MetalâOrganic Framework with Trifluoromethyl Groups for Selective

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Metal–Organic Framework with Trifluoromethyl Groups for Selective C2H2 and CO2 Adsorption Osamah Alduhaish, Rui-Biao Lin, Hailong Wang, Bin Li, Hadi D. Arman, Tong-Liang Hu, and Banglin Chen Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00506 • Publication Date (Web): 19 Jun 2018 Downloaded from http://pubs.acs.org on June 23, 2018

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Crystal Growth & Design

Metal–Organic Framework with Trifluoromethyl Groups for Selective C2H2 and CO2 Adsorption Osamah Alduhaish,a,b Rui-Biao Lin,*,b Hailong Wang,b Bin Li,b Hadi D. Arman,b Tong-Liang Hu,c and Banglin Chen*,b a

Department of Chemistry, Faculty of Science, King Saud University, Riyadh, Saudi Arabia. b Department of Chemistry, University of Texas at San Antonio, San Antonio, Texas 78249-0698, USA, Emails: [email protected] ; [email protected] c School of Materials Science and Engineering, National Institute for Advanced Materials, Nankai University, Tianjin 300350, China. Dedicated to Professor Xintao Wu on the occasion of his 80th birthday ABSTRACT: Reaction of CuSiF6·xH2O and 1,4-bis(4-pyridyl)-2-trifluoromethylbenzene (bpb-CF3) through liquid diffusion produced a porous SIFSIX-type metal-organic framework, [Cu(bpb-CF3)2(SiF6)] (UTSA-121) containing functional trifluoromethyl groups. Single-crystal X-ray diffraction analysis of UTSA-121 showed that bpb-CF3 can well substitute the prototypal dipyridine ligand to form a non-interpenetrated pcu framework, which is highly porous (void = 65.7%) with three-dimensional intersecting channels with functionalized trifluoromethyl groups on the pore surface. The Brunauer–Emmett–Teller (BET) surface area of the activated UTSA-121a is up to 1081 m2 g−1. Gas sorption measurements of UTSA-121a revealed high C2H2 and CO2 uptakes at room temperature. Furthermore, IAST calculations revealed that UTSA-121a shows highly selective adsorption of C2H2 and CO2 over CH4 and N2 under ambient condition. Keywords: Metal-Organic Framework, SIFSIX, Trifluoromethyl, Methane, Carbon dioxide. 1

ACS Paragon Plus Environment

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INTRODUCTION The development of modern human society is highly dependent on the application of fossil fuels, whereas the ensuing environmental concerns drive up demands for clean energy and technologies. For lower carbon emission, energy-efficient carbon dioxide capture and separation using physical adsorbents such as metal–organic frameworks (MOFs, or PCPs for porous coordination polymers) during energy production process have attracted great interest.1 It is because the exceptional uptake capacities and selectivities for carbon dioxide under ambient conditions demonstrate that MOFs can serve as excellent candidates during related process.2 Another approach is using natural gas consisting primarily of methane, which is the cleanest fossil fuel, considering its carbon dioxide emission per joule delivered energy is 25–30% and 40–45% less than those of oil and coal respectively.3 Simultaneously, its natural abundance and high energy intensity contribute together to a worldwide gas consumption of over 3.5 trillion cubic meters in 2015. There are certain contaminants in raw natural gas, such as higher hydrocarbons, carbon dioxide, nitrogen, hydrogen sulfide, and helium. In some sources, like biogas, the level of carbon dioxide even exceeding 40% is unacceptable. This is because the presence of carbon dioxide will not only lower the energy level of the gas but also induce corrosion problem of the pipeline. Therefore, pre-combustion upgrading of raw natural gas including removal of carbon dioxide and nitrogen is necessary for commercial quality gas to the end markets. All above process have spurred the exploration of new porous materials.4-7 As a unique class of porous material, MOFs are very promising adsorbents for gas separation and purification owing to their exceptional porosity, high modularity and diverse functionality.8-13 The pore engineering of MOFs now allows precise control of pore 2


