Screening of Metal-Organic Frameworks for Highly Effective Hydrogen

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Screening of Metal-Organic Frameworks for Highly Effective Hydrogen Isotope Separation by Quantum Sieving Guopeng Han, Yu Gong, Hongliang Huang, Dawei Cao, Xiaojun Chen, Dahuan Liu, and Chongli Zhong ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b10201 • Publication Date (Web): 04 Sep 2018 Downloaded from http://pubs.acs.org on September 4, 2018

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ACS Applied Materials & Interfaces

Screening of Metal-Organic Frameworks for Highly Effective Hydrogen Isotope Separation by Quantum Sieving Guopeng Han,† Yu Gong,‡ Hongliang Huang,§ Dawei Cao,‡ Xiaojun Chen,*, ‡ Dahuan Liu,*,† Chongli Zhong*,†,§ †

State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical

Technology, Beijing, 100029, China ‡

Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang,

Sichuan, 621900, China §

State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin Polytechnic

University, Tianjin, 300387, China KEYWORDS: hydrogen isotope, metal-organic framework, quantum sieving, screening, separation

ABSTRACT: Separation of hydrogen isotopes is of great importance to produce highly pure hydrogen isotopes for numerous applications, which is however very difficult because of their almost identical thermodynamic properties. Adsorptive separation is considered as a simple, highly efficient and cost-effective technique compared to the traditional methods, where the key

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is the suitable adsorbent. Herein, SIFSIX-3-Zn was screened out from the reported metal-organic frameworks (MOFs), exhibiting high selectivities for D2/H2 mixture by quantum sieving effect. Advanced cryogenic thermal desorption spectroscopy (ACTDS) confirms the calculation results, indicating that the selectivities for 1:1 D2/H2 mixture at 20 K are larger than the values reported so far, especially it shows a record value of 53.8 at 25 kPa. This demonstrates that this MOF is a promising candidate for highly effective hydrogen isotope separation.

1. INTRODUCTION Highly pure hydrogen isotopes (deuterium and tritium) have numerous important applications, such as in nuclear fusion reactors,1 hydrogen nuclear magnetic resonance spectroscopy,1 lighting,1 isotopic tracing,2,3 and neutron scattering.4,5 However, the separation of hydrogen isotopes is very difficult due to their almost identical size, shape and thermodynamic properties.6 The current industrial separation technology is mainly using cryogenic distillation at 20-24 K,7,8 while it faces the main obstacles from the practical point of view, including complex operation procedures and the low separation efficiency (for example, SD2/H2 = 3.0 at 20 K),9 resulting in high costs. Alternatively, adsorptive separation using nanoporous materials by quantum cryosieving effect is considered as a simple, highly efficient and cost-effective technique.10-14 The difference in the effective particle size at low temperatures can be applied to the separation, which is induced by different de Broglie wavelengths of H2 and D2. The key is to develop suitable adsorbents for hydrogen isotope separation. During the past several decades, metal-organic frameworks (MOFs) have exhibited many unique advantages compared to other traditional adsorbents including carbon nanotubes and zeolites, thanks to their highly tunable and designable pore structure and chemical


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functionality.15-25 Though almost an infinite number of combinations of metal ions and organic linkers endow MOFs with promising applications in hydrogen isotope separation,26 it is still a great challenge to efficiently identify optimal candidates from the extremely large number of existed MOFs. Thus, MOFs have not been fully utilized as novel adsorbents in such applications up to now, by taking advantage of their unique features. Herein, a screening method is used to find the most promising MOFs for highly effective hydrogen isotope separation. The separation of D2/H2 mixture at 20 K is taken as an example, considering the operating temperature of the most commonly used cryogenic distillation in practical, as well as the fact that the quantum sieving effect is more evident at lower temperatures.27,28 SIFSIX-3-Zn was screened out and exhibits high selectivities for 1:1 D2/H2 mixture at 20 K, which are larger than the values reported so far. These results may also provide useful information for screening MOFs for other given adsorptive separation targets. 2. EXPERIMENTAL SECTION 2.1. Screening of MOFs Before performing extensive studies, it would be helpful if we can screen out a small number of suitable MOFs from a large variety of candidates. The screening methodology mainly includes the following steps. First, MOFs with too small aperture sizes are not suitable for the adsorption, among which those with too large aperture sizes are also excluded that may play a negative role on separation. Then, the zero-point-energy (ZPE) of D2 and H2 in these MOFs were considered since ZPE in confined systems would influence the energy barriers through the diffusion pathway.10,29,30 ZPE should be not very large in order to facilitate the adsorption, while the difference in ZPE of D2 and H2 (∆ZPE) should be as large as possible to enhance the selectivity.


