Water-Stable Anionic MetalâOrganic Framework for Highly Selective

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A Water-Stable Anionic Metal-organic Framework for Highly Selective Separation of Methane from Natural Gas and Pyrolysis Gas Lan Li, Xusheng Wang, Jun Liang, Yuan-Biao Huang, Hong-Fang Li, Zu-Jin Lin, and Rong Cao ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b00706 • Publication Date (Web): 30 Mar 2016 Downloaded from http://pubs.acs.org on March 31, 2016

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ACS Applied Materials & Interfaces

A Water-Stable Anionic Metal-organic Framework for Highly Selective Separation of Methane from Natural Gas and Pyrolysis Gas Lan Li, †,‡ Xusheng Wang, ‡ Jun Liang, ‡ Yuanbiao Huang, ‡ Hongfang Li, ‡ Zujin Lin,* ‡ Rong Cao *,†,‡ †

Department of Chemistry, University of Science and Technology, Hefei, Anhui, 230026, P. R.

China ‡

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of

Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China.

ABSTRACT:

A

3D

water-stable

anionic

metal-organic

framework

[Zn4(hpdia)2]·[NH2(CH3)2]·3DMF·4H2O (FJI-C4) was constructed based on an elaborate phosphorous-containing ligand 5,5'-(hydroxyphosphoryl)diisophthalic acid (H5hpdia). FJI-C4 with narrow one-dimensional (1D) pore channels exhibits high selectivity of C3H8/CH4 and C2H2/CH4. It is the first time for the MOF which containing phosphorous for selective separation of methane from natural gas and pyrolysis gas.

KEYWORDS: MOFs, phosphorous, light hydrocarbons, selectivity, water-stable, adsorption 1. INTRODUCTION

ACS Paragon Plus Environment

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Energy consumption and environment degradation are dilemmas in recent industry and society since fossil energy has dominated market share. Among the available fossil energies, natural gas which consisting primarily of methane and varying amounts of C2H6, C3H8, H2O, CO2 etc., deemed to be a preferable alternative fuel since it is naturally abundant and environmentally friendly compared to petrol and diesel.1-2 Pyrolysis gas, the main source of small hydrocarbons, also contains large amounts of methane. Since small hydrocarbons (C2-C3), such as acetylene, ethylene, and ethane are basic feedstock in petro-chemical industry, it is essential to separate such light hydrocarbons from methane to fully utilize them. However, the traditional cryogenic distillation method for the light hydrocarbons separation is not only very energy-consuming but also requires harsh work-conditions, such as high pressure and/or low temperature. Hence, an advanced and energy-efficient separation technology is highly desirable. Among the several newly-developed separation methods, adsorptive separation is a cost- and energy-efficient methods. Metal-organic frameworks (MOFs), which can be straightforwardly self-assembled from organic linkers and metal ions/clusters, have been intensively investigated for applications in gas storage and separation.3-4 Very recently, MOFs have also been employed as a new kind of solid sorbents for separation of light hydrocarbons.5-8 Several strategies, including tailoring pore surface function, tuning pore size and shape, and utilizing structural flexibility, have been adopted to enhance the efficiency of the gas selective adsorption and separation.9-12 Among them, the pore sizes and shapes of the MOFs sorbents are first and foremost for their separation performance. The pore size of an adsorbent which is comparable to or slightly larger than the kinetic diameters of the adsorbates will significantly promote the separation selectivity of these light hydrocarbons. Hence, the design and synthesis of MOFs with narrow pores close to 4.4 Å