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structure, facilitating specific binding with target gas molecules for selective adsorption.14-17 The accuracy of size control can even be achieved to sub-angstrom level.18 In term of carbon dioxide and light hydrocarbons separation,19-24 the SIFSIX materials are notable for their exceptional capture performance under ambient condition.25-29 The pore chemistry and size control in this type of MOFs is straightforward considering their concise reticular networks. An effective approach is organic linker substitution involving length extension,30 which allows many SIFSIX-type MOFs to be state-of-art adsorbents for certain

important

gas

processing.25,26,29

However,

other

strategies

like

ligand

functionalization featuring the immobilization of certain functional groups are rarely reported.31-33 Our recent results demonstrated that trifluoromethyl group plays an important role in hydrocarbons adsorption, giving not only large uptake capacity but also high selectivity.34,35 Herein, to introduce trifluoromethyl group into SIFSIX-MOFs, we used 1,4-bis(4-pyridyl)-2-trifluoromethylbenzene (bpb-CF3) as a substituted ligand to construct a SIFSIX-type MOF, [Cu(bpb-CF3)2(SiF6)] (UTSA-121), showing highly porous, large gas uptake capacity and gas-adsorption selectivity under ambient condition.

EXPERIMENTAL SECTION Synthesis of UTSA-121 [Cu(bpb-CF3)2(SiF6)]. Purple cubic crystals of UTSA-121 were obtained

from

slow

diffusion

of

2

mL

methanol

solution

of

1,4-bis(4-pyridyl)-2-trifluoromethylbenzene (bpb-CF3, 0.1 mmol, 30.0mg) into an aqueous solution (2 mL) of CuSiF6·xH2O (0.15 mmol, 30.9 mg) with a buffered layer of 3



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MeOH/H2O mixture (1:1, 4 mL). After 10 days, purple crystals were then collected, washed with methanol, and dried (yield: 62% based on bpb-CF3). IR /cm-1 (KBr): 1617 (s), 1486 (m), 1429 (m), 1327(s), 1279 (w), 1259 (m), 1226 (m), 1189 (m), 1121 (s), 1080 (w), 1048 (w), 1014 (w), 908(w), 826 (s), 729 (w), 687 (s), 659 (s), 605 (m), 578 (w), 557 (w), 530 (w), 485 (w), 469 (s). Gas Selectivities Calculation. Based on the IAST (ideal absorbed solution theory) method proposed by Myers and Prausnitz36, the separation performance of UTSA-121a for different binary gases mixtures were calculated. The involving mixtures are C2H2/CH4 (50/50 in v/v, the same as followed), CO2/CH4 (50/50) and CO2/N2 (15/85). Experimental data from related adsorption isotherms at ambient temperatures (273 and 298 K) were used to conduct the calculation. The fitting parameters and results are presented in Figures 5 and S7, Tables 1 and S3.

Figure

1.

Single-crystal

structure

of

[Cu(bpb-CF3)2(SiF6)]

(UTSA-121);

the 4


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two-dimensional dipyridine layers are connected through SiF62− anions to give a 3D framework with rectangular channels viewed along the crystallographic [001] direction. Color code: gray, C; light blue, N; bright green, F; light orange, Si; green polyhedra, Cu.

RESULTS AND DISCUSSION Slow diffusion of a methanol solution of bpb-CF3 into an aqueous solution of copper hexafluorosilicate hydrate at room temperature afforded purple block crystals of [Cu(bpb-CF3)2(SiF6)] (UTSA-121). X-ray diffraction analysis reveals that UTSA-121 crystallizes in tetragonal P4/mmm space group (Table S1), showing isostructural structure with the previously reported MOF [Zn(bpb)2(SiF6)] (bpb = 1,4-bis(4-pyridyl)benzene).37 Each copper center is octahedrally coordinated by the four different pyridyl N atoms (from bpb-CF3 ligands) and two different F atoms (from SiF62− anions) (Figures 1 and S1). The coordination framework in UTSA-121 is a non-interpenetrated three-dimensional (3D) pcu net composed of octahedral Cu(py)4(SiF6)2 (py = pyridyl groups) cores and 2-connected bpb-CF3 and SiF62− linkers. The introduced trifluoromethyl groups randomly dangling near the center of organic ligands, results in undulating pore surface. In UTSA-121, the apertures along the crystallographic a- and c-axis are 5.0 Å × 6.2 and 7.1 × 14.5 Å2, respectively (Figure 2). The potential accessible volume is estimated to 1224 Å3 per unit cell (volume = 1864 Å3), determined by PLATON calculation, that is 65.7% void per unit volume for UTSA-121. The phase purity of the as-synthesized sample was confirmed through powder X-ray diffraction (PXRD) analysis (Figure S3). The thermogravimetric analysis (TGA) of UTSA-121 revealed that it lost all guests molecules 5



at ca. 90 °C (10% weight loss) and decomposed at ca. 200 °C (Figure S2).

