of the adsorption analyzer for 10 hours at 80 oC.

X-ray crystallography Single-crystal X-ray diffraction measurement were carried out on a Bruker Apex II CCD diffractometer with graphite-monochromated Mo-Kα (λ = 0.71073 Å) radiation

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at room temperature. The structure of compound 1 was solved by direct methods and refined on F2 by full-matrix least-squares with the SHELXTL-NT version 5.1.59 All the metal atoms were located first, and then the oxygen, carbon and nitrogen atoms of the compound were subsequently found in difference Fourier maps. All non-hydrogen atoms were refined with anisotropic displacement parameters. The hydrogen atoms of the ligand were located geometrically. The final formula of the compound was designated from crystallographic data combined with experimental data (elemental analyses) and thermogravimetric analysis data (TG analyses). The detailed crystallographic data and selected bond lengths and angles for the compound have been listed in Tables S1, S2, respectively. Related topology information of compound 1 was calculated by TOPOS software.60

RESULTS AND DISCUSSION

Structure description

Single-crystal X-ray crystallographic analysis reveals that compound 1 crystallizes in the orthorhombic crystal system with the space group of Imma. There exists vibration of the ligands in the structure. As presented in Fig. 1a and 1d, compound 1 is composed of three types of SBUs: an organic SBU composed of three-connected ligands that have triazole and carboxyl groups; an inorganic SBU consisted of classical paddlewheels and a inorganic SBU formed by [Cu2I]n chain.61-62 In the infinite zigzag SBU, each Cu(I) atom is four-coordinated by two µ4-I atoms and two N atoms from two organic ligands and iodine atom adopts four-coordination mode to 7



link four copper(I) atoms. As displayed in Fig. 1b and 1c, along the [100] direction, there exists a relatively large channel (13.3 Å × 4.7 Å) and a small one (6.7 Å × 4.0 Å) excluding the van der Waals radius. From the view of topology, the [Cu2I]n chain can be regarded as a 4-connected zigzag ladder,61 the organic linker is considered as a 3-connected node with a triangular geometry and the paddlewheel can be viewed as a 4-connected node with a square-planar geometry. Accordingly, the whole structure can be considered as a new (3, 4, 4)-connected topology with a Schläfli symbol of (42·63·8)4(62·82·102)(62·82·92)(62·8)4. The topological characteristics presented by different tiles are displayed in Fig. 1e and Fig. S6. The entire topology is composed of five types of tiles of [8·92], [62·102], [62·8·102], [42·62·92] and [42·62·82·92]. The total solvent-accessible volume of 4968.1 Å3 per unit cell has been calculated by PLATON,63 which takes up about 58.7% of the cell volume. The result indicates that compound 1 shows large porosity and potential application for gas storage.

Thermal gravimetric analyses (TGA)

TGA measurement was investigated to explore the thermal stability of compound 1, which shows that compound 1 can be stable up to about 230 oC (Fig. S2). The approximately 30% weight loss was witnessed prior to 200 oC, which can be ascribed to the removal of solvent molecules. The weight loss of about 47% between 230 and 500 oC can be attributed to the removal of organic ligands and the collapse of the structure. The rest of weight loss (22%) at 530 oC is ascribed to the remaining of CuO.

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Figure 1 Single-crystal structure for compound 1: (a) topology simplification of Cu paddlewheel SBUs, [Cu2I]n chain and the ligand; (b) ball and stick model of 3D framework of compound 1 viewed along the [100] direction; (c) space-filling view of the structure of compound 1 along the [100] direction; (d) polyhedron view of the framework; (e) topological features of the compound displayed by tiles. For clarity, disordered atoms were simplified, and H atoms on ligands are omitted. Property characterization Gas adsorption and separation behaviors 9



N2 adsorption measurement at 77 K has been carried out to verify the porosity of compound 1. As shown in Fig. S4, the N2 uptake of activated compound 1 displays a typical type-I sorption isotherm, which is the feature of microporous materials, with an uptake amount of 230 cm3 g−1 under 1 bar. The BET and Langmuir surface area were calculated to be 692 and 932 m2 g-1, respectively. The BET surface area of compound 1 was higher than many reported Cu4I4 based MOFs, such as COZ-1 (514 m2 g-1) and JLU-Liu23 (584 m2 g-1).64-65 The experimental pore volume was 0.36 cm3 g-1, which was close to the theoretical one (0.40 cm3 g-1). It indicated that the structure of compound 1 can be kept intact after the guest molecules removed, which ensures its good adsorption performance.

