Tuning Gas Adsorption Properties of Zeolite-like ... - ACS Publications

Jul 11, 2017 - Tuning Gas Adsorption Properties of Zeolite-like Supramolecular. Assemblies with gis Topology via Functionalization of Isoreticular. Me...
9 downloads 8 Views 2MB Size
Download PDF
Forum Article www.acsami.org

Tuning Gas Adsorption Properties of Zeolite-like Supramolecular Assemblies with gis Topology via Functionalization of Isoreticular Metal−Organic Squares Shuang Wang,†,‡ Youssef Belmabkhout,†,§ Amy J. Cairns,§ Guanghua Li,‡ Qisheng Huo,‡ Yunling Liu,*,‡ and Mohamed Eddaoudi*,§ ‡

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, P. R. China § Division of Physical Sciences and Engineering, Advanced Membranes & Porous Materials Center, Functional Materials Design, Discovery & Development (FMD3), King Abdullah University of Science and Technology (KAUST), 4700, Thuwal 23955-6900, Kingdom of Saudi Arabia S Supporting Information *

ABSTRACT: A strategy based on metal−ligand directed assembly of metal−organic squares (MOSs), built-up from fourmembered ring (4MR) secondary building units (SBUs), has been employed for the design and construction of isoreticular zeolite-like supramolecular assemblies (ZSAs). Four porous Co-based ZSAs having the same underlying gis topology, but differing only with respect to the capping and bridging linkers, were successfully isolated and fully characterized. In this series, each MOS in ZSA-3−ZSA-6 possess an ideal square geometry and is connected to four neighboring MOS via a total of 16 hydrogen bonds to give a 3-periodic porous network.To systematically assess the effect of the pore system (size and functionality) on the gas adsorption properties, we evaluated the MOSs for their affinity for different probe molecules such as CO2 and light hydrocarbons. ZSA-3−ZSA-6 showed high thermal stability (up to 300 °C) and was proven highly porous as evidenced by gas adsorption studies. Notably, alkyl-functionalized MOSs were found to offer potential for selective separation of CO2, C3H6, and C3H8 from CH4 and H2 containing gas stream, such as natural gas and refinery-off gases. KEYWORDS: porous materials, metal−organic squares, MOFs, zeolite-like supramolecular assemblies, alkyl-functionalization, gas separation

■

INTRODUCTION Metal−organic frameworks (MOFs) are regarded as a cornerstone of crystalline porous solid-state materials that offer great promise to address various key challenging societal needs pertaining to gas storage and separation, design catalysts, and controlled drug release.1−9 Zeolite-like metal−organic frameworks (ZMOFs), a special subclass of MOFs first introduced by Eddaoudi and co-workers, are of particular interest and offer great prospective for applications pertaining to adsorption/ separation of gases,10−18 due to their zeolitic network underlying topologies associated with relatively extra-large cavities, cation exchange ability, high chemical and thermal stabilities. It is to be noted that construction of MOFs with © XXXX American Chemical Society

novel zeolite and zeolite-like topologies is a continuous challenge in crystal chemistry. Accordingly, three synthetic strategies have been implemented to target synthesis of ZMOFs: (i) construction of 4-connected super tetrahedron molecular building blocks (MBBs);19−25 (ii) metal−ligand directed assembly where the O2− in traditional inorganic zeolites is substituted by suitable ditopic angular linkers to give Special Issue: Hupp 60th Birthday Forum Received: April 29, 2017 Accepted: June 26, 2017

A

DOI: 10.1021/acsami.7b06010 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

ACS Applied Materials & Interfaces

■

decorated and expanded ZMOFs;26−34 (iii) supermolecular building block (SBB) approach using functionalized metal− organic polygons or polyhedral (e.g., metal−organic cubes (MOCs) or metal−organic squares (MOSs)).35−37 As previously described by us, rigid and directional metal− organic squares (MOSs), having square planar geometry, are ideal targets for the construction of novel zeolite-like supramolecular assemblies (ZSAs). It is to be noted that 4membered rings (4MRs) are the most common secondary building unit (SBU) in inorganic zeolites and therefore MOSs offer great prospective for the directed construction of novel zeolite-like networks containing 4MRs. Because of their unique prospective to provide additional uncoordinated oxygen centers, when chelated in a N-, O-bis(monodentate) fashion to a metal ion, we employed imidazoledicarboxylate-based ligands as bridging linkers to afford appropriate functional MOS. Furthermore, bis(monodentate) diamines capping ligands were used because of their potential to offer additional hydrogen-bonding sites on MOSs, appropriate for the plausible assembly via N−H···O hydrogen bonds. It is to be stated that the selection of an organic ligand with desired structural features, geometry and coordination modes, and functionality is critical for the rational construction of MOFs with unique structural and chemical feature.38−40 Markedly, controlled pore size/shape and functionality were shown to directly impact gas adsorption capacities and energetics.41−45 Nevertheless, systematic studies correlating the MOF adsorbent properties to the associated pore system, pore size, and functionality are scarce because of the encountered difficulties in changing a given MOF composition and dimensions without altering its underlying network topology. Inspired by the above consideration, we focused our work on the use of two types of ligands, i.e. 4,5-imidazoledicarboxylic acid derivatives with distinct 2-position on the imidazole ring, and bis(monodentate) amines for the deliberate construction of ZSAs based on MOSs with gis topology. The MOSs are constructed by four metal ions, four functionalized bridging linkers and four functionalized capping ligands, as depicted in Scheme 1. Interestingly, the results indicate that altering the

