A Porous Zn(II)-Metal–Organic Framework Constructed from

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A Porous Zn(II)-Metal-Organic Framework Constructed from Fluorinated Ligands for Gas Adsorption Cheng-Xia Chen, Zhang-Wen Wei, Qian-Feng Qiu, Yan-Zhong Fan, ChenChen Cao, Hai-Ping Wang, Ji-Jun Jiang, Dieter Fenske, and Cheng-Yong Su Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00086 • Publication Date (Web): 15 Mar 2017 Downloaded from http://pubs.acs.org on March 20, 2017

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Crystal Growth & Design

A Porous Zn(II)-Metal-Organic Framework Constructed from Fluorinated Ligands for Gas Adsorption Cheng-Xia Chen, ⊥ Zhang-Wen Wei, ⊥ Qian-Feng Qiu, Yan-Zhong Fan, Chen-Chen, Cao, Hai-Ping Wang, * Ji-Jun Jiang, * Dieter Fenske and Cheng-Yong Su MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional materials, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China. Supporting Information Placeholder ABSTRACT: A 3D functional metal-organic framework (LIFM38) has been successfully synthesized with fluorinated bicarboxylate ligand. LIFM-38 exhibits good stability and surface area of 803 m2 g-1. Owing to the synergistic effect of different functional groups, co-crystallized amine active sites, and suitable pore space, LIFM-38 shows good selective CO2 and C2+ hydrocarbons adsorption over CH4 and N2; In addition, LIFM-38 exhibits good selective C3 hydrocarbons adsorption over C2 hydrocarbons.

Recently, greenhouse effect results from the discharge of carbon dioxide in the atmosphere has become a worldwide issue needing to be addressed with urgency.1-4 Up to now, several methods have been developed to settle these problems.5-10 Using clean energy instead of conventional fossil energy and capturing carbon dioxide from emission sources are good strategies.11-12 As a main component of natural gas, methane is considered to be a predominant cleaner energy source based on its lower carbon emission. However, a small quantity of carbon dioxide and hydrocarbons as impurities will seriously hinder its performance. Hence the purification of methane has become an important issue.13-15 On the other hand, capturing the carbon dioxide from burning nature gas can eventually suppress carbon emission. A variety of adsorbents, such as active carbons, molecular sieves, etc, have been developed to purify natural gas and capture carbon dioxide.7, 8 However, these materials have shown their limit in tuning structures and properties for applications. Hence the exploration of new porous materials has become urgent in energy and environment fields. Over the last two decades, porous metal-organic frameworks (MOFs) constructed from inorganic metal ions and organic ligands have been proved to be promising materials in gas storage & separation5-10, heterogeneous catalysis16-20 and drug delivery21-23, owing to their high tunable functionalities and permanent porosities.24-29 So far, a lot of excellent adsorbents based on MOFs for carbon dioxide and hydrocarbon capture have been developed by functionalizing organic ligands30-31, introducing open metal sites32-33, tuning the surface area and pore volume34, and utilizing catenation35. In this regard, Omary and co-workers have synthesized the fluorinated MOFs (FMOF-1) using perfluorinated polycarboxylated ligands, instead of our previous strategy to construct FMOFs by introducing fluoride bridging atoms.36 FMOF-1 with exposed fluorine atoms in channels expresses high H2 and hydrocarbon adsorption.37-39 By introducing partially fluorinated ligands, Bu et al can enhance the CO2-framework interaction and increase the carbon dioxide storage capacity.40 Recently, Eddaoudi and

colleagues have reported a series of fcu-MOFs with enhancement of carbon dioxide and hydrocarbon adsorption energetics and uptake by using the fluorinated ligands with highly localized charge density.41 In these reports, it is revealed that MOFs with fluoro-coated channels are expected to express enhanced affinity and selectivity for gas adsorption compared with nonfluorinated counterparts. Herein, a new fluorinated metal-organic framework LIFM-38 has been constructed for the capture and separation of carbon dioxide and hydrocarbons. It is noteworthy that LIFM-38 consists of abundant trifluoromethyl functional groups, uncoordinated carboxyl groups and co-crystallized dimethylamine cation active sites at the same time, which can boost the preferential synergistic interactions with carbon dioxide, C2+ hydrocarbons over CH4 and N2, and C3 hydrocarbons over C2 hydrocarbons. LIFM-38, formulated as Zn (L1)1.5(Me2NH22+)⋅guest, has been successfully synthesized by solvothermal reaction between Zn(NO3)2 · 6H2O and 3,3’-bis(trifluoromethyl)-4,4’biphenyldicarboxylic acid (H2L1) in N,N-dimethylformamide (DMF) and ethanol (see Supporting Information for details). Single crystal X-ray diffraction reveals that LIFM-38 crystallizes in orthorhombic space group Aba2. There are one crystallographically independent Zn (II), one and a half L1, and one dimethylamine cation in an asymmetric unit (Figure S1). There are two types of coordination modes of L1 ligands: one is a µ2-bridging mode, constructed from two carboxylate groups both connecting to one Zn (II); another is a µ3-bridging mode, where one carboxylate group connecting to one Zn (II) and another carboxylate group adopts µ2-bridging mode. Each Zn (II) has tetrahedral geometry and is coordinated by four O atoms from one ordinary carboxylate group of one µ2-bridging L1, one ordinary carboxylate group of one µ3-bridging L1, and two µ3-bridging carboxylate group of two L1, respectively (Figure 1a). If the µ3-bridging L1 ligands and Zn (II) cations are simplified as 3- and 4-connect nodes, respectively, the framework can be simplified as a 3,4-c 2-nodal net with stoichiometry (3-c)(4-c) and topological point symbol of {63;103}{63} (Figure 1c). The average Zn-O bond length is 1.969 Å varying from 1.941 Å to 2.006 Å, which corresponds to those reported in related Zn (II) MOFs.32,42 LIFM-38 is a anionic framework in which the dimethylamine cations accommodate in the rectangular channel (9.9× 9.6 Å2) along a-axis (Figure 1b). The trifluoromethyl functional groups point to the interior of the channels to bring hydrophobic character (Figure 1d). The solvent-accessible volume of ca. 34.6% of the crystal volume was found by the PLATON program.43 The voids are filled by the structurally disordered DMF, ethanol and water guest molecules.