Figure 2. The pore surface of 3D channels viewed along [001] and [100], highlighted as yellow and gray curved planes for the inner and outer side, respectively. 400

Uptake (cm3/g, STP)

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300

200

100

0

0.0

0.2

0.4

0.6

0.8

1.0

P/P0 Figure 3. N2 sorption isotherms of UTSA-121a at 77 K (solid circles: adsorption, open circles: desorption). The permanent porosity of UTSA-121 was examined N2 sorption experiment at 77 K. 6


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Prior to gas sorption, methanol-exchanged UTSA-121 was degassed under high vacuum at 298 K for 24 hours, resulting in the activated phase UTSA-121a. The PXRD pattern revealed that UTSA-121a can well retain the framework after solvent removal as compared with its simulated one obtained from crystallographic data (Figure S3). As shown in Figure 3, the N2 sorption isotherm for UTSA-121a at 77 K shows a type IV feature with an uptake capacity of about 354 cm3 g−1. Its corresponding pore volume is 0.55 cm3 g−1, which is lower than its theoretical one of 0.91 cm3 g−1 (based on its crystal structure) owing to the insufficient filling of N2 on the undulating pore surfaces of UTSA-121 (Figure 2). The accompanied two-step hysteresis might be attributed to the rotations of dynamic organic linker implied by their disorder distribution, or to the possible crystal defects implied by the mesoporous feature of sorption isotherm. The Brunauer−Emmett−Teller (BET) and Langmuir surface areas can be calculated up to 1081 and 1447 m2 g−1 (Figure S4), respectively, which are comparable to that of SIFSIX-1-Cu (1346 m2 g−1)38 but higher than UTSA-48a (285 m2 g−1)39 in the same type MOFs. Additionally, the measured pore size distribution centered at about 8.6 Å (Figure S5) is comparable with the crystal structure of UTSA-121. Hence, the immobilization of trifluoromethyl groups does not substantially reduce the porosity of such framework.

7



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Figure 4. C2H2 (bright green), CO2 (blue), CH4 (red), and N2 (black) sorption isotherms of UTSA-121a at (a) 273 K and (b) 298 K, respectively (adsorption and desorption are showed as solid and open symbols, respectively).

The considerably large surface area combined with possible active sites like other SIFSIX materials enable UTSA-121a to serve as potential candidate for important gas separation such as methane purification. Consequently, single-component gas sorption isotherms of UTSA-121a for C2H2, CO2, CH4, and N2 at 273 and 298 K have been collected to evaluate its separation capacity and selectivity. As shown in the Figure 4, at 1 atm and 273 K, UTSA-121a can take up considerable amounts of C2H2 (103 cm3 g−1) and CO2 (59.4 cm3 g−1), far higher than that of CH4 (11.0 cm3 g−1), and N2 (3.9 cm3 g−1). And at 298 K, the uptake capacities for C2H2, CO2, CH4, and N2 were measured to be 71.3, 36.4, 6.3 and 2.2 cm3 g−1, respectively. Obviously, the C2H2 and CO2 uptake capacity of UTSA-121a are higher than those of M’MOF-3, Mg(HCOO)2, UTSA-48a,39 and so on,40 although lower than some benchmark materials such as SIFSIX-1-Cu.27,41 Notably, the uptake capacity of UTSA-121a for CH4 is far lower than many MOFs, e.g. SIFSIX-2-Cu-i (10.5 cm3 g−1), SIFSIX-3-Zn (17.6 cm3 g−1), Mg-MOF-74 (24.9 cm3 8


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g−1),25 which means it can avoid the loss of methane and the capture capacity for impurity during separation process. The coverage-dependent adsorption enthalpies of UTSA-121a for C2H2 and CO2 were then calculated using the virial method (Figure S6), based on the fittings of their single-component adsorption isotherms at ambient temperatures. The adsorption heats of UTSA-121a at zero coverage for C2H2 and CO2 were calculated to be 22.6, 21.9 kJ mol −1, respectively, which is comparable to some MOFs with open metal sites, e.g. HKUST-1 (30.4 and 25.3 kJ mol