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are crucial for their performances in the separation of these light hydrocarbons as the light hydrocarbons (C1-C3) kinetic diameters range from 3.3 to 4.4 Å.8, 12-13 In addition, tailoring pore surface function, such as the immobilization of polar functional groups -OH, -NH2, and / or the formation of charge skeletons, is another effective strategy to improve the MOFs’ separation efficiency based on adsorbate–surface interactions.11, 14-16 Charged MOFs constructed by polar phosphorus-based ligand have usually been exploited for selective separation for CO2 from CH4 or N2, however, to the best of our knowledge, this is the first time we use this type of MOF for selective separation of light hydrocarbons.16-18 Along this line, we have designed and synthesized a novel ligand, 5,5'-(hydroxyphosphoryl)-diisophthalic acid (H5hpdia), to construct microporous MOFs for the selective separation of light hydrocarbons (C1-C3). Since the largest distance between P and C in H5hpdia is 5.260 Å, the pore sizes of the expected MOFs may be close to the kinetic diameters of light hydrocarbons by assumption that both the carboxylate and the O=P-OH are connected to zinc center, which are highly desirable for MOFs’ applications in the separation of light hydrocarbons. Herein, based on H5hpdia, we synthesized a new 3D MOF (denoted as FJI-C4, FJI is short for Fujian Institute of Research on the Structure of Matter, the C in FJI-C4 stands for Cao group) with a square pore size of ca. 5.9×5.9 Å2. The as-prepared anionic MOF FJI-C4 exhibits extraordinarily high selectivity of light hydrocarbons (C2-C3) as well as CO2 with respect to methane at room temperature. The selectivity of FJI-C4 for C3H8/CH4 and C2H2/CH4 is comparable to those of FJI-C119 and higher than JLU-Liu2220. Additionally, FJI-C4 is water-stable and may be a promising candidate for selective separation of methane towards natural gas and pyrolysis gas. 2. EXPERIMENTAL SECTION 2.1 General experimental chemicals and methods


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The starting reagents and solvents were ordered commercially and directly used in the experiments. H5hpdia Ligand was synthesized according to the reported method (Supporting information Scheme 1), and characterized by 1H NMR spectrum under room temperature on a BRUKER AVANCE III spectrometer. The single crystal structure of FJI-C4 was solved by SHELXTL software package using direct methods with difference Fourier techniques.21 The disordered guest molecules in FJI-C4 were eliminated by SQUEEZE program in PLATON22. The purity of FJI-C4 was confirmed by X-ray powder diffraction patterns, which were recorded on a MiniFlex 600 diffractometer with Cu Kα radiation(λ = 1.54056 Å) under room temperature. TG (Thermogravimetric) analysis data were collected on an SDT Q600 analyzer from 20 ºC to 1000 ºC (10 °C min−1) in N2 gas.23 The C, H and N content of FJI-C4 was determined on a Vario MICRO EL III elemental analyzer. Infrared (IR) spectrum was collected on a PerkinElmer Spectrum by using the sample of FJI-C4 diluted by KBr in the region of 400–4000cm−1. The N2, H2, CO2, and light hydrocarbons adsorption data were obtained on an ASAP 2020 equipment. 2.2 Synthesis of [Zn4(hpdia)2]·[NH2(CH3)2]·3DMF·4H2O A solvothermal reaction of Zn(NO3)2·6H2O (74 mg, 0.25 mmol) with H5hpdia (10 mg, 0.025 mmol) in 3ml acidified solvent of DMF/H2O/EtOH(1:1:1 v/v) under 85 ºC for 2days afforded colorless rodlike crystalline products [Zn4(hpdia)2]·[NH2(CH3)2]·3DMF·4H2O (FJI-C4) (Yield: 73%, based on H5hpdia). Elemental analysis for FJI-C4, calcd (%): C, 38.07; H, 3.74; N, 4.93. Found (%): C, 37.59; H, 3.93; N, 4.88. IR(cm-1): 457.70(w), 580.09(m), 682.99(w), 725.15(m), 779.25(m), 890.14(w), 1062.47(m), 1118.89(m), 1161.68(m), 1206.51(m), 1359.90(s), 1390.19(s), 1435.77(s), 1569.49(s), 1626.06(s), 2807.97(w), 3435.72(s). 3. RESULTS AND DISCUSSION


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Description of single crystal structure. Single-crystal X-ray diffraction study reveals that FJIC4 crystallizes in orthorhombic Pbcn space group. The asymmetric unit of FJI-C4 contains one crystallographically independent zinc (II) atom and one H5hpdia ligand locating at C2 axis (Figure S2). Each zinc (II) atom is coordinated by one phosphate oxygen atom and four carboxylate oxygen atoms (Figure 1a). Every hpdia5- ligand takes its four carboxylate and one phosphate groups to link to five separate zinc Secondary Building Units (SBUs). The adjacent zinc cations were connected by two carboxylate groups and a phosphate group to form a

Figure 1. (a) Coordination modes of hpdia5- ligand in FJI-C4 (C, green; P, pink; Zn, blue; O, red); (b) 3D structure of FJI-C4 with square channels view along c axis; (c) Topological presentation of FJI-C4 (benzene rings are indicated in light blue and zinc clusters are indicated in red); (d) The novel zinc SBU [Zn2(COO)4(POO)]- in the FJI-C4 (e) One-dimensional channels of FJI-C4 along c-axis; (f) Space-filling mode of framework in FJI-C4.