Considering the adsorption ability of compound 1, some other small gases adsorption properties have been also investigated. Firstly, the CO2 adsorption measurement was carried out and the adsorption isotherms were presented in Fig. 2a. The CO2 uptake of compound 1 is 92 and 59 cm3 g-1 at 273 and 298 K under 1 bar, respectively. The isosteric CO2 adsorption enthalpy (Qst) on compound 1 was also calculated by the virial model in order to explore the interaction between the framework and CO2 (Fig. S9). The Qst value of compound 1 was 32.4 kJ mol-1 near zero coverage. The amount of CO2 uptake (273 K) and Qst value of compound 1 are both higher than most of the CuxIy based MOFs, such as JLU-Liu23 (39 cm3 g-1, 19 kJ mol-1) and (Cu2I2)[Cu3PDC3(H2O)2]·2MeCN·2DMF (77 cm3 g-1, 27 kJ mol-1).65, 50 This result illustrates the strong vander Waals interactions between the framework and CO2 molecules. 10


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Also, compound 1 should have the ability for adsorption of other small hydrocarbons (such as CH4, C2H6 and C3H8, etc.), which are the main constituents of natural gas. The adsorption performance of compound 1 for CH4, C2H6 and C3H8 was investigated at 273 and 298 K under 1 bar. The maximum uptake for CH4 are 24 and 12 cm3 g-1, C2H6 are 70 and 55 cm3 g-1 and C3H8 are 61 and 53 cm3 g-1, respectively (Fig. 2b-2d). As calculated from the sorption isotherms at 273 and 298 K, the Qst values near zero coverage are 22.6, 28.5 and 33.5 kJ mol-1 for CH4, C2H6 and C3H8 adsorptions, respectively (Fig. S10-S12).

Figure 2 (a) CO2; (b) CH4; (c) C2H6; (d) C3H8 gas sorption isotherms of compound 1 at 273 K and 298 K under 1 bar.

To estimate the practical industrial separation ability of compound 1, the gas selectivity for CO2 (5% and 50%), C2H6 (50%) and C3H8 (50%) over CH4 was calculated by using IAST as a common approach to analyze binary mixture adsorption 11



according to the experimental single-component isotherms. By adopting the dual-site Langmuir-Freundlich equation data to match the experimental data (Fig. 3a and 3c),66-68 we make the models match the isotherms at 298 K successfully (R2>0.999).69-71 Afterwards, the fitting parameters were used for the calculation of multi-component adsorption via IAST (Table S3). According to the experimental data, the selectivity of compound 1 for CO2 over CH4 was 8.2 and 7.4 at 298 K under 1 bar as revealed in Fig. 3b, which was higher than the values of many reported microporous materials, especially most of the reported MOFs based on CuxIy SBUs, such as JLU-Liu31 (2.6, 2.7) and (Cu2I2)[Cu3PDC3(H2O)2]·2MeCN·2DMF (4) under the identical measurement conditions.3,

50

The practical separation application of

emblematic small hydrocarbons for compound 1 has been explored by IAST as well. The identical fitting method was used to obtain the fitting parameters (Table S3). As presented in Fig. 3d, the selectivity of the equimolar mixture of C2H6 over CH4 and C3H8 over CH4 for is 15 and 40 at 298 K under 1 bar. The high selective separation is ascribed to the difference of interaction strength between the framework and the small gases which has been shown by Qst. The Qst of compound 1 for CO2, CH4, C2H6, C3H8 is 32.4, 22.6, 28.5, 33.5 kJ mol-1, respectively, which indicates that compound 1 prefers CO2 to CH4, C3H8 to CH4, C2H6 to CH4 separation.