Forum Article

EXPERIMENTAL SECTION

Materials and Methods. The organic ligands 2-methyl-4, 5imidazoledicarboxylic acid (H3MeImDC) and 2-ethyl-4, 5-imidazoledicarboxylic acid (H3EtImDC) were prepared from 2-methylbenzimidazole and 2-ethyl-benzimidazole following the literature procedures.54,55 All other reagents were used without further purification and as obtained from commercial sources. Fourier-transform infrared (FT-IR) spectra (4000−400 cm−1) were collected in the solid state on a Nicolet Impact 410 FT-IR spectrometer using potassium bromide pellets. The relative peak intensities are labeled as very strong (vs), strong (s), medium (m), weak (w), and broad (br). Powder X-ray diffraction (PXRD) experiments were performed on a Rigaku D/max-2550 X-ray diffractometer at 50 kV, 200 mA for CuKα (λ = 1.5418 Å) equipped with a variable-temperature stage, with a scan speed of 2°/min. Thermogravimetric analysis (TGA) were performed under a continuous air flow and recorded on a NETZSCH STA 449C thermogravimetric analyzer with a heating rate of 10 °C per min. Elemental analyses were performed on a PerkinElmer 2400 element analyzer. Low pressure gas adsorption measurements were done on fully automated Autosorb-1C and Autosorb-iQ gas adsorption analyzers (Quantachrome Instruments). High -pressure gas sorption studies were performed on a magnetic suspension balance (by Rubotherm, Germany). Synthesis of Compounds. Synthesis of |(H 2 O) 2 5 | [Co4(C6H3N2O4)4(C3H10N2)4] (ZSA-3). 2-Methyl-4,5-imidazoledicarboxylic acid (H3MeImDC, 0.04 g, 0.25 mmol), Co(CH3COO)2·4H2O (0.06 g, 0.25 mmol), H2O (5 mL), and 1,2-propanediamine (1, 2PDA, 0.055 mL) were sealed in a Teflon-lined stainless steel autoclave and heated at 120 °C for 24 h, and then cooled to room temperature. The red polyhedral crystals were isolated, washed with distilled water, and dried in air. Elemental analysis (wt %) for ZSA-3, calcd: C 26.19, H 6.23, N 13.57, found: C 24.91, H 5.98, N 15.23. FT-IR (4000−400 cm−1): 3442 (br), 3220 (br), 3112 (br), 2976 (w), 2883 (w), 1654 (vs), 1453 (m), 1404 (vs), 1339 (vs), 1232 (m), 1118 (vs), 1025 (m), 825 (s), 799 (s), 721 (m), 683 (m), 688 (m), 550 (s), 502 (s), 446 (w). Synthesis of |(H2O)23|[Co4(C7H5N2O4)4(C3H10N2)4] (ZSA-4). 2-Ethyl4,5-imidazoledicarboxylic acid (H3EtImDC, 0.09 g, 0.50 mmol), Co(CH3COO)2·4H2O (0.12 g, 0.50 mmol), H2O (7 mL), and 1,2propanediamine (1, 2-PDA, 0.065 mL) were sealed in a Teflon-lined stainless steel autoclave and heated at 140 °C for 20 h, and then cooled to room temperature. The red polyhedral crystals were isolated, washed with distilled water, and dried in air. Elemental analysis (wt %) for ZSA-4, calcd: C 28.75, H 6.39, N 13.41, found: C 27.04, H 6.83, N 12.75. FT-IR (4000−400 cm−1): 3448 (br), 3220 (br), 3112 (br), 2984 (w), 2883 (w), 1662 (vs), 1425 (vs), 1339 (vs), 1215 (m), 1112 (s), 1025 (w), 892 (w), 825 (m), 798 (m), 740 (w), 702 (w), 511 (m), 473 (w), 436 (w). Synthesis of |(H2O)28|[Co4(C6H3N2O4)4(C2H8N2)4] (ZSA-5). 2Methyl-4, 5-imidazoledicarboxylic acid (H3MeImDC, 0.04 g, 0.25 mmol), Co(CH3COO)2·4H2O (0.06 g, 0.25 mmol), H2O (2 mL), ethylenediamine (EN, 0.035 mL) were sealed in a Teflon-lined stainless steel autoclave and heated at 110 °C for 24 h, and then cooled to room temperature. The red polyhedral crystals were isolated, washed with distilled water, and dried in air. Elemental anal. (wt %) for ZSA-5, calcd: C 23.31, H 6.11, N 13.59, found: C 22.52, H 7.02, N 12.95. FT-IR (4000−400 cm−1): 3448 (br), 3227 (br), 3120 (br), 2970 (w), 2883 (w), 1661 (vs), 1468 (w), 1404 (vs), 1338 (vs), 1215 (w), 11153 (w), 1118 (s), 1066 (m), 996 (w), 882 (m), 825 (m), 779 (m), 721 (w), 683 (w), 550 (w), 502 (w). Synthesis of |(H2O)25|[Co4(C7H5N2O4)4(C2H8N2)4] (ZSA-6). 2-Ethyl4,5-imidazoledicarboxylic acid (H3EtImDC, 0.045 g, 0.25 mmol), Co(CH3COO)2·4H2O (0.060 g, 0.25 mmol), H2O (2 mL), ethylenediamine (EN, 0.035 mL) was sealed in a Teflon-lined stainless steel autoclave and heated at 100 °C for 20 h, and then cooled to room temperature. The red polyhedral crystals were isolated, washed with distilled water and dried in air. Elemental analysis (wt %) for ZSA-6, calcd: C 26.19, H 6.23, N 13.57, found: C 25.51, H 5.21, N 14.26. FT-