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negatively charged aircraft-like dinuclear SBU. As far as we know, this anionic aircraft-like zinc SBU [Zn2(COO)4(POO)]- is unprecedented, which serves as nodes to propagate the skeleton of FJI-C4. Thus, the interconnection of the zinc SBUs with V-shaped ligand H5hpdia composes an anionic infinite framework with square channels along the crystallographic c-axis. The channels with a size of 5.9×5.9 Å2 were occupied by free solvents and highly disordered Me2NH2+ cations (Figure 1c). For clarity, the phenyl rings from the ligands are viewed as 3-connected nodes whilst the aircraft-like SBUs can be regarded as 6-connected nodes. Topological analysis using TOPOS software indicates that FJI-C4 can be regarded as a 3, 6-connected dinodal net as of apo topology with the point symbol of {4·62}2{42·69·84}. PLATON analysis shows that the effective free volume of FJI-C4 is about 52.1% of the crystal volume (1521.0 Å3out of the 2920.7 Å3 unit cell volumes). Gas adsorption and separation properties. To investigate the permanent porosity of FJI-C4, N2 and CO2 sorption experiments were carried out. The N2 sorption isotherm of FJI-C4 at 77 K shows a reversible typical type-Ι isotherm as expected for microporous materials. Derived from N2 sorption isotherm, the Brunauer-Emmett- Teller (BET) surface area and the Langmuir surface area of FJI-C4 are 690 m² g-1 and 781 m² g-1, respectively. A narrow distribution of micropores at appropriate 5.5 Å is calculated by Horvath-Kawazoe method (Figure 2), which is slightly smaller than the value derived from the single crystal structure. The pore volume from t-plot analysis is 0.27 cm3 g-1, which is also smaller than theoretical value from single crystal structure (0.44 cm3 g-1); these discrepancies can be explained by the existence of disorder Me2NH2+ counteractions occupied in the pores of FJI-C4. Since CO2 is dominated component of greenhouse gas and main contaminant of natural gas, it is meaningful to investigate capacity for


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CO2 and selectivity of CO2/CH4. Low pressure CO2 sorption isotherms were also measured at 273 K and 298 K (Figure S9).The amount of CO2

Figure 2. N2 sorption isotherm of FJI-C4 at 77 K. Inset is pore distribution analysis by HorvathKawazoe method. uptake for FJI-C4 is 111.0 cm3g-1 (21.8 wt%) at 273 K and 60.3 cm3 g-1 (11.2 wt%) at 298 K under 1 bar, respectively. Compared with the enormous MOFs, the amount of MOFs which exhibit over 20.0 wt% CO2 uptakes at 273 K and 1 bar is relatively small.24-25 The heat of adsorption (Qst) for CO2 in FJI-C4 ranges from 22 kJ mol-1 to 35 kJ mol-1 calculated by Clausius-Clapeyron equation (Figure S10). Considering the small pore size, charged skeleton and intrinsic permanent porosity of FJI-C4, we have investigated its potential application for light hydrocarbons adsorption and separation. Although many MOFs with excellent gas sorption capacity (such as H2, CO2, and CH4) have been reported, only a few MOFs show high sorption capacity and selectivity towards light hydrocarbons. To examine the sorption and separation of light hydrocarbons of FJI-C4, single component gas sorption isotherms of FJI-C4 for various light hydrocarbons (CH4, C2H2, C2H4,