−1

for C2H2 and CO2, respectively).42 In

contrast, the adsorption heat for CH4 is only 15.0 kJ mol −1, which can be attributed to the less polar nature of CH4 that results a weaker interaction with the pore surface. Accordingly, the IAST calculation is further applied to UTSA-121a for different binary gas mixtures including 50/50 C2H2/CH4 and 50/50 CO2/CH4. The adsorption selectivities of UTSA-121a for these binary gas mixtures at different temperatures have been calculated (Figures 5 and S7-9, Table 1 and S3). At 100 kPa, the selectivities of UTSA-121a for equimolar C2H2 and CO2 over CH4 were calculated to be 82 and 11 at 273 K, and 96 and 10 at 298 K, respectively, being higher than those of UTSA-48a and HKUST-1.39,43 Additionally, the CO2/N2 selectivity at 100 kPa and 298 K was calculated to be 42, which is higher than that of SIFSIX-2-Cu and comparable with that of SIFSIX-2-Cu-i.25 The above results have demonstrated that the functionalization of SIFSIX-type MOFs can result in new adsorbent materials of remarkable separation performance.

9



(a)

Page 10 of 16

(b)

(c)

(d)

Figure 5. Calculated mixture adsorption isotherms (a-c) and corresponding selectivities (d) of UTSA-121a for 50/50 C2H2/CH4, 50/50 CO2/CH4 and 15/85 CO2/N2 at 298 K, obtained from IAST calculation.

Table 1. IAST selectivities of 50/50 C2H2/CH4, 50/50 CO2/CH4 and 15/85 CO2/N2. mixture

Temperature (K)

Component proportion[a]

IAST selectivity[b]

C2H2/CH4

273

50/50

82

CO2/CH4

273

50/50

11

CO2/N2

273

15/85

46

C2H2/CH4

298

50/50

96

CO2/CH4

298

50/50

10

CO2/N2

298

15/85

42

[a]

The volume ratio of mixtures. [b]IAST selectivity value at 100 kPa.

10


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CONCLUSION In summary, linker substitution based on functional dipyridyl ligand, a new SIFSIX-type MOF UTSA-121 with immobilized trifluoromethyl groups on the pore surfaces was successfully obtained. This MOF shows highly selective adsorption for acetylene and carbon dioxide, as revealed by gas sorption measurements and selectivity calculations. In addition, its limited methane uptake but high impurity capacity makes UTSA-121 likely applicable to natural gas separation and purification. These results will facilitate the design and synthesis of novel functional SIFSIX-MOF materials for some important gas separations during energy and chemical processing.

Supporting information The supporting information is available free of charge on the ACS Publications website at DOI: xxx Experimental details and additional figures/tables.

Corresponding Author *E-mail: [email protected]; [email protected]. Notes The authors declare no competing financial interest.

ACKNOWLEDGEMENT This work was supported by the grant AX-1730 from the Welch Foundation (B.C.). 11