Scheme 1. Representation of the Synthetic Strategy for the Construction of MOS-Based ZSAs

substitutional groups of ligands, in combination with distinct bis(monodentate) amines, greatly influences the gas adsorption and separation properties of ZSAs. Prominently, the ability to tune the MOF adsorbent affinity toward important gas commodities such as CO2 and light hydrocarbons i.e., ethane (C2H6), propane (C3H8), and propylene (C3H6) is of prime importance in upgrading/separation of valuable industrial products such as methane (CH4), hydrogen (H2), and polymer grade C3H6 from natural gas (NG) and refinery off-gases (ROG).1,46−53 B

DOI: 10.1021/acsami.7b06010 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

Forum Article

ACS Applied Materials & Interfaces IR (4000−400 cm−1): 3456 (br), 3219 (br), 3127 (br), 2970 (w), 2883 (w), 1662 (vs), 1425 (vs), 1332 (vs), 1234 (w), 1140 (w), 1121 (s), 1054 (m), 1006 (w), 882 (w), 835 (m), 779 (m), 731 (w), 692 (w), 588 (w), 531 (m), 473 (w), 436 (w). Single-Crystal X-ray Crystallography. Data were collected on a Bruker Smart CCD diffractometer for ZSA-3 and ZSA-5, and a Rigaku RAXIS-RAPID IP diffractometer for ZSA-4 and ZSA-6, using graphitemonochromated Mo−Kα radiation (λ = 0.71073 Å). Data integration and reduction were performed using Saint for ZSA-3 and ZSA-5, RAPID AUTO processing program for ZSA-4 and ZSA-6. Absorption corrections were applied by using SADABS for ZSA-3 and ZSA-5, RAPID AUTO processing for ZSA-4 and ZSA-6. The structures were solved by direct methods, and all non-hydrogen atoms were subjected to anisotropic refinement by full-matrix least-squares on F2 by using the SHELXTL program.56 Non-hydrogen atoms were refined with anisotropic temperature parameters. It is to be noted that carbon atoms of the 1, 2-PDA ligand are disordered over two positions with occupancy factors 0.45 and 0.55 in ZSA-3, and 0.20 and 0.80 in ZSA-4, respectively. The ethyl groups of H3EtImDC ligand are disordered over two positions with occupancy factors 0.40 and 0.60 in ZSA-4, and 0.50 and 0.50 in ZSA-5, respectively. The final formula resulted from the combination of crystallographic data and elemental and thermogravimetric analysis data. The supplementary crystallographic data, CCDC-972819−972822, can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ data_request/cif. Crystal data and refinement conditions are presented in Tables S1−S5.

ligands orientation alternate to give a calixarene-like 1, 3alternating atropisomer molecular square. The four squares are regular as evidenced by the vertex angles of 90° and the Co− Co edge distances are identical, affirming the ideal square geometry. The two nitrogen atoms of each bis(monodentate) amines and the two oxygen atoms of each μ2-RImDC3− ligand form hydrogen bonds with associated oxygen/nitrogen atoms of the neighboring square. Accordingly, each MOS is connected to four neighboring squares in a tetrahedral geometry, via 16 hydrogen bonds. As a result, molecular squares are arranged parallel to each other and assemble in a ladder-like network via edge to edge intermolecular N−H···O hydrogen bonds (Figure S6), generating a 3-periodic framework with underlying gis topology. Substitution of H3ImDC bridging linkers in ZSA-1 by H3MeImDC, H3EtImDC led to the assembly of ZSA-3 and ZSA-4, respectively (Figure 1). Geometric analysis of the MOSs confirmed that ligand modification yields Co−Co distance along the edge of 6.066 and 6.100 Å for ZSA-3 and ZSA-4, respectively, which are slightly longer than the corresponding distance for ZSA-1 (6.003 Å). Although the N−H···O hydrogen bond length between vertices of two neighboring squares is 2.831 and 2.853 Å, respectively (Figure S6). In addition, the vertices Co−Co distance of two adjacent squares is 6.30 and 6.42 Å (Figure 2), which consequently

■

RESULTS AND DISCUSSION Analogous to our previous work, each Co3+ ion is coordinated in the octahedral trans-CoN4O2 fashion with two oxygen and two nitrogen atoms from two individual chelating μ2-RImDC3− (R = Me or Et) ligands and two nitrogen atoms from the chelating bis(monodentate) amines. Each μ2-RImDC3− connects two Co3+ centers in a bis(bidentate) mode. The four bis(monodentate) amines serving as terminal ligands and four Co3+ ions connected by four bridging μ2-RImDC3− ligands generate a MOS in the ab plane (Figure 1). The μ2-RImDC3−

Figure 2. Crystal structure of ZSA-3− ZSA-6: (a) Ball-and-stick representations of MOSs, (b) schematic illustration of the gis cage showing the distance between two MOSs, (c) CPK model of the 3periodic framework showing open channels along the a direction. Hydrogen atoms and guest water molecules are omitted for clarity. (Color code: carbon = gray, nitrogen = blue, oxygen = red, cobalt = green, H-bond as shown in purple dots).