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C2H6, and C3H8) were performed both at 273 K and 298 K. As expected, FJI-C4 can take up high amount of C3H8 (74.7 cm3 g-1), C2H2 (82.8 cm3 g-1), C2H6 (73.4 cm3 g-1), C2H4 (70.1 cm3 g-1) but relatively lower amount of CH4 (32.7 cm3 g-1) at 273 K and 1 bar (Figure 3a, ). It should be noted that, the sorption capacity of FJI-C4 for C3H8 (71.5 cm3 g-1), C2H2 (72.5cm3 g-1), C2H6 (66.3 cm3 g-1), C2H4 (61.4 cm3 g-1) and CH4 (18.4 cm3 g-1) at 298 K and 1 bar are higher than those of UTSA-35a and UTSA-36a (Figure 3b).8, 13 The magnitude of the adsorption enthalpies reveals the affinity of the pore surface toward adsorbents, which plays a significant part in determining the adsorptive selectivity.23 To evaluate the affinity of such light hydrocarbons in FJI-C4, the heats of adsorption were calculated by Clausius-Clapeyron equation. The adsorption enthalpy for CH4, C2H2, C2H4, C2H6 and C3H8 were in the range of 20.8-23.1 kJ mol−1, 27.0-31.7 kJ mol−1, 33.1-42.6 kJ mol−1, 32.7-40.9 kJ mol−1, and 31.1-42.9 kJ mol−1， respectively. (Figure S11). The C2-C3 light hydrocarbons with higher adsorption enthalpy may provide stronger affinity with skeleton, which resulting these gases are preferentially adsorbed on skeleton of FJI-C4. Thus， it may have high selectivity of C2-C3 light hydrocarbons with respect to CH4. Therefore, the potential for separation of methane from C2-C3 light hydrocarbons have appraised by ideal solution adsorbed theory (IAST) for binary equimolar components (Figure 3c). At 1 bar and 298 K, the selectivity of C3H8, C2H2, C2H4 and C2H6 with respect to CH4 are 293.4, 51.0, 22.1 and 39.7, respectively. These calculated selectivities are higher than the corresponding values of USTA-35a, JIU-Liu22 and many other reported MOFs (Table S1).15,

26-29

Remarkably, the

selectivity of C3H8/CH4 on FJI-C4 ranges from 293.4 to 469.7, which is nearly equivalent to the current highest values of FJI-C1 (range from 78.7 to 471).19 The results indicate that FJI-C4 is a prospective absorbent for effectively selective adsorptive separation of CH4 from C2-C3


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hydrocarbons at room temperature. It should be noted that, for equimolar gas-phase mixtures at 1 bar, the predicted CO2/CH4 selectivity by IAST is 12.4 at 273 K and 8.0 at 298 K (Figure S12 and Figure S13), respectively, which is comparable to QI-Cu and outperform Cu3(BTC)2, JLULiu5.30-32 Such high selectivities further imply that FJI-C4 has considerable potential natural gas

Figure 3. (a)The light hydrocarbons (CH4, C2H2, C2H4, C2H6, and C3H8) adsorption isotherms of FJI-C4 at 298 K; (b)The light hydrocarbons adsorption isotherms of FJI-C4 at 273 K; (c) Adsorption selectivity of C3H8, C2H2, C2H4, and C2H6 with respect to CH4 are predicted by IAST at 298 K for binary equimolar mixtures.


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purification. The high adsorption selectivity of C2-C3/CH4 could be attributed to three factors: (i) the narrow pore size of FJI-C4 matches with the kinetic diameters of C2-C3 light hydrocarbons resulting in their high C2-C3/CH4 sieving effects; (ii) the charged skeleton and cationic counterions (Me)2NH2+ enhance adsorbent–adsorbate interaction through charge-induced force, whereas, C2-C3 light hydrocarbons as well as CO2 generate stronger interactions between adsorbent–adsorbate due to their higher polarizability compared with CH4; and (iii) π–π interactions of benzene rings of FJI-C4 towards acetylene and ethene may improve their adsorption capacities.11,

19-20, 33-35

The polarizability and quadrupole moment of these gases

showed in Table S2. Water-Stable and Thermal-Stable Properties. The water-stability and thermal-stability are prerequisites for the practical applications in natural gas purification and the adsorptive separation of light hydrocarbons. Factors influencing structural stability of MOFs in water including basicity of the ligand, metal–ligand bond strength, type of metal center and coordination number oxidation state of the metal center, chemical functionality of the linker, etc.36 To date, in order to improve the water-stability of MOFs, several methods have been explored in previous work, for instance, mimicking of the zeolite structure such as ZIFs and using of high charged metal centers, such as Cr3+, Ti4+ and Zr4+ to build MOFs.37-38 The zincbased water-stable MOFs, however, are rare. Remarkably, FJI-C4 exhibit extraordinary waterstability when immersed in deionized water and even in boiling water (Figure S14). As we know, the phosphonates form stronger bonds than carboxylates do with metal atoms and try to synthesized phosphonate-based MOFs is a promising way to obtain stable MOFs.39 In our case, the water-stable FJI-C4 may benefit from the stronger coordination bonds between the metal and phosphorous-containing ligands. Therefore, the unprecedented zinc-based water-stable