Iodine sorption and release experiments The I2 sorption and release performance in organic solvents of compound 1 has been investigated. Before the iodine adsorption testing, the microcrystalline samples were solvent exchanged with renewed ethanol for 3 days in order to ensure complete 12


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removal of DMF molecules. Afterwards, 100 mg activated samples were immersed in 3 mL cyclohexane solution (0.01 M) of I2 sealed in a hermetic vial and placed under room temperature. As shown in Fig. 4a, the iodine adsorption procedure can be detected with the colour fading from deep purple to light pink after 48 hours in the cyclohexane solution of I2, while the iodine release procedure can be witnessed with the colour changing to dark brown after 12 hours of soaking 20 mg iodine-adsorbed samples in ethanol as presented in Fig. 4b. In the I2 adsorption process, the total uptake of I2 is about 1 each formula unit.

Figure 3 CO2, CH4, C2H6 and C3H8 adsorption isotherms at 298 K along with the dual-site Langmuir Freundlich (DSLF) fits (a and c); gas mixture adsorption selectivity is predicted by IAST at 298 K and 100 kPa for compound 1 (b and d).

The I2 release dynamic process has been monitored by the liquid state UV-vis spectra. As Fig. 5 illustrated, the absorption bands of UV-vis spectra presented λmax at 204, 13



288 and 360 nm which can be attributed to I2 and polyiodide I3- that from the reaction of I2 with decomposed iodide.72-74 The I2 release rate of compound 1 in ethanol was shown in the insert in Fig. 5, which was plotted based on the intensity versus time at 204 nm. The release of iodine rises abruptly and mildly afterwards, with a release rate of about 5.2 × 10-6 mol L-1 min-1 according to the standard curve (Fig. S13 and S14), which was faster than JLU-Liu32 based on Cu4I4 clusters and [Cu4I3(DABCO)2]I3 based on [Cu8I6]2+ clusters.3, 72

Figure 4 (a) Photographs of the time-dependent I2 adsorption process of 100 mg compound 1 in 3 mL cyclohexane. (b) Photographs of the time-dependent I2 release process of 20 mg compound 1 in 3 mL ethanol.

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Figure 5 UV-vis spectra of I2 release in ethanol for compound 1 (outside); dynamic intensity (monitored at 208 nm) vs. time plots (inside).

CONCLUSION

In summary, by using the helpful SBU synthesis strategy, a novel microporous heterovalent Cu-MOF based on multiple SBUs with a new topology has been successfully solvothermally synthesized. Compound 1 displays moderate surface area and better adsorption ability for CO2 than most of the reported MOFs based on CuxIy SBUs. Meanwhile, it exhibits a good selectivity for CO2 over CH4. In addition, compound 1 shows well performance for iodine sorption and release in organic solvents. ASSOCIATED CONTENT

Supporting Information

Structure information (CCDC 1843778), PXRD, TGA, XPS spectra of compound 1. This information is available free of charge via the Internet at http://pubs.acs.org/.

AUTHOR INFORMATION

Corresponding Author *(L. Z.) E-mail: [email protected]. *(Y. L.) Fax: +86-431-85168624. E-mail: [email protected]. Notes 15



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The authors declare no competing financial interests. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (No. 21771078, 21671074, and 21621001), the 111 Project (B17020), the National Key Research and Development Program of China (2016YFB0701100). REFERENCES

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For Table of Contents Use Only A Microporous Heterovalent Copper-Organic Framework Based on [Cu2I]n and Cu2(CO2)4 SBUs: High Performance for CO2 Adsorption and Separation, Iodine Sorption and Release

Jiaqi Yuan, Jiantang Li, Liang Kan, Lifei Zou, Jun Zhao, Dong-Sheng Li, Guanghua Li, Lirong Zhang* and Yunling Liu*

A microporous Cu-MOF based on mixed [Cu2I]n and Cu2(CO2)4 SBUs has been constructed by using the SBU synthesis strategy. It exhibits high performance for CO2 adsorption and selective separation, and good I2 sorption and release properties.

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A Microporous Heterovalent Copper-Organic Framework Based on

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