altered the relative size (6.51 Å for ZSA-1) and configuration of the gis cage. Interestingly, in addition to introducing distinct bridging linker, e.g. H3MeImDC, H3EtImDC in the case of ZSA-3 and ZSA-4 respectively, the original capping/terminal 1, 2-propanediamine (1, 2-PDA) can also be substituted by another chelating terminal ligand such ethylenediamine (EN), in this case permitting the isolation of ZSA-5 and ZSA-6. In both ZSA-5 and ZSA-6, the Co−Co distance along the edge is 6.068 and 6.112 Å, and the N−H···O hydrogen bond length between the vertices of two neighboring squares is 2.862 and 2.847 Å, respectively. As in the case of ZSA-3, the size and shape/configuration of the gis cages changed in ZSA-5 and ZSA-6, for the vertices Co−Co distance of two adjacent squares is 6.36 and 6.40 Å (Figure 2b), respectively. All ZSAs

Figure 1. Crystal structure of the original ZSA-1 and isoreticular ZSA3−ZSA-6: Ball-and-stick representations of the MOSs, and schematic representation of MOS showing the Co−Co distance. Hydrogen atoms and guest water molecules are omitted for clarity. (Color code: carbon = gray, nitrogen = blue, oxygen = red, cobalt = green). C

DOI: 10.1021/acsami.7b06010 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

Forum Article

ACS Applied Materials & Interfaces have the expected type of cage (a 4684 gis cage enclosing 20 Co centers), generating two intersecting orthogonal channels with estimated dimensions of 8.8 × 8.8 Å, 7.7 × 6.5 Å, 9.9 Å × 8.5 Å, 8.2 Å × 6.5 Å along the a or b axes in ZSA-3, ZSA-4, ZSA-5, and ZSA-6, respectively (Figure 2c, not including van der Waals radius). Argon adsorption isotherms for the isostructural ZSA-3, ZSA-4, ZSA-5, and ZSA-6 were measured at 87 K in order to assess the structural porosity. Prior the adsorption measurement, the as-synthesized microcrystalline samples were exchanged by dichloromethane for 48 h, during which the dichloromethane solution was refreshed 12 times a day. The dichloromethane exchanged samples were degassed under vacuum at 120 °C for 12 h, affording the fully desolvated samples. Argon adsorption isotherms for the four samples revealed reversible type-I isotherms characteristic of porous materials with permanent microporosity (Figure S7, S9, and S11). The apparent Brunauer−Emmett−Teller (BET) surface areas for ZSA-3, ZSA-4, ZSA-5, and ZSA-6 were estimated to be 1426, 1158, 985, and 945 m2/g, respectively. The pore size distribution for ZSA-3, ZSA-4, ZSA-5, and ZSA-6 calculated from Ar adsorption data using NLDFT model agrees well with the each associated single crystal structure (Figures S8, S10, and S12). ZSA-3, ZSA-4, ZSA-5, and ZSA-6 maintained their structural integrity upon solvent removal under vacuum and thermal treatment, as supported by the fully reversible Ar adsorption isotherms. Thermogravimetric analysis (TGA) showed that ZSA-3−ZSA-6 compounds are stable to temperatures up to 300 °C, and upon full removal of solvent guest molecules (Figure S1). Powder X-ray diffraction (PXRD) further confirmed that the four compounds were stable and retained their crystallinity up to about 300 °C (Figures S2−S4). This exceptional stability is remarkable and rare for ZMOFs and MOFs,37 given that the resultant extended network is entirely supported by hydrogen bonds. To further elucidate the effect of functionalizing the bridging ligands with methyl or ethyl groups, pure component lowpressure gas adsorption of CO2 as well as high-pressure adsorption of CO2, CH4, O2, N2, H2 (Figures S13−S23), C2H4, C2H6, C3H6 and C3H8 (Figure 3) were carried out on ZSA-3 and ZSA-4 and the parent ZSA-1. ZSA-3 and ZSA-4 were selected for further investigation because of the similar windows dimension that will allow to unveil the effect of methyl and ethyl functionalization. Interestingly, the adsorption isotherms were observed to show a marked steepness for CO2 and C2+, as reflected from the adsorption uptake at 0.5 bar. In fact upon introduction of methyl and ethyl functionalized bridging ligand (ZSA-3 and ZSA-4), the uptake at 0.5 bar total pressure showed enhanced adsorption for C2H4, C3H6, C2H6, and C3H8, whereas no significant changes were observed for CO2. To further evaluate the effect of substituting the H3ImDC bridging linkers in ZSA-1 by H3MeImDC, H3EtImDC on the CO2 separation, and light hydrocarbon separation (C2+/CH4) from CH4, we performed ideal adsorption solution theory (IAST) analysis on single gas adsorption data of C3H8, C3H6, C2H6, C2H4, CH4, and CO2, using best fitting by the Toth model. The employement of IAST is supported by the structural and chemical homogeneity of these compounds. IAST analysis showed that the parent sample ZSA-1 exhibited a much higher selectivity for CO2 vs CH4 than ZSA-3 and ZSA4, in the whole pressure range studied (Figure 4), in good agreement with the relatively higher Qst of CO2 adsorption at

Figure 3. CO2, CH4, C2H4, C2H6, C3H6, and C3H8 sorption data for (a) ZSA-1, (b) ZSA-3, and (c) ZSA-4.