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[Zn2(COO)4(POO)]- may serve as a platform to the design and synthesis of new zinc-based water-stable MOFs. Thermogravimetric analysis (TGA) performed on the as-prepared FJI-C4 reveals that materials underwent a continuous weight loss below 250 °C, which can be ascribed to the loss of all free molecules. Thereafter, the weight remains almost constant until the framework begins to collapse at 390 °C. These observations suggest FJI-C4 is water-stable and thermal-stable and can be a potential candidate for real application. 4. CONLUSION In summary, we have developed and characterized a new microporous MOF FJI-C4 based on a predesigned phosphoryl carboxylate ligand. The zinc-based FJI-C4 is water-stable and thermal-stable. Moreover, FJI-C4 has just the right pore size of features to maximize interactions between gases and frameworks, so it exerts high separation selectivity for C2 -C3 light hydrocarbons as well as CO2 with respect to CH4. These results indicate that FJI-C4 could be a promising candidate for fuel gas purification and separation of light hydrocarbons in the near future.

ASSOCIATED CONTENT Supporting Information NMR spectrum, experimental procedure, additional structural figures, PXRD patterns, TGA curves, gas adsorption isotherms, derivation of the isosteric heats of adsorption for light hydrocarbons, and CO2, selectivity of CO2/CH4, CO2/N2 and crystallographic data for FJI-C4. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION


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Corresponding Author E-mail: [email protected], Fax: (+86)-591-83796710, Tel:(+86)-591-63173153 (Rong Cao) E-mail: [email protected]; (+86)-591-63173153 (Zujin Lin) Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was financially supported by the 973 Program (2012CB821705, 2013CB933203), NSFC (21521061, 21331006, 21303205 and 21571177), the "Strategic Priority Research Program" of the Chinese Academy of Sciences (XDA09030102), and the Natural Science Foundation of Fujian Province of China (2014J05020). REFERENCES 1.

He, Y. B.; Zhou, W.; Qian, G. D.; Chen, B. L. Methane Storage in Metal-Organic

Frameworks. Chem. Soc. Rev. 2014, 43, 5657-5678. 2.

Makal, T. A.; Li, J. R.; Lu, W.; Zhou, H. C. Methane Storage in Advanced Porous

Materials. Chem. Soc. Rev. 2012, 41, 7761-7779. 3.

Lin, Z. J.; Lv, J.; Hong, M. C.; Cao, R. Metal-Organic Frameworks Based on Flexible

Ligands (FL-MOFs): Structures and Applications. Chem. Soc. Rev. 2014, 43, 5867-5895. 4.

Lin, Z. J.; Huang, Y. B.; Liu, T. F.; Li, X. Y.; Cao, R. Construction of a Polyhedral

Metal-Organic Framework Via a Flexible Octacarboxylate Ligand for Gas Adsorption and Separation. Inorg. Chem. 2013, 52, 3127-3132.


12

Page 13 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


5.

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. 6.

Hu, T. L.; Wang, H.; Li, B.; Krishna, R.; Wu, H.; Zhou, W.; Zhao, Y.; Han, Y.; Wang,

X.; Zhu, W.; Yao, Z.; Xiang, S. C.; Chen, B. L. Microporous Metal-Organic Framework with Dual Functionalities for Highly Efficient Removal of Acetylene from Ethylene/Acetylene Mixtures. Nat. Commun. 2015, 6, 7328. 7.

He, Y. B.; Krishna, R.; Chen, B. L. Metal–Organic Frameworks with Potential for

Energy-Efficient Adsorptive Separation of Light Hydrocarbons. Energy & Environ. Sci. 2012, 5, 9107-9120. 8.

