Improvement of the CO2 Capture Capability of a Metal–Organic

Article pubs.acs.org/crystal

Improvement of the CO2 Capture Capability of a Metal−Organic Framework by Encapsulating Dye Molecules inside the Mesopore Space Published as part of a Crystal Growth and Design virtual special issue on Crystal Engineering of Nanoporous Materials for Gas Storage and Separation Min Zhao, Sha Ou, and Chuan-De Wu* State Key Laboratory of Silicon Materials, Center for Chemistry of High-Performance & Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou, 310027, P. R. China S Supporting Information *

ABSTRACT: Capturing CO2 to mitigate carbon emission is an outstanding challenge. The design and synthesis of new porous materials capable of selectively capturing CO2 are critical to sequestrate the rising atmospheric CO2. Herein we report a dye encapsulating approach to tune the CO2 capture capability of metal−organic frameworks (MOFs). A new mesoporous MOF material CZJ-10 and three dye-encapsulated composite MOF materials RB@CZJ-10, CR@CZJ-10, and melanin@CZJ-10 are investigated for their ability to capture CO2. We show that the interior pore space of CZJ-10 can be functionalized with different dyes, which allow exploration of the effect of increasing CO2 uptakes of the MOF. This work offers a promising approach for the development of new composite materials to sequestrate CO2 molecules. Additionally, CZJ-10 demonstrates high catalytic efficiency on CO2 chemical conversion to form cyclic carbonate.

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INTRODUCTION Emitting CO2 into our living environment has attracted widespread public concern associated with global warming and climate change.1,2 CO2 is also an undesirable impurity component of many industrial gases, such as natural gas, syngas, and biogas.3−5 These issues have been becoming the powerful drivers for development of efficient CO2 capture strategies. Currently, employing liquid amines as chemisorbents dominates this field, largely because of their potential to form carbamates through H−N···CO2 interactions. However, the regeneration process is highly energy-intensive and environmental hazardous.6−8 To effectively address this challenging issue, alternative pathways are highly desirable. Accordingly, numerous traditional porous materials, such as zeolites, mesoporous silica, polymeric resins, cellulose, and porous carbon materials, have been selected and decorated with different CO2 affinity groups onto their pore surfaces to improve the CO2 capture capability.9−14 However, those efficient CO2 sorbent materials at an economically viable cost for this application have yet to emerge. Compared with traditional porous materials, porous metal− organic frameworks (MOFs) offer super features of tunable chemical functionality and pore microenvironment, structural diversity, and high surface area.15,16 MOFs have been demonstrated as a class of great promise materials for gas capture, purification, storage, and separation.17−24 Within these fields, the interactions between gas molecules and sorption sites © 2017 American Chemical Society

on the pore walls of MOFs play a dominant role. Accordingly, an efficient strategy to realize highly efficient CO2 capture has been developed by introducing CO2 affinity binding sites onto the pore surfaces of MOFs.25−30 In the past few years, many MOFs, combining various CO2 binding sites, such as aromatic N-heterocycles, aromatic amino groups, alkylamines, open metal sites, on the pore walls, have been rationally designed and systematically synthesized to improve the physical adsorption and/or chemical absorption capability of CO2 molecules.31−37 Indeed, numerous benchmarks for CO2 capture in voluminous amounts have been reported.38−51 However, one of the critical issues has not been given much attention for those MOFs that feature large mesopore space, in which it is difficult to achieve high CO2 uptakes because of their large vacant pore space. To meet the above considerations, we report an approach by in situ encapsulating dye molecules inside the pore space of a mesoporous MOF [Cu6L4(H2O)6]·13DMF·39H2O (CZJ-10) to improve the utilization of large vacant pore space with dynamic binding sites for CO2 capture (H3L = 4,4′,4″-benzene1,3,5-triyl-tricinnamic acid; Scheme 1). The mesoporous MOF CZJ-10 is assembled from new organic linker L ligands and binuclear Cu2(CO2)4 paddle-wheel secondary building units (SBUs). The connection between the new expanded organic Received: February 7, 2017 Revised: March 30, 2017 Published: March 30, 2017 2688