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Crystal Growth & Design

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Figure 1 (a) The coordination environment of LIFM-38; (b) the 3D structure of LIFM-38; (c) the topology of LIFM-38; (d) the space filled mode of LIFM-38 (H atoms were omitted for clarity). The powder X-ray diffraction (PXRD) patterns reveal that the patterns of as-synthesized and activated samples are in good agreement with the simulated patterns (Figure S2). The thermogravimetric analysis (TGA) indicates that LIFM-38 is stable up to 220 °C (Figure S7). The first weight loss region from 30 to 150 °C in the TGA curve corresponds to the loss of DMF, ethanol and water molecules. The variable temperature PXRD (VT-PXRD) patterns reveal that LIFM-38 can maintain its high crystallinity up to 190 °C, and subsequently transformed to another structure at 200 °C (Figure S8). Because the poor single crystal X-ray diffraction data, the structure transformed from LIFM-38 at 200 °C was not obtained. Besides, LIFM-38 can retain its high crystallinity after exposing to air for one month (Figure S4). Furthermore, the chemical stability has been investigated by soaking the samples of LIFM-38 on general solvents, such as DMF, THF, CH3CN, CH3OH and EtOH. The as-synthesized samples were soaked in the desired solvent for one week at room temperature. As shown in Figure S3, all PXRD patterns of the samples agree very well with those of synthesized samples, proving that LIFM-38 is very stable. More importantly, the N2 sorption isotherm remained almost the same after the treatment with different organic solvents and air for 7 days (Figure S6). In order to further investigate the chemical stability, the synthesized samples of LIFM-38 were exposed to water vapour with RH at about 75.8%. PXRD indicates that LIFM-38 can retain its main original skeleton after one year (Figure S5). However, the extra peak appeared at 2θ = 9.5 indicates a slight collapse of the host framework. To our surprise, the slight collapse of framework can be recovered after soaking the above samples in anhydrous ethanol for 18 h. (Figure S5). The permanent porosity of LIFM-38 was confirmed by the reversible N2 sorption measurements at 77 K, which showed type I adsorption isotherm behavior with the saturated adsorption amount of 239 cm3 g-1 (Figure 2a). The apparent BrunauerEmmett-Teller (BET) surface area is 803 m2 g-1, and the pore size is about 12.1 Å (Figure S10-S12 & Table S2), which matches with the structure analysis well. The total pore volume is 0.37 cm3 g-1 at P/P0 = 0.97. The permanent porosity as well as good chemical stability of LIFM-38 encouraged us to explore the potential application in gas separation. Thus, the pure component sorption for hydrogen, carbon dioxide and hydrocarbons were carried out to test its gas uptake capacity. As shown in Figure 2b, the H2 uptake for LIFM-38

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reaches ca. 66 cm3 g-1 (2.9 mmol g-1) at 77 K and 1 atm. This storage capacity is comparable with many reported MOFs under the same conditions.44-45 By carefully analyzing the structure of LIFM-38, we speculate that there will be good selectivity for CO2 over CH4 and N2, owing to the significant quadrupole moment of CO2, which might induce a stronger interaction with the trifluoromethyl functional groups, uncoordinated carboxyl groups and dimethylamine cations.32 As the experiment reveals, LIFM-38 shows good selective gas adsorptions for CO2 over CH4 and N2 at 273 K and 1 atm (Figure 2c). The CO2 uptake is 25 cm3 g-1 (1.1 mmol g-1) while the CH4 (5.7 cm3 g-1) and N2 (1.7 cm3 g-1) uptake are very low. The isosteric heat for CO2 calculated by Clausius-Clapeyron equation is 43.2 kJ mol-1 at zero coverage (Figure S17), which is higher than many known MOFs.46-47 The high isosteric heat is mainly because of the strong interactions of CO2 with the trifluoromethyl functional groups, uncoordinated carboxyl groups and dimethylamine cations.30-31 Furthermore, the binary CO2/CH4 and CO2/N2 adsorption selectivities were calculated by the idea adsorbed solution theory (IAST).48-49 In a range of pressures up to 1 atm at 273 K, the selectivities of CO2 with respect to CH4 and N2 are 3.6 and 17.0 (Figure 2d), which is comparable with some famous MOFs50-510. All the results indicate that LIFM-38 can be a good CO2 separation material.

Figure 2 (a) The N2 adsorption isotherm of LIFM-38 at 77 K; (b) H2 adsorption isotherms; (c) selective uptake of CO2 over CH4 and N2 at 273 K; (d) selectivities of CO2 over CH4 and N2 calculated from the IAST based method. Additionally, the potential application of LIFM-38 for separation of light hydrocarbons was also investigated by measuring the uptake of C3H8, C3H6, C2H6, C2H4 and CH4 at 273 and 298 K, respectively (Figure 3a & 3b). At 1 atm, the maximum uptake of C3H8, C3H6, C2H6, C2H4 and CH4 are 71 cm3 g-1 (3.2 mmol g-1), 75 cm3 g-1 (3.3 mmol g-1), 45 cm3 g-1 (2.0 mmol g-1), 35 cm3 g-1 (1.6 mmol g-1) and 5.7 cm3 g-1 (0.25 mmol g-1) at 273 K, and 55 cm3 g-1 (2.4 mmol g-1), 58 cm3 g-1 (2.6 mmol g-1), 24 cm3 g-1 (1.1 mmol g-1), 20 cm3 g-1 (0.9 mmol g-1) and 3.4 cm3 g-1 (0.15 mmol g-1) at 298 K, respectively. Obviously, LIFM-38 exhibits adsorption capacity in the trend with C2+ ＞ C1 and C3 ＞ C2. The preferential adsorption of C3 hydrocarbons with respect to C2 hydrocarbons is because of the higher molecular weight. For molecules with similar structure, their interactions with adsorbents are positive corelated to their molecular weight. Since the pores of LIFM38 are large enough to accommodate C2 and C3 molecules, the C3 molecules with higher molecular weight and stronger van der Waals force will be selectively adsorbed. The isosteric heats of

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Crystal Growth & Design

C3H8, C3H6, C2H6 and C2H4 are 28.3, 27.3, 28.5 and 28.1 kJ mol-1 at zero coverage, respectively (Figure S17). To evaluate the adsorption selectivities of C2+ hydrocarbons with respect to CH4 and C3+ hydrocarbons over C2+ hydrocarbons at 273 and 298 K, the IAST calculation was employed to predict the muti-component adsorption behaviors. In a range of pressures up to 1 atm, the selectivities of C2H4, C2H6, C3H6 and C3H8 with respect to CH4 are 8.5, 11.9, 84.0 and 90.9 at 273 K, and 6.5, 8.2, 34.4 and 35.8 at 298 K, respectively (Figure 3c & 3d), which is comparable with some reported MOFs under the similar conditions52-53. The results suggest that LIFM-38 may be a candidate material for the separation of C2+ hydrocarbons over CH4. In addition, LIFM-38 exhibits good selectivities of C3H8, C3H6 over C2H6 and C2H4 (Figure S19). The selectivities of C3H8 with respect to C2H4 and C2H6 are 6.7 and 5.1 at 298 K and 1 atm. Besides, the selectivity values for C3H6/C2H4 and C3H6/C2H6 are 6.4 and 4.9 at 298 K and 1 atm.

Figure 3 (a) selective uptake of C2+ hydrocarbons over CH4 at 273 K; (b) selective uptake of C2+ hydrocarbons over CH4 at 298 K; (c) selectivities of C2+ hydrocarbons versus CH4 calculated from the IAST based method at 273 K; (d) selectivities of C2+ hydrocarbons over CH4 calculated from the IAST based method at 298 K. In summary, a fluorinated 3D metal-organic framework has been successfully synthesized. LIFM-38 exhibits good thermal and chemical stability. Moreover, LIFM-38 shows good selectivities of CO2 and C2+ hydrocarbons over CH4 and N2, and C3 hydrocarbons over C2 hydrocarbons, mainly due to the introduction of trifluoromethyl functional groups, uncoordinated carboxyl groups and dimethylamine cations. All the interesting findings reveal that LIFM-38 may be an excellent candidate material for gas capture and separation.

ASSOCIATED CONTENT Supporting Information. Crystallographic details (CIF). This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author *E-mail:[email protected]. *E-mail:[email protected].

Notes

Author Contributions C.-X. C., J.-J. J. and C.-Y. S. planned and executed the synthesis and characterization. Z.-W W. performed the structure characterization. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. ⊥C.-X. C. and Z.-W W. contributed equally.

ACKNOWLEDGMENT This work was supported by the NSF of China (21121061, 91222201, 21173272) the STP Project of Guangzhou (15020016, 201607010378) and the NSF of Guangdong Province (S2013030013474).

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The authors declare no competing financial interest.

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A porous Zn(II)-Metal-Organic framework constructed from fluorinated ligands shows good selective CO2 over CH4 and N2; and good selective C3 hydrocarbons adsorption over C2 hydrocarbons.

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