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Finally, pore structure was considered, in combination of the convenience of synthesis, the stability of framework and the functional groups in the framework. During the screening procedure, only the aperture size and the ZPE should be calculated using the reported methods in literature. The reliability of the calculations was confirmed by repeating the reported values. Details can be found in Supporting Information. 2.2. Reagents and Materials. All reagents and solvents used in this work were commercially available and used as supplied without further purification. All of the MOFs were synthesized following the approaches in literatures, and details can be found in Supporting Information. 2.3. Characterization of MOFs. Powder X-ray diffraction (PXRD) analysis of the porous materials were collected at room temperature. It was carried out on a D8 ADVANCE XRD-6000 X-ray diffractometer in reflection mode using Cu Kα radiation (λ = 1.54056 Å). The 2 θ range from 5° to 50° was scanned with a step size of 0.02°. Thermogravimetric analyses were recorded on a TGA/DSC 1/1100 SF STA at a heating rate of 10 K/min under nitrogen atmosphere from 293 K to 650 K. The morphologies of the MOFs were characterized using a Hitachi S-4700 scanning electron microscope (SEM) with an accelerating voltage of 20.0 kV. 2.4. Procedure of adsorption and desorption for D2/H2 mixture separation. ACTDS measurements were performed to study the adsorption and desorption for D2/H2 mixture separation and the illustration of apparatus can be found in Supporting Information.31 MOF sample (about 5.0 mg) was put into the sample cell. The vacuum system was started. V4


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and auxiliary heater (6) were opened so that the sample can be activated under the ultra-high vacuum (UHV) (1.0×10-9 bar) and 378~423 K for 12 h according to TGA of sample. After activation, V4 was closed and V1, V2, V3 were adjusted to keep the external cavity in a vacuum state and inner chamber in a helium atmosphere (0.5 bar). Then the sample was cooled down to exposure temperature (such as 20 K) by cold finger. The cooling capacity came from refrigerator with compressed helium. Subsequently, V6 and V7 were opened so that the sample was exposed to1:1 D2/H2 mixture (V6 and V7 were adjusted to keep the sample cell with the specified pressure) at the exposure temperature for 10 mines. Afterward, V4 was adjusted again and the sample cell was quickly evacuated to remove residual gases (5.5×10-8 bar) at exposed temperature, and then cooled down to 20 K. Finally, the quadrupole mass spectrometer (MS) with the molecular pump, V5 and auxiliary heater (6) were opened in turn. A linear heating ramp was applied in order to thermally activate desorption. The desorbing gas was continuously detected using a quadrupole mass spectrometer, recognizing a pressure increase in the sample cell when gas desorbs. The result could be obtained after analyzing the data from MS. 3. RESULTS AND DISCUSSION 3.1 Separation performance of SIFSIX-3-Zn SIFSIX-3-Zn was synthesized using the reported procedure in literature,32,33 and the detailed characterizations provided in Figures S2(a), S3 and S4 indicate the successful preparation of this MOF with good crystallinity and thermal stability. As shown in Figure 1, Zn(II) center is octahedrally coordinated to the pyrazine linkers through four N atoms and to two hexafluorosilicate (SiF62-) anions. The pyrazine linkers bridge Zn(II) to generate pyrazine/metal two-dimensional periodic square grids, and SiF62- are coordinated axially to get the 2D square


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grid sheets. The framework contains saturated metal centers and exhibits pcu topology,34 resulting in an open framework with 1D channels.

Figure 1. Illustration of the crystal structure of SIFSIX-3-Zn: (a) overall structure along c axis (a) and b axis (b). (Zn, purple; Si, yellow; F, cyan; C, gray; H, white; N, blue. 1D Channel, transparent column with pale yellow). To examine the separation performance of SIFSIX-3-Zn for D2/H2 mixtures, ACTDS measurements were performed. The principle of thermal desorption is that an adsorbate can leave the material when the material is heated. The reliability of our schematic diagram of volumetric adsorption apparatus and experimental procedure of ACTDS can be verified by repeating the reported data as provided in Figure S6 and Table S1.31 The general procedure of ACTDS is as follows. After being cooled in high vacuum to a given temperature, the pre-activated MOF sample is exposed to a 1:1 D2/H2 mixture with different loading pressures. Then, the chamber is evacuated after 10 mins, and the MOF sample is cooled rapidly to 20 K to start ACTDS measurements. Figure 2 shows the ACTDS spectra of D2 and H2 in the temperature range between 20 K and 120 K at different pressures. It can be seen that the areas under the desorption curve of H2 are very small and significantly lower than those of D2, indicating that quantum sieving effects are actually occurred during the adsorption process. The direct selectivity for 1:1


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D2/H2 mixture can be calculated from the ratio of desorbed amount of D2 over H2 from these ACTDS spectra (as shown in Supporting Information),31 and the results are listed in Figure 3. Interestingly, SD2/H2 is larger than 35.0 at the whole range of pressure, which is as high as 53.8 at 25 kPa.