DOI: 10.1021/acs.cgd.7b00188 Cryst. Growth Des. 2017, 17, 2688−2693

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washed with water several times, and dried at 50 °C. Yield: 97%. 1H NMR (400 MHz, DMSO): δ = 6.64 (d, 3H, J = 16.0 Hz), 7.69 (d, 3H, J = 16.0 Hz), 7.84 (d, 6H, J = 8.0 Hz), 7.97 (d, 6H, J = 8.0 Hz), 8.01 (s, 3H). 13C NMR (100 MHz, DMSO): δ = 119.3, 124.7, 127.7, 128.8, 133.7, 140.9, 141.4, 143.4, 167.6. IR (KBr pellet, v/cm−1): 1690 (s), 1625 (s), 1599 (m), 1559 (w), 1410 (m), 1211 (s), 1070 (w), 976 (m), 883 (w), 818 (s), 693 (m), 595 (w), 517 (m). Synthesis of CZJ-10. H3L (52 mg, 0.1 mmol), Cu(NO3)2·2.5H2O (70 mg, 0.3 mmol), and 1 M HCl (1 mL) in DMF (10 mL) were heated at 80 °C for 2 days. Blue crystals were collected by filtration, washed with DMF, EtOH, and Et2O, and dried at room temperature. Yield: 63%. Anal. Calcd for C171H265N13O82Cu6 (%): C, 48.95; H, 6.37; N 4.34. Found (%): C, 48.98; H, 6.15; N, 4.27. IR (KBr pellet, v/ cm−1): 1638 (s), 1601 (w), 1550 (w), 1504 (m), 1369 (s), 1231 (m), 1100 (m), 981 (s), 884 (w), 821 (s), 719 (s), 605 (w), 519 (m). Synthesis of RB@CZJ-10, CR@CZJ-10, melanin@CZJ-10, and TPM@CZJ-10. Similar processes were employed to synthesize RB@ CZJ-10, CR@CZJ-10, and melanin@CZJ-10 by adding a certain amount of corresponding dye of rhodamine B (RB), Congo Red (CR) and melanin, and triphenylmethane (TPM). IR for RB@CZJ-10 (KBr pellet, v/cm−1): 1637 (s), 1590 (m), 1560 (m), 1512 (w), 1398 (s), 1240 (w), 1182 (w), 983 (m), 827 (s), 727 (w), 612 (w), 523 (w). IR for CR@CZJ-10 (KBr pellet, v/cm−1): 1636 (s), 1601 (m), 1509 (s), 1393 (s), 1236 (w), 1182 (w), 1109(m), 979 (s), 876 (m), 823 (s), 727 (m), 606 (w), 516 (w). IR for melanin@CZJ-10 (KBr pellet, v/ cm−1): 1634 (s), 1593 (w), 1561 (w), 1512 (s), 1396 (s), 1301 (m), 1240(w), 1184 (w), 982 (m), 826 (s), 756 (w), 719 (s), 698 (w), 520 (w). IR for TPM@CZJ-10 (KBr pellet, v/cm−1): 1714 (s), 1653 (s), 1605 (w), 1418 (s), 1385 (m), 1348(s), 1210 (w), 1187(m), 1048(s), 982 (m), 888 (w), 826 (s), 679 (w), 512 (m). Single-Crystal X-ray Data Collection and Structure Determination. The determination of the unit cell and the data collection for the crystal of CZJ-10 were performed on an Oxford Xcalibur Gemini Ultra diffractometer with an Atlas detector. The data were collected using graphite−monochromatic enhanced ultra Cu radiation (λ = 1.54178 Å) at 293 K. The data sets were corrected by empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.53 The structure of CZJ-10 was solved by direct methods and refined by full-matrix least-squares methods with the SHELX-97 program package.54 Because the solvent molecules in CZJ-10 are highly disordered, SQUEEZE subroutine of the PLATON software suit was used to remove the scattering from the highly disordered guest molecules.55 The resulting new files were used to further refine the structures. The H atoms on C atoms were generated geometrically. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Center as supplementary publication no. CCDC-1531376. Copy of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (Fax: (+44) 1223-336-033; E-mail: [email protected]. ac.uk). Crystal data for CZJ-10: C132H96Cu6O30, M = 2543.33, cubic space group Pn3̅n, a = 33.3261(5) Å, V = 37012.9(10) Å3, Z = 4, μ = 0.582 mm−1, F(000) = 5208, ρ = 0.456 g cm−3, R1 = 0.0788, wR(F2) = 0.1444 (I > 2σ(I)), and S = 1.027. A Typical Procedure for Cycloaddition Reaction between CO2 and Styrene Oxide To Form Cyclic Carbonate Catalyzed by CZJ-10. Styrene oxide (2 mmol), CZJ-10 (0.001 mmol), and TBAB (0.2 mmol) were stirred at room temperature under an atmosphere of CO2 (1 atm). The identity of the product was determined by GC-MS using a flame-ionization detector (FID) with a capillary SE-54 column and compared with the authentic samples analyzed under the same conditions. The aliquots were regularly taken out for GC analysis to determine the conversion of styrene oxide, the yield of styrene carbonate, and turnover numbers (TONs). A Typical Procedure for Substrate Adsorption Experiments. An activated sample of CZJ-10 (50 mg) was immersed in styrene oxide (0.5 mL) at room temperature for 24 h and centrifugated. The solid was recovered and thoroughly washed with ethyl ether to remove surface adsorbed molecules, which was subsequently submersed in acetonitrile (2.5 mL) under stirring for 18 h. The supernatant liquid