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References (1) Li, H.; Wang, K.; Sun, Y.; Lollar, C. T.; Li, J.; Zhou, H.-C., Recent advances in gas storage and separation using metal–organic frameworks. Mater. Today 2018, 21, 108-121. (2) Cui, Y.; Li, B.; He, H.; Zhou, W.; Chen, B.; Qian, G., Metal–Organic Frameworks as Platforms for Functional Materials. Acc. Chem. Res. 2016, 49, 483-493. (3) Herberg, M., Natural Gas in Asia: History and Prospects. ed.; Pacific Energy Summit: Jakarta, Indonesia, 2011. (4) Ye, Y.; Xiong, S.; Wu, X.; Zhang, L.; Li, Z.; Wang, L.; Ma, X.; Chen, Q.-H.; Zhang, Z.; Xiang, S., Microporous Metal–Organic Framework Stabilized by Balanced Multiple Host–Couteranion Hydrogen-Bonding Interactions for High-Density CO2 Capture at Ambient Conditions. Inorg. Chem. 2016, 55, 292-299. (5) Chen, Y.; Li, Z.; Liu, Q.; Shen, Y.; Wu, X.; Xu, D.; Ma, X.; Wang, L.; Chen, Q.-H.; Zhang, Z.; Xiang, S., Microporous Metal–Organic Framework with Lantern-like Dodecanuclear Metal Coordination Cages as Nodes for Selective Adsorption of C2/C1 Mixtures and Sensing of Nitrobenzene. Cryst. Growth Des. 2015, 15, 3847-3852. (6) Wang, L.; Ye, Y.; Li, Z.; Lin, Q.; Ouyang, J.; Liu, L.; Zhang, Z.; Xiang, S., Highly Selective Adsorption of C2/C1 Mixtures and Solvent-Dependent Thermochromic Properties in Metal–Organic Frameworks Containing Infinite Copper-Halogen Chains. Cryst. Growth Des. 2017, 17, 2081-2089. (7) Yao, Z.; Zhang, Z.; Liu, L.; Li, Z.; Zhou, W.; Zhao, Y.; Han, Y.; Chen, B.; Krishna, R.; Xiang, S., Extraordinary Separation of Acetylene ‐ Containing Mixtures with Microporous Metal–Organic Frameworks with Open O Donor Sites and Tunable Robustness through Control of the Helical Chain Secondary Building Units. Chem. Eur. J. 2016, 22, 5676-5683. (8) Rungtaweevoranit, B.; Diercks, C. S.; Kalmutzki, M. J.; Yaghi, O., Spiers Memorial Lecture: Progress and prospects of reticular chemistry. Faraday Discuss. 2017, 201, 9-45. (9) Banerjee, D.; Wang, H.; Gong, Q.; Plonka, A. M.; Jagiello, J.; Wu, H.; Woerner, W. R.; Emge, T. J.; Olson, D. H.; Parise, J. B.; Li, J., Direct structural evidence of commensurate-to-incommensurate transition of hydrocarbon adsorption in a microporous metal organic framework. Chem. Sci. 2016, 7, 759-765. (10) Huang, Y.-B.; Liang, J.; Wang, X.-S.; Cao, R., Multifunctional metal-organic framework catalysts: synergistic catalysis and tandem reactions. Chem. Soc. Rev. 2017, 46, 126-157. (11) Pang, J.; Yuan, S.; Qin, J.; Liu, C.; Lollar, C.; Wu, M.; Yuan, D.; Zhou, H.-C.; Hong, M., Control the Structure of Zr-Tetracarboxylate Frameworks through Steric Tuning. J. Am. Chem. Soc. 2017, 139, 16939-16945. (12) Zhai, Q.-G.; Bu, X.; Mao, C.; Zhao, X.; Daemen, L.; Cheng, Y.; Ramirez-Cuesta, A. J.; Feng, P., An ultra-tunable platform for molecular engineering of high-performance crystalline porous materials. Nat. Commun. 2016, 7, 13645. (13) Zhang, Z.; Nguyen, H. T. H.; Miller, S. A.; Ploskonka, A. M.; DeCoste, J. B.; Cohen, S. M., Polymer–Metal–Organic Frameworks (polyMOFs) as Water Tolerant Materials for 12