Figure 4. CO2/CH4:5/95 gas mixture selectivity on ZSA-1, ZSA-3, and ZSA-4 calculated using IAST at 298 K.

low loading for ZSA-1 than ZSA-3 and ZSA-4. Particularly, the presence of the methyl and ethyl groups in the bridging linkers resulted in a decrease in CO2 /framework interactions, which in turn led to the noticeable decrease in CO2 adsorption selectivity. D

DOI: 10.1021/acsami.7b06010 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

Forum Article

ACS Applied Materials & Interfaces The potential separation of C2+/CH4 is exemplified by C3H8/CH4 gas-mixture. Interestingly, in the case of C3H8/CH4 separation (Figure 5), ZSA-1 showed the lowest selectivity

■

crystallographic information file for C36H102Co4N16O41 (CIF)

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (Y. L.). *E-mail: [email protected] (M. E.). ORCID

Guanghua Li: 0000-0003-3029-8920 Yunling Liu: 0000-0001-5040-6816 Mohamed Eddaoudi: 0000-0003-1916-9837 Author Contributions †

S.W. and Y.B. contributed equally.

Notes

The authors declare no competing financial interest.

■

Figure 5. C3H8/CH4:5/95 gas mixture selectivity for ZSA-1, ZSA-3, and ZSA-4 calculated using IAST.

ACKNOWLEDGMENTS Research reported in this publication was supported by King Abdullah University of Science and Technology (KAUST). M.E. and Y.B. gratefully acknowledge Internal KAUST FUND FCC/1/1972-8-01. We also gratefully acknowledge the financial support of the National Natural Science Foundation of China ( 21373095 and 21621001) and supported by the 111 Project (B17020).

toward C3H8, whereas ZSA-3 and ZSA-4 exhibited enhanced selectivity. The enhancement in the affinity toward C2+ in general and C3H8 in particular is most likely associated with the enhanced interaction of C3H8 with the framework surface bearing alkyl groups. Prominently, the resultant molecular organic squares exhibit tunable separation performances for CO2 and C2+, a key separation feature offering great prospective for the selective removal of condensable gases such as C3H8, C3H6 from NG or ROG and the subsequent satisfaction of the requisite requirements in term of gas pipeline quality or polymer grade olefins.

■

■

CONCLUSIONS We have successfully synthesized a series of ZSAs with the gis underlying topology derived from a MOS-directed approach. MOSs, as a rigid and directional SBB, offer the potential to direct the construction of zeolitic frameworks containing 4MR SBUs. Markedly, this design strategy permitted the aptitude to direct and control the assembly of the SBBs into 3-periodic networks, novel molecular square frameworks with targeted properties. Notably, the construction of molecular square frameworks using bridging linkers bearing methyl/ethyl groups, pending in the pore system/channels, resulted in the finetuning of the selectivity toward CO2 and C2+, and the plausible removal of C2+ from different hydrocarbons containing gases. Work is in progress to extend this approach to include different metal organic polygons, e.g. five-, six-, or eight-membered rings, for the construction of ZSAs and their exploration for other gas separations and sensing applications.

■

REFERENCES

(1) Cadiau, A.; Adil, K.; Bhatt, P. M.; Belmabkhout, Y.; Eddaoudi, M. A Metal-Organic Framework-based Splitter for Separating Propylene from Propane. Science 2016, 353, 137−140. (2) Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.; Bloch, E. D.; Herm, Z. R.; Bae, T.-H.; Long, J. R. Carbon Dioxide Capture in Metal-Organic Frameworks. Chem. Rev. 2012, 112, 724−781. (3) Li, J. R.; Sculley, J. L.; Zhou, H. C. Metal-Organic Frameworks for Separations. Chem. Rev. 2012, 112, 869−932. (4) Tranchemontagne, D. J.; Park, K. S.; Furukawa, H.; Eckert, J.; Knobler, C. B.; Yaghi, O. M. Hydrogen Storage in New Metal-Organic Frameworks. J. Phys. Chem. C 2012, 116, 13143−13151. (5) Nugent, P.; Belmabkhout, Y.; Burd, S. D.; Cairns, A. J.; Luebke, R.; Forrest, K.; Pham, T.; Ma, S.; Space, B.; Wojtas, L.; Eddaoudi, M.; Zaworotko, M. J. Space B.; Wojtas L.; Eddaoudi M.; Zaworotko, M. J. Porous Materials with Optimal Adsorption Thermodynamics and Kinetics for CO2 Separation. Nature 2013, 495, 80−84. (6) Cui, X. L.; Chen, K. J.; Xing, H. B.; Yang, Q. W.; Krishna, R.; Bao, Z. B.; Wu, H.; Zhou, W.; Dong, X. L.; Han, Y.; Li, B.; Ren, Q. L.; Zaworotko, M. J.; Chen, B. L. Pore Chemistry and Size Control in Hybrid Porous Materials for Acetylene Capture from Ethylene. Science 2016, 353, 141−144. (7) Peters, A. W.; Li, Z. Y.; Farha, O. K.; Hupp, J. T. Toward Inexpensive Photocatalytic Hydrogen Evolution: A Nickel Sulfide Catalyst Supported on a High-Stability Metal-Organic Framework. ACS Appl. Mater. Interfaces 2016, 8, 20675−20681. (8) Motkuri, R. K.; Thallapally, P. K.; Nune, S. K.; Fernandez, C. A.; McGrail, B. P.; Atwood, J. L. Role of Hydrocarbons in Pore Expansion and Contraction of a Flexible Metal-Organic Framework. Chem. Commun. 2011, 47, 7077−7079. (9) Thallapally, P. K.; Tian, J.; Kishan, M. R.; Fernandez, C. A.; Dalgarno, S. J.; McGrail, P. B.; Warren, J. E.; Atwood, J. L. Flexible (Breathing) Interpenetrated Metal-Organic Frameworks for CO2 Separation Applications. J. Am. Chem. Soc. 2008, 130, 16842−16843. (10) Eddaoudi, M.; Sava, D. F.; Eubank, J. F.; Adil, K.; Guillerm, V. Zeolite-like Metal-Organic Frameworks (ZMOFs): Design, Synthesis, and Properties. Chem. Soc. Rev. 2015, 44, 228−249. (11) Phan, A.; Doonan, C. J.; Uribe-romo, F. J.; Knobler, C. B.; O’Keeffe, M.; Yaghi, O. M. Synthesis, Structure, and Carbon Dioxide