He, Y. B.; Zhang, Z. J.; Xiang, S. C.; Fronczek, F. R.; Krishna, R.; Chen, B. L. A Robust

Doubly Interpenetrated Metal-Organic Framework Constructed from a Novel Aromatic Tricarboxylate for Highly Selective Separation of Small Hydrocarbons. Chem. Commun. 2012, 48, 6493-6495. 9.

Li, J. R.; Sculley, J.; Zhou, H. C. Metal-Organic Frameworks for Separations. Chem. Rev.

2012, 112, 869-932. 10. Lin, Z. J.; Liu, T. F.; Huang, Y. B.; Lu, J.; Cao, R. A Guest-Dependent Approach to Retain Permanent Pores in Flexible Metal-Organic Frameworks by Cation Exchange. Chem. Eur. J. 2012, 18, 7896-7902. 11. Li, J. R.; Kuppler, R. J.; Zhou, H. C. Selective Gas Adsorption and Separation in MetalOrganic Frameworks. Chem. Soc. Rev. 2009, 38, 1477-1504.


13


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 18

12. 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. 13. He, Y. B.; Zhang, Z. J.; Xiang, S. C.; Fronczek, F. R.; Krishna, R.; Chen, B. L. A Microporous Metal-Organic Framework for Highly Selective Separation of Acetylene, Ethylene, and Ethane from Methane at Room Temperature. Chem. Eur. J. 2012, 18, 613-619. 14. 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. 15. Xu, H.; Cai, J..F; Xiang, S. C.; Zhang, Z. J.; Wu, C. D.; Rao, X. T.; Cui, Y. J.; Yang, Y.; Krishna, R.; Chen, B. L.; Qian, G. D. A Cationic Microporous Metal–Organic Framework for Highly Selective Separation of Small Hydrocarbons at Room Temperature. J. Mater. Chem. A 2013, 1, 9916-9921. 16. Bohnsack, A. M.; Ibarra, I. A.; Hatfield, P. W.; Yoon, J. W.; Hwang, Y. K.; Chang, J. S.; Humphrey, S. M. High Capacity CO2 Adsorption in a Mg(II)-Based Phosphine Oxide Coordination Material. Chem. Commun. 2011, 47, 4899-4901. 17. Li, X. J.; Jiang, F. L.; Wu, M. Y.; Chen, L.; Qian, J. J.; Zhou, K.; Yuan, D. Q.; Hong, M. C. Construction of Two Microporous Metal-Organic Frameworks with flu and pyr Topologies Based on Zn4(µ3-OH)2(CO2)6 and Zn6(µ6-O)(CO2)6 Secondary Building Units. Inorg. Chem. 2014, 53, 1032-1038.


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18. Lee, W. R.; Ryu, D. W.; Lee, J. W.; Yoon, J. H.; Koh, E. K.; Hong, C. S. Microporous Lanthanide-Organic Frameworks with Open Metal Sites: Unexpected Sorption Propensity and Multifunctional Properties. Inorg. Chem. 2010, 49, 4723-4725. 19. Huang, Y. B.; Lin, Z. J.; Fu, H. R.; Wang, F.; Shen, M.; Wang, X. S.; Cao, R. Porous Anionic Indium-Organic Framework with Enhanced Gas and Vapor Adsorption and Separation Ability. ChemSusChem 2014, 7, 2647-2653. 20. Wang, D. M.; Liu, B.; Yao, S.; Wang, T.; Li, G. H.; Huo, Q. S.; Liu, Y. L. A Polyhedral Metal-Organic Framework Based on the Supermolecular Building Block Strategy Exhibiting High Performance for Carbon Dioxide Capture and Separation of Light Hydrocarbons. Chem. Commun. 2015, 51, 15287-15289. 21. Sheldrick, G. M. SHELXS-97. Program for Crystal Structure Solution and Refinement; University of Göttingen: Göttingen, Germany, 1997. 22. Spek, A. L. Single-Crystal Structure Validation with Program PLATON. J. Appl. Crystallogr. 2003, 36, 7-13. 23. Yang, Y. Y.; Lin, Z. J.; Liu, T.-T.; Liang, J.; Cao, R. Synthesis, Structures and Physical Properties of Mixed-Ligand Coordination Polymers Based on a V-Shaped Dicarboxylic Ligand. CrystEngComm 2015, 17, 1381-1388. 24. 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.


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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 18

25. D'Alessandro, D. M.; Smit, B.; Long, J. R. Carbon Dioxide Capture: Prospects for New Materials. Angew. Chem. Int. Ed. 2010, 49, 6058-6082. 26. Li, J.; Fu, H. R.; Zhang, J.; Zheng, L. S.; Tao, J. Anionic Metal-Organic Framework for Adsorption and Separation of Light Hydrocarbons. Inorg. Chem. 2015, 54, 3093-3095. 27. Fu, H. R.; Wang, F.; Zhang, J. A Stable Zinc-4-Carboxypyrazole Framework with High Uptake and Selectivity of Light Hydrocarbons. Dalton Trans. 2015, 44, 2893-2896. 28. Li, J.; Guo, Y.; Fu, H. R.; Zhang, J.; Huang, R. B.; Zheng, L. S.; Tao, J. A Spin-Canted NiII4-Based Metal-Organic Framework with Gas Sorption Properties and High Adsorptive Selectivity for Light Hydrocarbons. Chem. Commun. 2014, 50, 9161-9164. 29. Duan, X.; He, Y. B.; Cui, Y. J.; Yang, Y.; Krishna, R.; Chen, B. L.; Qian, G. D. Highly Selective Separation of Small Hydrocarbons and Carbon Dioxide in a Metal–Organic Framework with Open Copper(II) Coordination Sites. RSC Adv. 2014, 4, 23058-23063. 30. Wang, D. M.; Zhao, T. T.; Cao, Y.; Yao, S.; Li, G. H.; Huo, Q. S.; Liu, Y. L. High Performance Gas Adsorption and Separation of Natural Gas in Two Microporous Metal-Organic Frameworks with Ternary Building Units. Chem. Commun. 2014, 50, 8648-8650. 31. Xiang, Z. H.; Peng, X.; Cheng, X.; Li, X. J.; Cao, D. P. CNT@Cu3(BTC)2 and Metal– Organic Frameworks for Separation of CO2/CH4 Mixture. J. Phys. Chem. C 2011, 115, 1986419871. 32. 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.


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Page 17 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


33. Das, M. C.; Xu, H.; Xiang, S. C.; Zhang, Z. J.; Arman, H. D.; Qian, G. D.; Chen, B. L. A New Approach to Construct a Doubly Interpenetrated Microporous Metal-Organic Framework of Primitive Cubic Net for Highly Selective Sorption of Small Hydrocarbon Molecules. Chem. Eur. J. 2011, 17, 7817-7822. 34. Humphrey, S. M.; Oungoulian, S. E.; Yoon, J. W.; Hwang, Y. K.; Wise, E. R.; Chang, J. S. Hysteretic Sorption of Light Gases by a Porous Metal-Organic Framework Containing Tris(Para-Carboxylated) Triphenylphosphine Oxide. Chem. Commun. 2008, 2891-2893. 35. Chaemchuen, S.; Kabir, N. A.; Zhou, K.; Verpoort, F. Metal-Organic Frameworks for Upgrading Biogas Via CO2 Adsorption to Biogas Green Energy. Chem. Soc. Rev. 2013, 42, 9304-9332. 36. Qadir, N. u.; Said, S. A. M.; Bahaidarah, H. M. Structural Stability of Metal Organic Frameworks in Aqueous Media – Controlling Factors and Methods to Improve Hydrostability and Hydrothermal Cyclic Stability. Microporous Mesoporous Mater. 2015, 201, 61-90. 37. Burtch, N. C.; Jasuja, H.; Walton, K. S. Water Stability and Adsorption in Metal-Organic Frameworks. Chem. Rev. 2014, 114, 10575-10612. 38. Jasuja, H.; Jiao, Y.; Burtch, N. C.; Huang, Y. G.; Walton, K. S. Synthesis of Cobalt-, Nickel-, Copper-, and Zinc-Based, Water-Stable, Pillared Metal-Organic Frameworks. Langmuir 2014, 30, 14300-14307. 39. Gagnon, K. J.; Perry, H. P.; Clearfield, A. Conventional and Unconventional MetalOrganic Frameworks Based on Phosphonate Ligands: MOFs and UMOFs. Chem. Rev. 2012, 112, 1034-1054.


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Water-Stable Anionic MetalâOrganic Framework for Highly Selective

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Water-Stable Anionic MetalâOrganic Framework for Highly Selective