Page 13 of 16 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


Selective Carbon Dioxide Separations. J. Am. Chem. Soc. 2016, 138, 920-925. (14) Lin, R.-B.; Xiang, S.; Xing, H.; Zhou, W.; Chen, B., Exploration of porous metal–organic frameworks for gas separation and purification. Coord. Chem. Rev. 2017, https://doi.org/10.1016/j.ccr.2017.09.027. (15) Zhang, M.; Zhou, W.; Pham, T.; Forrest Katherine, A.; Liu, W.; He, Y.; Wu, H.; Yildirim, T.; Chen, B.; Space, B.; Pan, Y.; Zaworotko Michael, J.; Bai, J., Fine Tuning of MOF ‐ 505 Analogues To Reduce Low ‐ Pressure Methane Uptake and Enhance Methane Working Capacity. Angew. Chem. Int. Ed. 2017, 56, 11426-11430. (16) Luo, F.; Yan, C.; Dang, L.; Krishna, R.; Zhou, W.; Wu, H.; Dong, X.; Han, Y.; Hu, T.-L.; O’Keeffe, M.; Wang, L.; Luo, M.; Lin, R.-B.; Chen, B., UTSA-74: A MOF-74 Isomer with Two Accessible Binding Sites per Metal Center for Highly Selective Gas Separation. J. Am. Chem. Soc. 2016, 138, 5678-5684. (17) Li, B.; Wen, H.-M.; Zhou, W.; Chen, B., Porous Metal–Organic Frameworks for Gas Storage and Separation: What, How, and Why? J. Phys. Chem. Lett. 2014, 5, 3468-3479. (18) He, C.-T.; Ye, Z.-M.; Xu, Y.-T.; Zhou, D.-D.; Zhou, H.-L.; Chen, D.; Zhang, J.-P.; Chen, X.-M., Hyperfine adjustment of flexible pore-surface pockets enables smart recognition of gas size and quadrupole moment. Chem. Sci. 2017, 8, 7560-7565. (19) Bao, Z.; Chang, G.; Xing, H.; Krishna, R.; Ren, Q.; Chen, B., Potential of microporous metal-organic frameworks for separation of hydrocarbon mixtures. Energy Environ. Sci. 2016, 9, 3612-3641. (20)Bao, S.-J.; Krishna, R.; He, Y.-B.; Qin, J.-S.; Su, Z.-M.; Li, S.-L.; Xie, W.; Du, D.-Y.; He, W.-W.; Zhang, S.-R.; Lan, Y.-Q., A stable metal-organic framework with suitable pore sizes and rich uncoordinated nitrogen atoms on the internal surface of micropores for highly efficient CO2 capture. J. Mater. Chem. A 2015, 3, 7361-7367. (21) Fu, H. R.; Zhang, J., Structural Transformation and Hysteretic Sorption of Light Hydrocarbons in a Flexible Zn–Pyrazole–Adenine Framework. Chem. Eur. J. 2015, 21, 5700-5703. (22)Bae, Y. S.; Lee Chang, Y.; Kim Ki, C.; Farha Omar, K.; Nickias, P.; Hupp Joseph, T.; Nguyen SonBinh, T.; Snurr Randall, Q., High Propene/Propane Selectivity in Isostructural Metal–Organic Frameworks with High Densities of Open Metal Sites. Angew. Chem. Int. Ed. 2012, 51, 1857-1860. (23) Li, P.; He, Y.; Zhao, Y.; Weng, L.; Wang, H.; Krishna, R.; Wu, H.; Zhou, W.; O'Keeffe, M.; Han, Y.; Chen, B., A Rod‐Packing Microporous Hydrogen‐Bonded Organic Framework for Highly Selective Separation of C2H2/CO2 at Room Temperature. Angew. Chem. Int. Ed. 2014, 54, 574-577. (24) Wang, H.; Li, B.; Wu, H.; Hu, T.-L.; Yao, Z.; Zhou, W.; Xiang, S.; Chen, B., A Flexible Microporous Hydrogen-Bonded Organic Framework for Gas Sorption and Separation. J. Am. Chem. Soc. 2015, 137, 9963-9970. (25) 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., Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation. Nature 2013, 495, 80-84. (26) 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, 13