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.7b06010. PXRD, TGA, IR spectra, gas sorption data, crystallographic data, and additional structural figures (PDF) crystallographic information file for C36H102Co4N16O41 (CIF) crystallographic information file for C40H106Co4N16O39 (CIF) crystallographic information file for C32H100Co4N16O44 (CIF) E

DOI: 10.1021/acsami.7b06010 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

Forum Article

ACS Applied Materials & Interfaces Capture Properties of Zeolitic Imidazolate Frameworks. Acc. Chem. Res. 2009, 43, 58−67. (12) Li, K.; Olson, D. H.; Seidel, J.; Emge, T. J.; Gong, H.; Zeng, H.; Li, J. Zeolitic Imidazolate Frameworks for Kinetic Separation of Propane and Propene. J. Am. Chem. Soc. 2009, 131, 10368−10369. (13) Alkordi, M. H.; Liu, Y. L.; Larsen, R. W.; Eubank, J. F.; Eddaoudi, M. Zeolite-like Metal-Organic Frameworks as Platforms for Applications: On Metalloporphyrin-Based Catalysts. J. Am. Chem. Soc. 2008, 130, 12639−12641. (14) Banerjee, R.; Phan, A.; Wang, B.; Knobler, C.; Furukawa, H.; O’Keeffe, M.; Yaghi, O. M. High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture. Science 2008, 319, 939−943. (15) Nguyen, N. T. T.; Furukawa, H.; Gndara, F.; Nguyen, H. T.; Cordova, K. E.; Yaghi, O. M. Selective Capture of Carbon Dioxide under Humid Conditions by Hydrophobic Chabazite-Type Zeolitic Imidazolate Frameworks. Angew. Chem., Int. Ed. 2014, 53, 10645− 10648. (16) Wang, F.; Fu, H. R.; Kang, Y.; Zhang, J. A New Approach Towards Zeolitic Tetrazolate-Imidazolate Frameworks (ZTIFs) with Uncoordinated N-heteroatom Sites for High CO2 Uptake. Chem. Commun. 2014, 50, 12065−12068. (17) Cui, P.; Ma, Y. G.; Li, H. H.; Zhao, B.; Li, J. R.; Cheng, P.; Balbuena, P. B.; Zhou, H. C. Multipoint Interactions Enhanced CO2 Uptake: A Zeolite-like Zinc-Tetrazole Framework with 24-Nuclear Zinc Cages. J. Am. Chem. Soc. 2012, 134, 18892−18895. (18) Barea, E.; Navarro, J. A. R.; Salas, J. M.; Masciocchi, N.; Galli, S.; Sironi, A. Mineralomimetic Sodalite- and Muscovite-Type Coordination Frameworks. Dynamic Crystal-to-Crystal Interconversion Processes Sensitive to Ion Pair Recognition. J. Am. Chem. Soc. 2004, 126, 3014−3015. (19) Sun, L. B.; Xing, H. Z.; Liang, Z. Q.; Yu, J. H.; Xu, R. R. A 4 + 4 Strategy for Synthesis of Zeolitic Metal-Organic Frameworks: an Indium-MOF with SOD Topology as a Light-Harvesting Antenna. Chem. Commun. 2013, 49, 11155−11157. (20) Wang, D. M.; Zhao, T. T.; Li, G. H.; Huo, Q. S.; Liu, Y. L. A Porous Sodalite-type MOF Based on Tetrazolcarboxylate Ligands and [Cu4Cl]7+ Squares with Open Metal Sites for Gas Sorption. Dalton Trans. 2014, 43, 2365−2368. (21) Fang, Q. R.; Zhu, G. S.; Xue, M.; Sun, J. Y.; Qiu, S. L. Porous Coordination Polymers with Zeolite Topologies Constructed from 4Connected Building Units. Dalton Trans. 2006, 2399−2402. (22) Luo, X. L.; Cao, Y.; Wang, T.; Li, G. H.; Li, J. G.; Yang, Y. G.; Xu, Z. X.; Zhang, J.; Huo, Q. S.; Liu, Y. L.; Eddaoudi, M. Host-Guest Chirality Interplay: A Mutually Induced Formation of a Chiral ZMOF and Its Double-Helix Polymer Guests. J. Am. Chem. Soc. 2016, 138, 786−789. (23) Férey, G.; Draznieks, C. M.; Serre, C.; Millange, F.; Dutour, J.; Surblé, S.; Margiolaki, I. A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area. Science 2005, 309, 2040−2042. (24) Férey, G.; Serre, C.; Draznieks, C. M.; Millange, F.; Surblé, S.; Dutour, J.; Margiolaki, I. A Hybrid Solid with Giant Pores Prepared by a Combination of Targeted Chemistry, Simulation, and Powder Diffraction. Angew. Chem., Int. Ed. 2004, 43, 6296−6301. (25) Abrahams, B. F.; Haywood, M. G.; Robson, R.; Slizys, D. A. New Tricks for an Old Dog: The Carbonate Ion as a Building Block for Networks Including Examples of Composition [Cu6(CO3)12{C(NH2)3}8]4‑ with the Sodalite Topology. Angew. Chem., Int. Ed. 2003, 42, 1112−1115. (26) Zhang, J. P.; Zhang, Y. B.; Lin, J. B.; Chen, X. M. Metal Azolate Frameworks: From Crystal Engineering to Functional Materials. Chem. Rev. 2012, 112, 1001−1033. (27) Wang, B.; Cŏté, A. P.; Furukawa, H.; O’Keeffe, M.; Yaghi, O. M. Colossal Cages in Zeolitic Imidazolate Frameworks as Selective Carbon Dioxide Reservoirs. Nature 2008, 453, 207−212. (28) Sava, D. F.; Kravtsov, V. Ch.; Nouar, F.; Wojtas, L.; Eubank, J. F.; Eddaoudi, M. Quest for Zeolite-like Metal-Organic Frameworks:

On Pyrimidinecarboxylate Bis-Chelating Bridging Ligands. J. Am. Chem. Soc. 2008, 130, 3768−3770. (29) Liu, Y. L.; Kravtsov, V. Ch.; Eddaoudi, M. Template-Directed Assembly of Zeolite-like Metal-Organic Frameworks (ZMOFs): A usfZMOF with an Unprecedented Zeolite Topology. Angew. Chem., Int. Ed. 2008, 47, 8446−8449. (30) Hayashi, H.; Cŏté, A. P.; Furukawa, H.; O’Keeffe, M.; Yaghi, O. M. Zeolite A Imidazolate Frameworks. Nat. Mater. 2007, 6, 501−506. (31) Nguyen, N. T. T.; Furukawa, H.; Gándara, F.; Nguyen, H. T.; Cordova, K. E.; Yaghi, O. M. Selective Capture of Carbon Dioxide under Humid Conditions by Hydrophobic Chabazite-Type Zeolitic Imidazolate Frameworks. Angew. Chem., Int. Ed. 2014, 53, 10645− 10648. (32) Tang, Y. H.; Wang, F.; Liu, J. X.; Zhang, J. Diverse Tetrahedral Tetrazolate Frameworks with N-Rich Surface. Chem. Commun. 2016, 52, 5625−5628. (33) Liu, Y. L.; Kravtsov, V. Ch.; Larsen, R.; Eddaoudi, M. Molecular Building Blocks Approach to the Assembly of Zeolite-like MetalOrganic Frameworks (ZMOFs) with Extra-large Cavities. Chem. Commun. 2006, 1488−1490. (34) Park, K. S.; Ni, Z.; Cŏté, A. P.; Choi, J. Y.; Huang, R. D.; Uriberomo, F. J.; Chae, H. K.; O’Keeffe, M.; Yaghi, O. M. Exceptional Chemical and Thermal Stability of Zeolitic Imidazolate Frameworks. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 10186−10191. (35) Wang, S.; Zhao, T. T.; Li, G. H.; Wojtas, L.; Huo, Q. S.; Eddaoudi, M.; Liu, Y. L. From Metal-Organic Squares to Porous Zeolite-like Supramolecular Assemblies. J. Am. Chem. Soc. 2010, 132, 18038−18041. (36) Alkordi, M. H.; Brant, J. A.; Wojtas, L.; Kravtsov, V. Ch.; Cairns, A. J.; Eddaoudi, M. Zeolite-like Metal-Organic Frameworks (ZMOFs) Based on the Directed Assembly of Finite Metal-Organic Cubes (MOCs). J. Am. Chem. Soc. 2009, 131, 17753−17755. (37) Sava, D. F.; Kravtsov, V. Ch.; Eckert, J.; Eubank, J. F.; Nouar, F.; Eddaoudi, M. Exceptional Stability and High Hydrogen Uptake in Hydrogen-Bonded Metal-Organic Cubes Possessing ACO and AST Zeolite-like Topologies. J. Am. Chem. Soc. 2009, 131, 10394−10396. (38) Lu, W. G.; Wei, Z. W.; Gu, Z. Y.; Liu, T. F.; Park, J.; Park, J.; Tian, J.; Zhang, M. W.; Zhang, Q.; Gentle, T., III; Bosch, M.; Zhou, H. C. Tuning the Structure and Function of Metal-Organic Frameworks via Linker Design. Chem. Soc. Rev. 2014, 43, 5561−5593. (39) Han, Y.; Zheng, H.; Liu, K.; Wang, H. L.; Huang, H. L.; Xie, L. H.; Wang, L.; Li, J. R. In-Situ Ligand Formation-Driven Preparation of a Heterometallic Metal-Organic Framework for Highly Selective Separation of Light Hydrocarbons and Efficient Mercury Adsorption. ACS Appl. Mater. Interfaces 2016, 8, 23331−23337. (40) Farha, O. K.; Wilmer, C. E.; Eryazici, I.; Hauser, B. G.; Parilla, P. A.; O’Neill, K.; Sarjeant, A. A.; Nguyen, S. T.; Snurr, R. Q.; Hupp, J. T. Designing Higher Surface Area Metal-Organic Frameworks: Are Triple Bonds Better than Phenyls? J. Am. Chem. Soc. 2012, 134, 9860−9863. (41) Wang, C.; Li, L. J.; Tang, S. F.; Zhao, X. B. Enhanced Uptake and Selectivity of CO2 Adsorption in a Hydrostable Metal-Organic Frameworks via Incorporating Methylol and Methyl Groups. ACS Appl. Mater. Interfaces 2014, 6, 16932−16940. (42) Guo, X. Y.; Zhou, Z.; Chen, C.; Bai, J. F.; He, C.; Duan, C. Y. New rht-Type Metal-Organic Frameworks Decorated with Acylamide Groups for Efficient Carbon Dioxide Capture and Chemical Fixation from Raw Power Plant Flue Gas. ACS Appl. Mater. Interfaces 2016, 8, 31746−31756. (43) Liu, L. J.; Telfer, S. G. Systematic Ligand Modulation Enhances the Moisture Stability and Gas Sorption Characteristics of Quaternary Metal-Organic Frameworks. J. Am. Chem. Soc. 2015, 137, 3901−3909. (44) Banerjee, R.; Furukawa, H.; Britt, D.; Knobler, C.; O’Keeffe, M.; Yaghi, O. M. Control of Pore Size and Functionality in Isoreticular Zeolitic Imidazolate Frameworks and their Carbon Dioxide Selective Capture Properties. J. Am. Chem. Soc. 2009, 131, 3875−3877. (45) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O’Keeffe, M.; Yaghi, O. M. Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage. Science 2002, 295, 469−472. F