Scheme 1. 4,4′,4″-Benzene-1,3,5-triyl-tricinnamic Acid (H3L)

linker L and Cu2(CO2)4 paddle-wheel SBUs results in an interpenetrated metastable framework with large mesopore cages of about 2.5 nm in diameter. CO2 sorption experiments demonstrate that the CO2 capture capability can be significantly improved when organic dyes are partially filling in the mesopore space of CZJ-10. This work showed that introducing different dyes with CO2 affinity groups inside the pore space of CZJ-10 can improve CO2 uptakes by direct hydrogen bonding interaction between sorbent and adsorbate moieties.

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EXPERIMENTAL SECTION

Materials and Methods. All of the chemicals were obtained from commercial sources and were used without further purification, except 1,3,5-tris(4-bromophenyl)benzene was synthesized according to the literature.52 Fourier transform infrared (FT-IR) spectra were collected from KBr pellets on a FTS-40 spectrophotometer. Thermogravimetric analysis (TGA) was carried out under N2 atmosphere on a NETZSCH STA 409 PC/PG instrument at a heating rate of 10 °C min−1. Elemental analysis was performed on a ThermoFinnigan Flash EA 1112 element analyzer. Powder X-ray diffraction (PXRD) data were recorded on a RIGAKU D/MAX 2550/PC for Cu−Kα radiation (λ = 1.5406 Å). A Micromeritics ASAP 2020 surface area analyzer was used to measure N2 and CO2 gas sorption isotherms. UV−vis spectra were recorded on a UNICO 2802 spectraphotometer. 1H and 13C NMR spectra were recorded on a 400 MHz spectrometer, and the chemical shifts were reported relative to internal standard TMS (0 ppm). Gas chromatography mass spectrometry (GC-MS) data were recorded on a SHIMADZU GCMS-QP2010. Synthesis of 4,4′,4″-Benzene-1,3,5-triyl-tricinnamic Acid (H3L). 1,3,5-Tris(4-bromophenyl)benzene (10.88 g, 20 mmol), methyl acrylate (18 mL, 200 mmol), K2CO3 (10.35 g, 75 mmol), tetrabutyl ammonium bromide (TBAB) (0.805 g, 4 mmol), Pd(OAc)2 (0.4488 g, 2 mmol), and DMF (100 mL) were mixed in a 250 mL roundbottomed flask. The mixture was heated at 130 °C under stirring for 24 h. After the reaction mixture was cooled down to room temperature, the mixture was poured into 200 mL of water and extracted with ethyl acetate three times. The combined organic phase was dried over anhydrous Na2SO4 and concentrated under a vacuum. The residue was subjected to chromatography on silica gel (petroleum ether/CH2Cl2 = 5:1). The solvent was removed under reduced pressure to give a white power solid of Me3L (yield: 60%). Subsequently, Me3L (5.58 g, 10 mmol) and KOH (3.36 g, 60 mmol) in THF (50 mL) and H2O (50 mL) were heated at 60 °C under stirring for 12 h. The mixture was cooled down to room temperature, which was evaporated under reduced pressure to remove THF. The pH value of the resulting mixture was adjusted to 1 by using concentrated HCl. White precipitate was collected by filtration, 2689