Figure 2. H2 (black) and D2 (red) desorption spectra of different pressures (1:1 D2/H2 mixture) in SIFSIX-3-Zn. 60 48

S (D2/H2)

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36 24 12 0

0

5

10

15

20

25

Pressure (kPa)

Figure 3. Selectivity of D2/H2 in SIFSIX-3-Zn for 1:1 D2/H2 mixture as a function of pressure at 20 K. To understand the excellent separation performance, we carefully examined the structure of SIFSIX-3-Zn. The ideal aperture of 1D channel is about 3.86 Å, which is evidently smaller than the effective diameter of H2 accounting for the quantum effect at 20 K (about 5.66 Å), inducing


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the difficult adsorption of H2. Moreover, ∆ZPE for D2 and H2 is about 1.4 kJ/mol, which further hinders the adsorption of H2, providing the enhancement of preferential adsorption of D2 compared to H2. In addition, such ultramicro-channels show a relatively high affinity for guest molecules,32 and the abundant fluorine atoms of SiF62- could also strengthen the interaction between D2 and the framework through the possible hydrogen bond to improve the adsorption amount.35 As shown in Figure 2, the total areas under the desorption curve of mixture is almost unchanged from 1 to 25 kPa, indicating that this material could be saturated at low pressure due to the relatively strong interaction between framework and hydrogen isotope. The heavier D2 owns the larger rate constant and lower activation energy for diffusion at zero surface coverage than the corresponding values for H2.36 Thanks to the above cooperative effect of structure and interaction, this MOF exhibits excellent separation performance for D2/H2 mixture at 20 K. The selectivity is not only greatly larger than the commercial cryogenic distillation process (SD2/H2 = 3.0 at 20 K), but also is far more superior compared to all of the reported adsorbents up to date (as shown in Figure 4 and Table S2).

Figure 4. The comparison of selectivities for D2/H2 in porous materials at 20 K. (25 kPa: SIFSIX-3-Zn, HKUST-1, ox-SWCNT, SWCNT, band-SWCNT; 10 kPa: SIFSIX-3-Zn, FCTF-1-


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400, KAUST-7, STAM-1, SIFZIX-1-Cu, SIFZIX-3-Cu, COF-1, Cu-PYC, SIFSIX-3-Ni, Fluorinated-ACFs, ZIF-7, ZIF-8, COF-102). To further examine the reasonability of the screening method, we also synthesized several other MOFs which are not selected during the screening steps as control experiments. The detailed characterizations are provided in Figure S2. As shown in Figures S7 and S8, the materials, which have too large or too small aperture sizes, exhibit low selectivities for D2/H2. For example, SD2/H2 = 9.9 in STAM-1 with an aperture size of 6.19 Å, SD2/H2 = 2.2 in Cu-PYC with an aperture size of 6.49 Å, SD2/H2 = 26.0 in HKUST-1 with an aperture size of 6.66 Å, SD2/H2 = 7.1 in SIFSIX-1-Cu with an aperture size of 7.11 Å, SD2/H2 = 9.8 in KAUST-7 with an aperture size of 2.65 Å. Several other materials reported in the literature can also be compared, such as, fluorinated-ACFs (SD2/H2 = 1.3, the aperture size is 8.80 Å),37 COF-1 (SD2/H2 = 7.0, the aperture size is 9.00 Å),38 CPO-27-Co (SD2/H2 = 3.0, the aperture size is 10.00 Å)31 and SWCNT (SD2/H2 = 1.2, the aperture size is 20.00 Å).39 For those with suitable aperture sizes, SD2/H2 is about 1.0 in ZIF-7 with a large ZPE for D2 (656.7 kJ/mol), and SD2/H2 is about 12.8 in FCTF-1-400 with a small ∆ZPE (0.2 kJ/mol). In comparison, SIFSIX-3-Zn with a suitable aperture and a relatively large ∆ZPE for D2 and H2 realizes high selectivity (35.0-53.8). 4. CONCLUSIONS In summary, a suitable MOF was selected to effectively separate hydrogen isotopes by quantum sieving in consideration of the synergetic effect of aperture size, the ∆ZPE, and the pore structure. ACTDS measurements show that the selectivity for 1:1 D2/H2 mixture at 20 K is larger than 35.0 at the whole pressure range (1 kPa to 25 kPa), which is as high as 53.8 at 25 kPa. These values are superior to all the reported ones so far to the best of our knowledge. The results not only demonstrate that the SIFSIX-3-Zn is a promising candidate for highly effective