Page 14 of 16

137-140. (27)Cui, X.; Chen, K.; Xing, H.; Yang, Q.; Krishna, R.; Bao, Z.; Wu, H.; Zhou, W.; Dong, X.; Han, Y.; Li, B.; Ren, Q.; Zaworotko, M. J.; Chen, B., Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene. Science 2016, 353, 141-144. (28) Chen, K.-J.; Scott, H. S.; Madden, D. G.; Pham, T.; Kumar, A.; Bajpai, A.; Lusi, M.; Forrest, K. A.; Space, B.; Perry IV, J. J.; Zaworotko, M. J., Benchmark C2H2/CO2 and CO2/C2H2 Separation by Two Closely Related Hybrid Ultramicroporous Materials. Chem 2016, 1, 753-765. (29) Li, B.; Cui, X.; O'Nolan, D.; Wen, H. M.; Jiang, M.; Krishna, R.; Wu, H.; Lin, R.-B.; Chen, Y. S.; Yuan, D.; Xing, H.; Zhou, W.; Ren, Q.; Qian, G.; Zaworotko Michael, J.; Chen, B., An Ideal Molecular Sieve for Acetylene Removal from Ethylene with Record Selectivity and Productivity. Adv. Mater. 2017, 29, 1704210. (30) Lin, R.-B.; Li, T.-Y.; Zhou, H.-L.; He, C.-T.; Zhang, J.-P.; Chen, X.-M., Tuning fluorocarbon adsorption in new isoreticular porous coordination frameworks for heat transformation applications. Chem. Sci. 2015, 6, 2516-2521. (31) Larpent, P.; Jouaiti, A.; Kyritsakas, N.; Hosseini, M. W., Molecular tectonics: homochiral 3D cuboid coordination networks based on enantiomerically pure organic tectons and ZnSiF6. Chem. Commun. 2013, 49, 4468-4470. (32) Li, L.; Matsuda, R.; Tanaka, I.; Sato, H.; Kanoo, P.; Jeon, H. J.; Foo, M. L.; Wakamiya, A.; Murata, Y.; Kitagawa, S., A Crystalline Porous Coordination Polymer Decorated with Nitroxyl Radicals Catalyzes Aerobic Oxidation of Alcohols. J. Am. Chem. Soc. 2014, 136, 7543-7546. (33) Wen, H.-M.; Li, L.; Lin, R.-B.; Li, B.; Hu, B.; Zhou, W.; Hu, J.; Chen, B., Fine-tuning of nano-traps in a stable metal-organic framework for highly efficient removal of propyne from propylene. J. Mater. Chem. A 2018, 6, 6931-6937. (34) Chang, G.; Li, B.; Wang, H.; Bao, Z.; Yildirim, T.; Yao, Z.; Xiang, S.; Zhou, W.; Chen, B., A microporous metal-organic framework with polarized trifluoromethyl groups for high methane storage. Chem. Commun. 2015, 51, 14789-14792. (35) Li, L.; Lin, R.-B.; Krishna, R.; Wang, X.; Li, B.; Wu, H.; Li, J.; Zhou, W.; Chen, B., Flexible–Robust Metal–Organic Framework for Efficient Removal of Propyne from Propylene. J. Am. Chem. Soc. 2017, 139, 7733-7736. (36) Myers, A. L.; Prausnitz, J. M., Thermodynamics of mixed‐gas adsorption. AIChE J. 1965, 11, 121-127. (37) Lin, M.-J.; Jouaiti, A.; Kyritsakas, N.; Hosseini, M. W., Molecular tectonics: modulation of size and shape of cuboid 3-D coordination networks. CrystEngComm 2009, 11, 189-191. (38)Burd, S. D.; Ma, S.; Perman, J. A.; Sikora, B. J.; Snurr, R. Q.; Thallapally, P. K.; Tian, J.; Wojtas, L.; Zaworotko, M. J., Highly Selective Carbon Dioxide Uptake by [Cu(bpy-n)2(SiF6)] (bpy-1 = 4,4′-Bipyridine; bpy-2 = 1,2-Bis(4-pyridyl)ethene). J. Am. Chem. Soc. 2012, 134, 3663-3666. (39) Xiong, S.; He, Y.; Krishna, R.; Chen, B.; Wang, Z., Metal–Organic Framework with Functional Amide Groups for Highly Selective Gas Separation. Cryst. Growth Des. 2013, 13, 2670-2674. 14


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(40) Matsuda, R.; Kitaura, R.; Kitagawa, S.; Kubota, Y.; Belosludov, R. V.; Kobayashi, T. C.; Sakamoto, H.; Chiba, T.; Takata, M.; Kawazoe, Y.; Mita, Y., Highly controlled acetylene accommodation in a metal–organic microporous material. Nature 2005, 436, 238. (41) Lin, R.-B.; Li, L.; Wu, H.; Arman, H.; Li, B.; Lin, R.-G.; Zhou, W.; Chen, B., Optimized Separation of Acetylene from Carbon Dioxide and Ethylene in a Microporous Material. J. Am. Chem. Soc. 2017, 139, 8022-8028. (42) Xiang, S.; Zhou, W.; Gallegos, J. M.; Liu, Y.; Chen, B., Exceptionally High Acetylene Uptake in a Microporous Metal−Organic Framework with Open Metal Sites. J. Am. Chem. Soc. 2009, 131, 12415-12419. (43) Xiang, S.; He, Y.; Zhang, Z.; Wu, H.; Zhou, W.; Krishna, R.; Chen, B., Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions. Nat. Commun. 2012, 3, 954.

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Page 16 of 16

For Table of Contents Use Only

Metal–Organic

Framework

with

Trifluoromethyl

Groups for Selective C2H2 and CO2 Adsorption Osamah Alduhaish, Rui-Biao Lin,* Hailong Wang, Bin Li, Hadi D. Arman, Tong-Liang Hu, and Banglin Chen*

A new SIFSIX-type MOF is synthesized from a trifluoromethyl dipyridyl ligand showing selective acetylene and carbon dioxide adsorption.

16


MetalâOrganic Framework with Trifluoromethyl Groups for Selective

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MetalâOrganic Framework with Trifluoromethyl Groups for Selective