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was used for UV−vis spectroscopy analysis and compared with the authentic sample.

interpenetration does not significantly reduce the solvent accessible pore sizes. The diameter of the mesopore cages in CZJ-10 is about 2.5 nm in dimension with an effective pore window size of approximately 9.1 Å. PLATON calculations indicate that the total solvent accessible pore volume in CZJ-10 is of 28334.9 Å3 per unit cell volume 37012.9 Å3 (76.6%), which is occupied by DMF and water solvent molecules.58 The permanent porosity of CZJ10 has been examined by N2 adsorption experiments at 77 K (Figure S3). The as-synthesized CZJ-10 was guest-exchanged with dry acetone, followed by activation at room temperature under a high vacuum overnight to get the activated sample. PXRD analysis of the activated sample showed that the diffraction pattern is basically identical to that of the assynthesized one (Figure S5). The activated solid sample of CZJ-10 takes up 112 cm3 g−1 N2 at 77 K and 0.92 bar, resulting in a BET surface area of 173 m2 g−1. We speculate that the low N2 uptake of the activated CZJ-10 should be ascribed to the metastable and flexible structure nature of CZJ-10 consisting of mesopore space and two interpenetrated individual network structures. We further explored the CO2 capture capacity of CZJ-10. The CO2 uptake capacity of the activated CZJ-10 was obtained by measuring the sorption isotherms at 273 and 298 K (Figures 2 and S4). Because there exists a large vacant mesopore space

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RESULTS AND DISCUSSION The C3-symmetric organic ligand H3L was synthesized by Heck cross-coupling reaction between 4,4′,4″-benzene-1,3,5-triyltribromobenzene and methyl acrylate, followed by hydrolysis and acidification. Solvothermal reaction between H3L and copper nitrate in acidified DMF solvent at 80 °C for 2 days afforded blue crystals of CZJ-10. The structure of CZJ-10 was determined by single-crystal X-ray diffraction analysis, and the phase purity of the bulk material was confirmed by PXRD (Figure S5 in the Supporting Information). The formula of CZJ-10 was established based on single-crystal X-ray diffraction study, TGA (Figure S2), and microanalysis. Single-crystal X-ray diffraction analysis revealed that CZJ-10 crystallizes in the cubic space group Pn3̅n, which is a 2-fold interpenetrated three-dimensional (3D) framework structure. Each individual network is composed of in situ formed squareplanar Cu2(CO2)4 paddle-wheel SBUs that are linked by triangular L ligands (Figure 1a). According to the topology

Figure 1. (A) Single-crystal X-ray structure of CZJ-10 showing that square Cu2(CO2)4 paddle-wheel SBUs are linked by triangular L organic ligands. (B) The pto topology net in the crystal structure of CZJ-10. (C) The 2-fold interpenetrated 3D porous framework of CZJ10, highlighting the mesopore cage (cyan ball) with a diameter of about 2.5 nm. (D) Top and side views of the π−π tacked central benzene rings in two individual networks of interpenetrated CZJ-10. Color scheme: Cu, green square pyramids and balls; O, red; C, deep gray; H, light gray.

Figure 2. CO2 adsorption isotherms of CZJ-10, RB@CZJ-10, CR@ CZJ-10, melanin@CZJ-10, and TPM@CZJ-10, and N2 adsorption isotherm of CZJ-10 at 298 K.

without CO2 affinity site, the activated CZJ-10 only takes up 16.3 cm3 g−1 CO2 at 298 K and 1 atm, which is low compared with many reported MOF materials in the literature.46−51 However, the mesopore space in CZJ-10 provides us an opportunity to introduce additional CO2 binding sites by encapsulating CO2 affinity moieties inside the vacant pore space. In consideration that there are abundant CO2 affinity sites in many dye molecules (e.g., N−H and O−H groups), different dye molecules, including cationic rhodamine B (RB), anionic CR, and neutral melanin, were selected and further encapsulated in the pore space of CZJ-10 by an in situ synthesis method. When RB, CR, and melanin were added into the reaction mixtures during synthesis of CZJ-10, different dye molecules were readily imbedded inside the pore space of CZJ10, denoted as RB@CZJ-10, CR@CZJ-10, and melanin @CZJ10, respectively. Analyzed by UV−vis absorption spectroscopy,

analysis method,56 the network of CZJ-10 is a 3,4-connected net with pto topology which is the same as UTSA-28,57 when L ligand serves as a three connected branch point, and the Cu2(CO2)4 paddle-wheel SBU is considered as the planar four points of extension (Figure 1b). In the crystal structure, the cinnamate benzene ring of L ligand is twisted from the center benzene ring with a dihedral angle of 36.5°. Two individual networks are interwoven in each other to form a 2-fold interpenetrated network structure (Figure 1c). Weak π−π interactions exist between the neighboring benzene rings from two individual networks with a center-to-center benzene distance of 3.76(1) Å (Figure 1d). It is interesting that such 2690

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the encapsulated dyes of RB, CR, and melanin are of 0.28, 0.04, and 13.1 mol per formula unit of CZJ-10, respectively. PXRD patterns of these dye encapsulated samples suggest that the network structures of these dye encapsulated samples are basically identical to that of original CZJ-10. It is interesting that the CO2 uptake capabilities of these dye encapsulated samples are significantly improved, even though the pore space is partially occupied by dye molecules (Figure 2). At 1 atm and 298 K, the CO2 uptakes of RB@CZJ-10, CR@CZJ-10, and melanin@CZJ-10 are of 35.0, 33.5, and 39.1 cm3 g−1, respectively. To make a comparison, we have encapsulated triphenylmethane (TPM) without CO2 affinity site instead of dyes in the pore space of CZJ-10 to conduct the CO2 sorption experiments (denoted as TPM@CZJ-10). As shown in Figure 2, the activated TPM@CZJ-10, consisting of 1.7 mol TPM per formula unit of CZJ-10, only takes up 13.3 cm3 g−1 CO2 at 298 K and 1 atm, which is lower than that of CZJ-10. The above results demonstrate that the improved CO2 adsorption capability of these dye encapsulated samples should be attributed to the introduction of strong CO2 interaction sites inside the pore space of CZJ-10. Another environmentally friendly strategy for CO2 capture is direct transformation of CO2 into invaluable fine chemicals.59−63 Recently, MOFs, consisting of Cu2(CO2)4 paddlewheel moieties, have been demonstrated as effective heterogeneous catalysts on the chemical conversion of CO2 into cyclic carbonates. We have therefore studied the catalytic properties of CZJ-10 on the cycloaddition between CO2 and styrene oxide to form cyclic carbonate. The reaction was performed at ambient temperature under 1 atm pressure and solvent free conditions in the presence of TBAB as a cocatalyst (Scheme 2).

Figure 3. Cycloaddition of styrene oxide with CO2 to form cyclic carbonate catalyzed by CZJ-10.

subsequently used in the successive runs for six cycles with almost retained catalytic efficiency (91% yield). To prove that the copper active sites inside the pore space of CZJ-10 are accessible, an activated sample of CZJ-10 was immersed in styrene oxide and styrene carbonate for 24 h at room temperature. UV−vis spectroscopy analysis indicates that CZJ-10 preferably takes up styrene oxide (10.7 mg/g) over styrene carbonate (trace). The preferred adsorption of styrene oxide reactant by CZJ-10 might facilitate the accumulation of the substrate molecules and the release of the product molecules inside the pore space, which can further improve the catalytic efficiency of CZJ-10 on the chemical transformation of styrene oxide and CO2 to cyclic carbonate.

Scheme 2. Catalytic Cycloaddition Reaction between Styrene Oxide and CO2

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CONCLUSIONS In summary, to make use of the new three-branched aromatic tricarboxylate ligand to connect with Cu2(CO2)4 paddle-wheel SBUs, we successfully constructed a mesoporous MOF material, consisting of 2-fold interpenetrated networks of pto topology. The two individual networks are interwoven and interconnected through weak π−π interactions between the neighboring central benzene rings, which result in mesopore cages of about 2.5 nm in diameter. To improve the CO2 capture capability, different dyes, including cationic RB, anionic CR, and neutral melanin, were introduced into the mesopore space of CZJ-10 by an in situ synthesis method. Even though the vacant pore space was obviously reduced, however, the CO2 uptakes of these dye encapsulated samples are significantly improved due to the introduction of additional CO2 affinity sites inside the pore space of CZJ-10. CZJ-10 also demonstrates high catalytic efficiency in the conversion of CO2 into valuable cyclic carbonate under mild conditions. Our work demonstrates the significance of the controlled introduction of different gas affinity moieties into the vacant pore space of mesoporous MOFs, and thus to realize high potential capabilities for gas capture, purification, storage, and separation.

CZJ-10 demonstrates high catalytic efficiency on the cycloaddition of styrene oxide with CO2 to form corresponding cyclic carbonate with high yield of >99%. When CZJ-10 was absent in the reaction system under otherwise identical conditions, the conversion of styrene oxide is of 24%. These results suggest that the copper sites in CZJ-10 play important roles on activation of epoxide substrate for the cyclization with CO2. According to the literature, the copper site on the pore surface of CZJ-10 performs as a Lewis acid site to combine and activate epoxide. The epoxy ring is then ring-opened by Br− from cocatalyst TBAB and further cyclizes with CO2 to form the corresponding cyclic carbonate.64 We also studied the catalytic properties of the dye encapsulated materials CR@CZJ10, melanin@CZJ-10, and RB@CZJ-10 under the identical conditions. GS-MS analysis showed that the cyclic carbonate yields are 82, 67, and 65% for CR@CZJ-10, melanin@CZJ-10, and RB@CZJ-10, respectively. These results should be ascribed to the access to the catalytic copper(II) sites which is partially blocked by the encapsulated dye molecules, even though these dye molecules can increase the CO2 uptakes of CZJ-10. As shown in Figure 3, the turnover number (TON) reaches 1998 after 48 h without loss of the catalytic activity for the following runs. CZJ-10 was easily recovered by centrifugation and

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.7b00188. 2691

DOI: 10.1021/acs.cgd.7b00188 Cryst. Growth Des. 2017, 17, 2688−2693

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FT-IR, TGA, UV−vis spectra, gas sorption isotherms, PXRD, GC-MS results, crystal data and structure refinement (PDF) Accession Codes

CCDC 1531376 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 data_ [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Chuan-De Wu: 0000-0001-8128-134X Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 21373180 and 21525312).

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DOI: 10.1021/acs.cgd.7b00188 Cryst. Growth Des. 2017, 17, 2688−2693