Two Microporous MetalâOrganic Frameworks with Suitable Pore Size

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Two Microporous Metal-Organic Frameworks with Suitable Pore Size Displaying the High CO2/CH4 Selectivity Jiang Li, Guoping Yang, Shi-Long Wei, Ruicheng Gao, Nan-nan Bai, and Yaoyu Wang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.5b00997 • Publication Date (Web): 05 Oct 2015 Downloaded from http://pubs.acs.org on October 5, 2015

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Crystal Growth & Design

Two Microporous Metal-Organic Frameworks with Suitable Pore Size Displaying the High CO2/CH4 Selectivity Jiang Li, Guo-Ping Yang*, Shi-Long Wei, Rui-Cheng Gao, Nan-Nan Bai, and Yao-Yu Wang* Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi’an 710069, P. R. China. E-mail: [email protected]; [email protected].

Two

microporous

metal-organic

frameworks,

[Zn2(HDDCBA)]·2DMF·2H2O

(1)

and

[Cd2(DDCBA)·DMA·H2O]·H2N(Me)2 (2) have been synthesized under solvothermal condition by using a less-exploited symmetrical pentacarboxylate ligand, 3,5-di(3′, 5′-dicarboxylphenyl)benozoic acid (H5L). Both compounds 1 and 2 reveal the (5,5)-connected nets based on the binuclear metal clusters and organic linkers. The desolvated structure of 1 (1a) contains two shapes of 1D channel with suitable pore size and polar system decorated by uncoordinated carboxylate groups. As a result, 1a possesses not only high CO2 loading but also excellent CO2/CH4 selectivity at 273 and 298 K. In addition, both compounds display solid-state luminescence stemming from the ligand-centered fluorescence of H5L. Introduction Effective capture and removal of CO2 from sources of anthropogenic emission is one of the grand challenges faced by modern science and engineering.1-4 Considerable effort has been made to develop effective methods and materials capable of capturing and sequestering CO2.5, 6 Recent works on numerous materials demonstrated their potential for adsorption-based separation, including zeolites7, 8, hybrid zeolite-polymer systems9, 10, porous organic materials11,12 and metal-organic frameworks (MOFs)13-16. Among these adsorbent materials, MOFs, as an exceptional class of CO2 capture and separation materials, have received considerable attention because of their advantages over other systems with structural diversity and tunability.17-22 The CO2 capture depends on selective adsorption base on electronic interactions with MOFs rather than on size as the kinetic diameters of CO2, CH4 and N2 are 3.30, 3.76, 3.64 Å, respectively.17-22 Therefore, it is common for improving CO2-MOFs interactions to focus on utilizing strongly polarizing functional group, open mental sites or amine grafting.23, 24 Among these strategies, polycarboxylate ligands are always dominant in MOFs for their flexible and diverse coordination modes.25, 26 Considering the rich diversity of carboxylate ligands, the incorporation of them and various metal nodes in the porous framework can afford the optimization of pore size and properties for specific applications.24, 27 In this regard, a typical example is employing a series of polycarboxylate ligands and paddle-wheel secondary building blocks (SBUs) to construct highly porous frameworks (such as PCN-61, PCN-66, PCN-68,28 NOTT-112,29 and NI-10030). Moreover, the recent advances in carboxylate-based MOFs validate excellent resistances toward water, organic solvent and acid chemical stimuli.31-33 With the aim to construct porous MOFs, a less-exploited 3,5-di(3′, 5′-dicarboxylphenyl)benozoic acid (H5L) ligand is employed to construct appropriate MOFs with suitable pore size and polar groups based on following advantages: (i) H5L possesses five carboxylate groups with multiple coordination sites, which is more conducive to form multi-pore systems; (ii) the isophthalate-containing ligands are inclined to form metal clusters, facilitating the interactions with CO2, as well as structural stability; (iii) similar to other 1, 4-benzenedicarboxylate or 1, 3, 5-benzenetricarboxylate, the symmetrical H5L can adjust proper configurations to meet the geometric requirement of the central metal atoms/clusters, which results in a variety of fascinating and multifunctional MOFs. Herein, using this functional ligand, two stable microporous MOFs, [Zn2(HDDCBA)]·2DMF·2H2O (1) and [Cd2(DDCBA)·DMA·H2O]·H2N(Me)2 (2) were synthesized under solvothermal condition. Gas adsorption

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measurements on 1 demonstrate its effective storage capacity for CO2 and H2. Ideal adsorbed solution theory (IAST) calculations predict the material shows high selectivity of CO2 over CH4 at ambient conditions.

Scheme 1 Experiment section Materials and methods All the reagents and solvents were purchased from commercial sources and used directly without further purification. Infrared spectra were obtained on Bruker EQUINOX-55 FT-IR spectrumeter in the 4000–400 cm-1 region. Thermogravimetric analyses (TGA) were carried out with NETZSCH STA 449C microanalyzer thermal analyzer under nitrogen at a heating rate of 5 oC min-1. Elemental analyses (C, H and N) were performed on Perkin-Elmer 2400C Elemental Analyzer. The luminescence properties were conducted in Hitachi F4500 fluorescence spectrophotometer. The powder X-ray diffraction (PXRD) patterns were collected on Bruker D8 ADVANCE X-ray powder diffractometer (Cu-Kα, 1.5418 Å) at room temperature. All the gas sorption isotherms were measured by using ASAP 2020 adsorption equipment. Single-crystal X-ray diffraction analysis. The single-crystal diffraction data of compounds 1 and 2 were conducted on a Bruker SMART APEX II CCD detector at 296(2) K using Mo-Kα radiation (λ = 0.71073 Å). The structures were solved using the direct methods and refined by full-matrix least-squares method based on F2 by SHELX-97.34 Non-hydrogen atoms were refined with anisotropic displacement parameters. The detailed crystal data as well structure refinements parameters of 1 and 2 are summarized in Table S1, and selected bond lengths and angles are given in Table S2. 1 contains heavily disordered solvent molecules, which cannot be identified from the difference Fourier map due to the weak diffraction intensity of crystal. The empirical formulas were determined by themogravimetric analysis and element analysis results. Crystallographic data for 1 and 2 have been deposited in the Cambridge Crystallographic Data Center with the reference numbers: 1404667 and 1404668, respectively. Synthesis of [Zn2(HDDCBA)]·2DMF·2H2O (1). A mixture of Zn(NO3)2·4H2O (0.0161 g, 0.1 mmol), H5DDCBA (0.0225 g, 0.05 mmol) and DMF-H2O (8.0 mL v/v: 2/1) were sealed in a 25 mL Teflon-lined autoclave which was then heated progressively at 105 °C for 72 h. After a gradual cooling procedure to room temperature, colorless rod-like crystals were obtained in ca.68.0% yield based on Zn. Anal. calcd for C29H28N2Zn2O14: C, 45.86; H, 3.71; N, 3.68. Found: C, 45.56; H, 3.81; N, 3.72%. Synthesis of [Cd2(DDCBA)·DMA·H2O]·H2N(Me)2 (2). A mixture of Cd(NO3)2·6H2O (0.0344 g, 0.1 mmol), H5DDCBA (0.0225 g, 0.05 mmol) and DMA-CH3OH (6 mL v/v: 2/1) were sealed in a 25 mL Teflon-lined autoclave which was then heated progressively at 105 °C for 72 h. After a gradual cooling procedure to room temperature, colorless block crystals were obtained in ca.63.0% yield based on Cd. Anal. calcd for C29H26N2Cd2O12: C, 42.51; H, 3.19; N, 3.41. Found: C, 42.49; H, 3.01; N, 3.42%.

Result and Discussion Figure 1 Structure Description Compound 1 crystallizes in the hexagonal space group P65. Meanwhile, the asymmetric unit of 1 contains two Zn2+ ions, one partly-deprotonated HDDCBA4- ligand (HL4-) (Fig. S1). Both Zn1 and Zn2 ions are four-coordinated with O atoms from carboxyl group of one HL4- to form a distinct [Zn2(COO)5] cluster as SBU (Fig. S3a). Moreover, a large amount of MOFs based on various kinds of [Zn2(COO)4] SBUs have been reported35-37, and a few MOFs constructed from [Zn2(COO)3] SBUs have also been obtained39-42, while the [Zn2(COO)5] SBUs are only found in MOAAF-2—MOAAF-6 and [H2N(Me)2]2[Zn4(L)2·(H2O)1.5]·5DMF·H2O


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(H5L = 2, 4-di(3′5′-dicarboxylphenyl)benozoic acid) according to the latest Cambridge Structural Database.43 The [Zn2(COO)5] SBU in the 1 is few obtained among the reported MOFs. All HL4- ligands in 1 joint to eight Zinc atoms and exhibit two distinct kinds of coordination modes, (κ1-κ1)-µ2-COO- and (κ1-κ0)-µ1-COO-. As shown in the Fig. 1b, the coexistence of left-handed (blue) and right-handed (red) helical chains stand along the c-axis, however, the helical chains are built on the same helical shaft. There are two types of 1D pore channel with different shapes along a-axis, labeled with A and B in Fig. 1d, with the effective aperture size of 4.7 × 10.5 Å2 and 4.7 × 4.7 Å2, respectively. The void volume calculated by PLATON program is 63.4% of total crystal volume. This arrangement leads to an extraordinary 3D porous framework. Topologically, all the [Zn2(COO)5] and HL4- can be viewed as five-connected nodes, therefore, the network of 1 belongs to a (5,5)-connected binodal topology with the Schlafli symbol as (46•64) (Fig. 1c).

Figure 2 Compound 2 crystallizes in the orthorhombic space group Pccn. As shown in the Fig. S2, the asymmetric unit consists of two independent Cd(II) ions, one fully-deprotonated DDCBA5- ligand, one free H2N(Me)2 cation, one coordinated H2O and one DMA molecules. Cd1 is seven connected by O atoms from four L5- ligand and one DMA molecules. Similar to Cd1, Cd2 is six connected by O atoms from four L5- ligand and one water molecule. Thus, Cd1 and Cd2 are bridged by two µ2-, one monodentate and one chelating carboxylate groups to give [Cd2(COO)5] SBU. All L5- ligand in 2 joint to eight Cd atoms and exhibit three coordination modes: (κ1-κ1)-µ2-COO-, (κ1-κ2)-µ2-COO- and (κ1-κ1)-µ1-COO-. The interlinkages of SBUs and L5- ligands generate an intricate 3D framework, which contains porous systems with 37.4% solvent accessible void after excluding H2N(Me)2 cations. Topologically, both [Cd2(COO)5] SBU and L5- ligand can be simplified as five-connected nodes, thus, 2 is a binodal (5,5)-connected net with the Schlafli symbol as (47•63) (Fig. 2a). The X-ray powder diffraction and thermal analysis To confirm the purity of the bulk sample in the solid state, the experimental PXRD patterns of 1 and 2 match with the simulated ones from the respective single crystal structures (Fig .S4). The thermogravimetric analysis (TGA) on 1 and 2 were performed in a N2 atmosphere, heating from 30 to 700 oC (Fig. S5). The TGA curve of 1 indicates a weight loss of 24.0% in the range of 30-220 oC, which consists of the release of two DMF molecules and two lattice H2O molecule per formula unit (calc. 23.6%). For 2, it lost surface water from 30 to 100 oC (calc. 5.0%), and a weight loss of 14.4% between 100-210 oC, corresponding to one coordinated DMA molecule, one H2O molecule and one H2N(Me)2 cation (calc. 14.2%). The desolvated samples (1a) were evacuated at 120 oC for 5 h and then followed by heating at 180 oC for 2 h under high vacuum. The PXRD of 1a displays shifting and weakening of some peaks, demonstrating the possible framework change due to the numerous solvent releases.

Figure 3 Gas sorption To confirm the permanent microporosity of the frameworks, gas-sorption measurements of 1a (N2, H2, CO2 and CH4) and 2 (N2) were performed. However, the uptakes of 2 at 77k and 1 bar only reach a trace of 5.24 cm3 g-1, and the results can be explained as that counterions (CH3)2NH2+ occupy the channels, decreasing the void of the channels (Fig. S6). As shown in the Fig. 3a, the reversible N2 sorption isotherm of 1a at 77 K reveals a type-I isotherm with a Brunauer-Emmett-Teller (BET) surface area up to 175 m2 g-1 (Langmuir surface area 231 m2 g-1), and a total micropore volume evaluated by Dubinin-Astakhov (DA) method of 0.0806 cm-3 g. The experiment pore size distribution (PSD) curve based on the NLDFT model demonstrates there exist two kinds of pores in the material with the average pore size of 6.5 and 10.7 Å, corresponding to the two shapes of channels. (Fig. 3 insert) The H2 sorption experiments at 77 K exhibits the uptakes of 38.84 cm3 g-1 (0.33 wt%) at 760 Torr, which is lower



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than the best Zeolite ZSM-5 (0.7 wt %) (Fig. 3b). Notably, the H2 adsorption isotherm is steep at low pressure

Figure 4 regions, displaying the strong interactions between frameworks and H2 molecules.44, 45 To evaluate the potential application in CO2/CH4 and CO2/N2 separation, the gas sorption properties on desolvated 1a at different temperatures (CO2 and CH4 at 195, 273 and 298 K; N2 at 298 K) were also investigated. As shown in the Fig. 4a, the CO2 uptake reaches 70.63 cm3 g-1 (13.87 wt%) at 1 bar and displays a type-I isotherm at 195 K. However, the CH4 uptakes of 29.48 cm3 g-1 (2.1 wt%) is much lower than the value of CO2 uptake at 195 K. Thus, such adsorption selectivity is more evident at high temperatures. The CO2 uptake are 26.13 cm3 g-1 (5.1 wt%) at 273 K and 14.94 cm3 g-1 (2.93 wt%) at 298 K and 1 bar (Fig. 4b). However, the CO2 uptake of 1a at 298 K is inferior to some Zinc frameworks with large pore size (9.0-32.0 Å), such as UMCM-1 (3.8 wt%),46 MOF-5, MOF-177 (3.5 wt%),47 and SNU-70 (3.5 wt%).48 Meanwhile, the CH4 uptakes are 8.9 cm3 g-1 (0.6 wt%) at 273 K and 4.37 (0.3 wt%) at 298 K and 1 bar. In addition, that N2 and H2 sorption isotherms were measured at 298 K, which exhibit only a trace of uptake (3.5 and 1.07 cm3 g-1, respectively). Overall, the examination of both CO2 and CH4 sorption at different temperature reveals that there is indeed existence of selectivity for respective sorbate

Figure 5 molecules. The selectivity for CO2/CH4 (at 273 and 298 K) in 1a were estimated using the ideal adsorbed solution theory (ISAT)49-52 (Fig. S7). To simulate typical compositions of biogas, the gas phase mole fraction for CO2/CH4 are set as 50/50 at 273 and 298 K. The IAST can be used to predict multicomponent adsorption behaviors and the result present that selectivity of CO2 over CH4 rapidly ascend with increasing loading for both mixture compositions in 1a. For different temperatures of the calculating the CO2 and CH4 selectivities, it is observed that the selectivity at 273 K are much higher than that at 298 K. At 1 bar, the calculated CO2/CH4 selectivity is 8.9 at 273 K and 8.1 at 298 K from equimolar gas-phase mixture (Fig. 5a and b), which is superior to those values at 273 K in (In2X)(Me2NH2)2(DMF)9(H2O)5 (6.40)53, ZIF-95 (4.3), ZIF-100 (5.9)54 and HKUST-1 (7.1).55 Remarkably, 1a shows high CO2/CH4 selectivity at 273 K and 1 bar (S = 8.9), which indicates that this material has high loading and affinity towards CO2. Overall, this study provided theoretical prediction in CO2 capture and the fact that 1a has high selectivity of CO2 implies that this material may be a promising adsorbent in the process of industrial application such as biogas treatment and natural gas clean up. The highly selectivity for CO2 adsorption over CH4 and N2 in 1a is mainly attributed to the differences in the electrostatic interactions between the porous surface and adsorbates. Moreover, recent computational and

Figure 6 experimental studies have demonstrated that charged porous framework materials exhibit much binding interactions with CO2 molecules.56 Besides, the narrow pore size of 1a and the small kinetic diameter of CO2 (3.30 Å) compared to CH4 (3.80 Å) N2 (3.64 Å) enable CO2 molecules to diffuse easily into the pores. To further explore the affinity of 1a for CO2, the CO2 adsorption enthalpies (Qst) were calculated according to the Virial equation from sorption isotherms at 273, 283 and 298 K (Fig. S8). The shape of Qst curves reveal that 1a has a far higher affinity towards CO2 at mid-high loading. At initial coverage, Qst start at 29.9 kJ mol-1, however, as the CO2 uptakes rise up to 0.47 mmol g-1, the Qst reaches 29.65 kJ mol-1 (Fig. 6). This value is superior to those MOFs decorated by typical active site such as Lewis basic sites and Open Mental Sites, such as Cu(Bcppm) (29 kJ mol-1) 57, 58

, PCN-16 (22.5 kJ mol-1) and Zn-MOF-74 (30 kJ mol-1)55, but lower than CuBTTri-en (80 kJ mol-1)59 MIL-100

(60 kJ mol-1) and MIL-101 (45 kJ mol-1).60 The high enthalpies of CO2 enthalpies is mainly related to the existence of uncoordinated carboxylate group (located within the wall of the porous surface), which make the frameworks


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highly polar and then cause specific interactions with CO2 due to its large quadrupole moment. Luminescent properties

Figure 7 The luminescent properties of two compounds and free ligand were investigated in solid state at room temperature. As shown in the Fig. 7 and Fig. S9, compounds 1 and 2 display emission bands at 442 nm and 445 nm upon excitation at 350 nm and 354 nm, respectively. These bands can be attributed to the π—π* intra-ligand luminescent emission since the emission band of free ligand is observed at 395 nm upon excitation at 340 nm. As a result, the luminescent properties of both compounds are similar to each other since the resemblance coordinative environment of them. As for the resemblance emission nature of 1 and 2, obvious red-shift of ~50 nm occurs in the maximum emission peaks in the compounds, which can be presumably associated to chelation of ligand to the metal center, leading to π→n ligand-to-metal charge transfer (LMCT).61

Conclusions In summary, two microporous MOFs based on a symmetric pentacarboxylate ligand have been successfully assembled. Interestingly, both compounds 1 and 2 possess the (5,5)-connected topologies. More importantly, the desolvated framework (1a) displays permanent porosity with suitable pore size and the polar pore surface decorated by uncoordinated carboxylate group, which afford high CO2 loading and highly selective capture for CO2 over CH4 at 273 and 298 K. The unique structures and excellent gas selectivity for CO2 may draw attention to the fabrication of functional MOF materials.

Acknowledgements We are grateful for financial support from the NSF of China (Grants 21201139, 21371142, and 21531007) and the NSF of Shaanxi, China (Grant 2013JQ2016), and the Open Foundation of Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education (Grant 338080049).

Notes and references Electronic Supplementary Information (ESI) available: Additional figures, selected bond and length table, PXRD, TG, IR spectra and crystallographic data of 1 and 2. CCDC: 1404667-1404668 (1-2).

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Scheme 1 Schematic structure of the organic linker H5L.



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Fig. 1 a) 3D structure of 1 viewed along the c axis; b) the coexistence of left-handed (blue) and right-handed (red) helical chain along c axis; c) the (5,5)-connected topology of 1 (purple nodes and green linkages represent SBUs and ligands, respectively); d) The 3D microporous framework of 1, A and B represent the different shapes of channels. All the H atom and guest molecules are omitted for clarity.

Fig. 2 a) 3D structure of 2 viewed along the c axis; b) the (5,5)-connected topology of 2 (purple nodes and green linkages represent SBUs and ligands, respectively). All the H atom and guest molecules are omitted for clarity.


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Fig. 3 a) N2 and H2 b) adsorption and desorption isotherm at 77 K and pore size distribution (inset) of 1a.



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Fig. 4 a) The adsorption isotherm of 1a: CO2 and CH4 at 195 K. b) N2, H2, CO2 and CH4 adsorption isotherm of 1a at different temperatures.

Fig. 5 IAST adsorption selectivity of 1a for equimolar mixtures of CO2 and CH4 at 273 and 298 K.


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Fig. 6 The isosteric heat of CO2 adsorption for 1a estimated by the virial equation from the adsorption isotherms at 273 and 298 K.

Fig. 7 Luminescent emission spectra of the free ligand H5DDCBA (black), 1 (red) and 2 (blue) in the solid state at room temperature.



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Jiang Li, Guo-Ping Yang*, Shi-Long Wei, Rui-Cheng Gao, Nan-Nan Bai, and Yao-Yu Wang* Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi’an 710069, P. R. China. E-mail: [email protected]; [email protected]. Two microporous frameworks have been constructed from the uncommon SBUs showing the (5,5)connected topologies. The complex of 1a contains the suitable pore sizes and high polarity porous system and exhibits the high selectivity of CO2 over CH4. 74x48mm (300 x 300 DPI)


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Two Microporous MetalâOrganic Frameworks with Suitable Pore Size

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