DOI: 10.1021/acsami.7b06010 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

Forum Article

ACS Applied Materials & Interfaces (46) Belmabkhout, Y.; Mouttaki, H.; Eubank, J. F.; Guillerm, V.; Eddaoudi, M. Effect of Pendant Isophthalic Acid Moieties on the Adsorption Properties of Light Hydrocarbons in HKUST-1-like tboMOFs: Application to Methane Purification and Storage. RSC Adv. 2014, 4, 63855−63859. (47) Luebke, R.; Belmabkhout, Y.; Weseliński, Ł. J.; Cairns, A. J.; Alkordi, M.; Norton, G.; Wojtas, Ł.; Adil, K.; Eddaoudi, M. Versatile Rare Earth Hexanuclear Clusters for the Design and Synthesis of Highly-Connected ftw-MOFs. Chem. Sci. 2015, 6, 4095−4102. (48) He, Y. B.; Zhou, W.; Krishna, R.; Chen, B. L. Microporous Metal-Organic Frameworks for Storage and Separation of Small Hydrocarbons. Chem. Commun. 2012, 48, 11813−11831. (49) Bloch, E. D.; Queen, W. L.; Krishna, R.; Zadrozny, J. M.; Brown, C. M.; Long, J. R. Hydrocarbon Separations in a Metal-Organic Framework with Open Iron(II) Coordination Sites. Science 2012, 335, 1606−1610. (50) Assen, A. H.; Belmabkhout, Y.; Adil, K.; Bhatt, P. M.; Xue, D. X.; Jiang, H.; Eddaoudi, M. Ultra-Tuning of the Rare-Earth fcu-MOF Aperture Size for Selective Molecular Exclusion of Branched Paraffins. Angew. Chem., Int. Ed. 2015, 54, 14353−14358. (51) Belmabkhout, Y.; Guillerm, V.; Eddaoudi, M. Low Concentration CO2 Capture Using Physical Adsorbents: Are Metal-Organic Frameworks Becoming the New Benchmark Materials? Chem. Eng. J. 2016, 296, 386−397. (52) Chen, Z. J.; Adil, K.; Weseliński, Ł. J.; Belmabkhout, Y.; Eddaoudi, M. A Supermolecular Building Layer Approach for Gas Separation and Storage Applications: the eea and rtl MOF Platforms for CO2 Capture and Hydrocarbon Separation. J. Mater. Chem. A 2015, 3, 6276−6281. (53) Belmabkhout, Y.; Pillai, R. S.; Alezi, D.; Shekhah, O.; Bhatt, P.; Chen, Z. J.; Adil, K.; Vaesen, S.; De Weireld, G.; Pang, M. L.; Suetin, M.; Cairns, A. J.; Solovyeva, V.; Shkurenko, A.; El Tall, O.; Maurin, G.; Eddaoudi, M. Metal-Organic Frameworks to Satisfy Gas Upgrading Demands: Fine-tuning the soc-MOF Platform for the Operative Removal of H2S. J. Mater. Chem. A 2017, 5, 3293−3303. (54) Sun, T.; Ma, J. P.; Huang, R. Q.; Dong, Y. B. The Inner Salt 4carboxy-2-(pyridinium-4-yl)-1H-imidazole-5-carboxylate Monohydrate. Acta Crystallogr., Sect. E 2006, 62, o2751−o2752. (55) Alcalde, E.; Dinares, I.; Perez-Garcia, L.; Roca, T. An Advantageous Synthesis of 2-Substituted Benzimidazoles Using Polyphosphoric Acid. 2-(Pyridyl)-1H-benzimidazoles, 1-Alkyl-(1Hbenzimidazol-2-yl)pyridinium Salts, their Homologues and Vinylogues. Synthesis 1992, 1992, 395−398. (56) Sheldrick, G. M. SHELXTL-NT, version 5.1; Bruker AXS Inc.: Madison, WI, 1997.

G

DOI: 10.1021/acsami.7b06010 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX