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A (3,6)-Connected MOF with pyr Topology and Highly Selective CO2 Adsorption Qian Wang, Jingjing Jiang, Mingxing Zhang, and Junfeng Bai Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b01484 • Publication Date (Web): 16 Dec 2016 Downloaded from http://pubs.acs.org on December 21, 2016
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Crystal Growth & Design
A (3,6)-Connected MOF with pyr Topology and Highly Selective CO2 Adsorption Qian Wang, Jingjing Jiang, Mingxing Zhang and Junfeng Bai* State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
Supporting Information Placeholder ABSTRACT: Based upon a bifunctional organic ligand with two carboxyl groups and one N donor, 5-(quinolin-4yl)isophthalic acid (H2L), a new (3,6)-connected MOF with pyr topology, [Cu(L)·DMF]n (NJU-Bai32), has been synthesized and exhibits highly selective CO2 adsorption.
acid was designed and used to synthesize a new (3,6)connected MOF with pyr topology, NJU-Bai32, which is the second reported pyr topological MOF constructed from bifunctional organic ligand with two carboxyl groups and one 23, 24 N donor and exhibits highly selective CO2 adsorption.
Global warming induced by the excessive emission of CO2 1– has been one of great concerns facing our civilization today. 4 As a major CO2 release source, flue gas from power plants composed mainly by 73-77% of N2, 15-16% of CO2, 5-7% of H2O et al. at a total pressure of ~1 bar has prompted the rapid development of post-combustion CO2 capture with different 5–10 kinds of materials. Conventional technologies for postcombustion CO2 capture involving the chemisorption by amine-solution systems encounter high cost and corrosion in 11, 12 their regeneration process. Therefore, recently, these alternative processes in relation to physisorption by solid po8, 13 rous adsorbents have been intensively developed. Compared to traditional porous materials (zeolite, active carbon et al.), metal–organic frameworks (MOFs) with more fascinating structures and properties of large porosity, functionalizable pore surface, tunable pore sizes and shapes have been considered to be the most promising materials for CO2 cap8–10, 12, 13 ture. Our work is focused upon the construction of MOFs possessing interesting properties from both symmetric and un11, 12, 14–21 symmetric multidentate organic ligands. For example, very recently, two (3,6)-connected MOFs with rtl topology, NJU-Bai7 and NJU-Bai8, were reported which were constructed from 5-(pyridin-3-yl)isophthalic acid and 5(pyrimidin-5-yl)isophthalic acid, respectively. Targeting the (3,6)-connected framework, SYSU, they were designed by shifting the coordination site of ligand to finely tune pore size and polarizing the inner surface with uncoordinated nitrogen atom, respectively, and both of them exhibited 14 highly selective adsorption for CO2. Herein, to further expand our work, a new bifunctional organic ligand with two carboxyl groups and one N donor, 5-(quinolin-4yl)isophthalic acid (H2L), with the pyrimidin-5-yl group substituting the pyridin-3-yl or pyrimidin-5-yl group in 5(pyridin-3-yl)isophthalic acid or 5-(pyrimidin-5-yl)isophthalic
Figure 1. (a,b) Cu-paddlewheel units linked by isophthalic acid moieties form the 2D sql layers (marked A and B in b) which are pillared by quinolin-4-yl group to construct the 3D porous frameworks. (c) Pillaring way of quinolin-4-yl groups between layers of A and B. (d) The pyr topology of NJU-Bai32 which more clearly exhibits the transformation of layer of A to B. (e) 1D zigzag channel perpendicular to the 2D sql layers generated in NJU-Bai32 with two kinds of pore sizes. H atom is omitted for clarity. C, gray; O, red; Cu, cyan; N, blue.
Solvothermal reaction of CuCl2·2H2O with H2L in N,Ndimethylacetamide/methanol containing HNO3 afforded 33 green block crystals of NJU-Bai32. Single X-ray crystal struc-
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ture revealed that it crystallizes in orthorhombic space group Pbca with a = 14.3026(10) Å, b = 12.0421(8) Å and c = 21.6987(15) Å. Similar to NJU-Bai7, in the structure of NJUBai32, Cu-paddlewheel units are linked by isophthalic acid moieties of the organic ligand leading to the formation of two-dimensional square topological layers (sql). Then, the 2D sql nets of Cu-paddelwheel units joined by isophthalic acid moieties are further pillared by the quinolin-4-yl group giving the formation of 3D porous frameworks (Figure 1). However, different to the structure of NJU-Bai7, along the opposite direction of c axis, these sql layers in NJU-Bai32 adopt the packing model of the AB stacking model, in which layer of B is turned from layer of A by a translation of 1/2a opposite the direction of a axis after a rotation of 180° along c axis. Interestingly, one-dimensional zigzag channels are generated to be perpendicular to the two-dimensional sql layers in NJUBai32. The pore size (determined by the van der Waals diameter of the inserted pseudoatom) around quinolin-4-yl group which may be rotated around the Cu-N bond and the linker 14 backbone as gas molecules adsorbed diffuse into the pores, is 2.8 Å and that around the sql layer is 4.5 Å (Figure 1e). To better describe the structure, NJU-Bai32 may be simplified as a (3,6)-connected network with pyr topology, calculated by 22 TOPOS software, in which the Cu-paddlewheel units serve as 6-connected nodes and the organic ligands are simplified as 3-connected nodes. As far as we know, it is the second reported pyr topological MOF based upon bifunctional organic ligands with two carboxyl groups and one N donor after the previous publication of unstable MCF-30 by Chen’s 23–25 group. The total potential solvent accessible volume in desolvated NJU-Bai32 is around 35.5% as determined by the 26 PLATON/SOLV program, and the calculated density is -3 1.261 g cm . The PXRD profiles of NJU-Bai32 also imply that the whole porous framework still retains the crystallinity even if the guest molecules have been removed from the pores.
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Figure 2. Low pressure gases adsorption isotherms and the dual-site Langmuir-Freundlich (DSLF) fit lines of CO2 and N2 in NJU-Bai32 at 298 K. The green line and symbol show the IAST predicted selectivity of CO2 over N2.
(0.15:0.85) mixture was calculated from the experimental single-component isotherms using the IAST (ideal adsorbedsolution theory) method (Figure 2). At 298 K, NJU-Bai32 exhibits a good selectivity for CO2/N2, which is ~70.5 at 1 bar. In addition, the separation ratio of CO2 versus N2 for NJU-Bai32 was also calculated from the ratio of the initial slopes based on the isotherms (Figure S8). At 298 K, it is ~48.2, which is greatly higher than the value of SYSU at 298 K, and even approaches that of NJU-Bai7 at 298 K (Table S3). It is worthy of note that the high CO2 adsorption uptake and selectivity for CO2/N2 may be derived from the narrow pores in NJU-Bai32.
To confirm the permanent porosity of NJU-Bai32, the acetone solvent-exchanged sample was degassed under high vacuum by heating for 10h to obtain the evacuated framework. As shown in Figure S3, the CO2 adsorption isotherms were measured at 195 K for NJU-Bai32 and the reversible type-I isotherm implies that this metal-organic framework is a microporous material. The estimated apparent BET surface area and Langmuir surface area of NJU-Bai32 are 751 and 842 2 -1 m g , respectively. The permanent porosity of NJU-Bai32 prompted us to investigate its selective adsorption properties of CO2 versus N2. The CO2 and N2 low-pressure (0-1 bar) sorption isotherms were collected for NJU-Bai32 at 273 and 298 K, as shown in Figure S4,6. Very interestingly, at 298 K, its uptake amount of 3 −1 CO2 is high up to 24 cm g , corresponding to ~4.7 wt % at 0.15 bar, which is substantially higher than the values of many well-known MOFs, such as ZIF-78 (3.4 wt%, at 298 K 27, 28 and 0.15 bar), NH2-MIL-53(Al) (3.2 wt%, at 298 K and 0.15 29 30 bar), en-Cu-BTTri (2.4 wt%, at 298 K and 0.15 bar), ZIF-8 31 (0.6 wt%, at 298 K and 0.15 bar) and MOF-177 (0.6 wt%, at 32 298 K and 0.15 bar). However, it is worthy of note that in sharp contrast to CO2, NJU-Bai32 can only adsorb a limited 3 −1 amount of N2 (3.6 cm g , corresponding to ~0.45 wt %) at 298 K and 0.75 bar. To evaluate the selective adsorption of CO2 over N2 for NJU-Bai32, its selectivity for CO2 over N2 based on a CO2/N2
Figure 3. The CO2 adsorption enthalpies of SYSU (green), NJU-Bai32 (pink) and NJU-Bai7 (purple).
To further understand these observations, the isosteric heat (Qst) of CO2 adsorption for NJU-Bai33 was calculated to evaluate the extent of CO2–framework interactions by the virial method using experimental isotherm data at 273 and 298 K (Figure 3). At zero loading, the CO2 adsorption enthal-1 py for NJU-Bai32 is calculated to be 33.5 kJ mol , which reflects a strong interaction between the framework and adsorbed CO2 molecule. This Qst that is lower than the value of NJU-Bai7 is still higher than that of its prototype, SYSU, which is constructed by the same sql layers to NJU-Bai32 with its final pore size much larger than the kinetic diameters of
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adsorbate molecules. Consequently, we attribute the higher Qst value in NJU-Bai32 to the pore sizes close to the kinetic diameter of CO2 molecule in the framework which could facilitate the adsorbent−adsorbate interaction. In summary, based upon a quinoline-heterocyclic bifunctional organic ligand, 5-(quinolin-4-yl)isophthalic acid (H2L), a new (3,6)-connected MOF with pyr topology, NJU-Bai32, has been successfully synthesized. Notably, it is the second reported pyr topological MOF based upon bifunctional organic ligand with two carboxyl groups and one N donor. Very interestingly, with suitable and narrowed pore size, it also exhibits high selective CO2 adsorption uptake, which is better than those of many well-known MOFs reported previously.
ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd. Synthesis of ligands and MOFs, X-ray single crystal structure determination, low pressure gas sorption measurements, estimation of the isosteric heats of gas adsorption, prediction of the gases adsorption selectivity by IAST, PXRD patterns, TGA plots, IR spectra, Mass spectrum and H-NMR spectrum (PDF) Accession Codes CCDC 1507741 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.
AUTHOR INFORMATION Corresponding Author * E-mail:
[email protected].
Notes The authors declare no competing financial interest.
ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (21371091).
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A (3,6)-Connected MOF with pyr Topology and Highly Selective CO2 Adsorption Qian Wang, Jingjing Jiang, Mingxing Zhang and Junfeng Bai*
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China. E-mail:
[email protected]. Tel: +86-25-89683384.
(1.375 inches high × 3.5 inches wide, 600 dpi) A (3,6)-connected MOF with pyr topology and highly selective CO2 adsorption has been synthesized.
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