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hydrogen isotope separation, but also will contribute to develop the efficient screening method of MOFs for a given adsorptive separation target. ASSOCIATED CONTENT Supporting Information. Screening of MOFs, calculation of PLD, calculation of zero-point energy, calculation method for selectivity, preparation and characterization of porous materials, illustration of volumetric adsorption apparatus, desorption spectra of D2/H2 mixture, and comparison of selectivities supplied as Supporting Information. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected] (D.L.). *E-mail: [email protected] (X.C.). *E-mail: [email protected] (C.Z.). Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work is supported by the Natural Science Foundation of China (NO. 21536001). Y.G., D.C., and X.C. thank the support of the National Magnetic Confinement Fusion Science Program (2015GB106004).

ABBREVIATIONS


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CCDC, Cambridge Crystallographic Data Centre; PLD, pore limiting diameters; ZPE, zeropoint-energy; ACTDS, advanced cryogenic thermal desorption spectroscopy; UHV, ultra-high vacuum; MS, mass spectrometer. REFERENCES (1) Wang, Y.; Bhatia, S. K. Quantum Effect-Mediated Hydrogen Isotope Mixture Separation in Slit Pore Nanoporous Materials. J. Phys. Chem. C 2009, 113, 14953-14962. (2) Kerr, W. J.; Lindsay, D. M.; Reid, M.; Atzrodt, J.; Derdau, V.; Rojahnb, P.; Weck, R. Iridium-Catalysed Ortho-H/D and-H/T Exchange under Basic Conditions: C–H Activation of Unprotected Tetrazoles. Chem. Commun. 2016, 52, 6669-6672. (3) Povinec, P. P.; Bokuniewicz, H.; Burnett, W. C.; Cable, J.; Charette, M.; Comanducci, J. F.; Kontar, E. A.; Moore, W. S.; Oberdorfer, J. A.; de Oliveira, J.; Peterson, R.; Stieglitz, T.; Taniguchi, M. Isotope Tracing of Submarine Groundwater Discharge Offshore Ubatuba, Brazil: Results of the IAEA–UNESCO SGD Project. J. Environ. Radioact. 2008, 99, 1596-1610. (4) Luchini, A.; Delhom, R.; Demé, B.; Laux, V.; Moulin, M.; Haertlein, M.; Pichler, H.; Strohmeier, G. A.; Wacklin, H.; Fragneto, G. The Impact of Deuteration on Natural and Synthetic Lipids: A Neutron Diffraction Study. Colloids Surf. B: Biointerfaces 2018, 168, 126133. (5) Machida, A.; Saitoh, H.; Sugimoto, H.; Hattori, T.; SanoFurukawa, A.; Endo, N.; Katayama, Y.; Lizuka, R.; Sato, T.; Matsuo, M.; Orimo, S-i.; Aoki, K. Site Occupancy of Interstitial Deuterium Atoms in Face-Centred Cubic Iron. Nat. Commun. 2014, 5, 5063-5069.


11


Page 12 of 17

(6) Hankel, M.; Jiao, Y.; Du, A.; Gray, S. K.; Smith, S. C.; Asymmetrically Decorated, Doped Porous Graphene as an Effective Membrane for Hydrogen Isotope Separation. J. Phys. Chem. C 2012, 116, 6672-6676. (7) Trenin, V. D.; Alekseev, I. A.; Baranov, I. A.; Bondarenko, S. D.; Karpov, S. P.; Konoplev, K. A.; Vasyanina, T. V.; Fedorchenko, O. A.; Kortikov, V. S.; Bronstein, A. S.; Golovchenko, A. K. Full-Scale Experimental Assembly for Hydrogen Isotopes Separation Studies by Cryogenic Distillation: Assembly and Results of the Studies. Fusion Technol. 1995, 28,761-766. (8) Kinoshita, M.; Matsuda, Y.; Naruse, Y.; Tanaka, K. Computer Analysis on Steady State Separation Characteristics of Hydrogen Isotope Separation System by Cryogenic Distillation. J. Nucl. Sci. Technol. 1981, 18, 525-539. (9) Oh, H.; Hirscher, M. Quantum Sieving for Separation of Hydrogen Isotopes Using MOFs. Eur. J. Inorg. Chem. 2016, 27, 4278-4289. (10) Beenakker, J. J. M.; Borman, V. D.; Krylov, S. Y. Molecular Transport in Subnanometer Pores: Zero-Point Energy, Reduced Dimensionality and Quantum Sieving. Chem. Phys. Lett. 1995, 232, 379-382. (11) Krkljus, I.; Steriotis, T.; Charalambopoulou, G.; Gotzias, A.; Hirscher, M. H2/D2 Adsorption and Desorption Studies on Carbon Molecular Sieves with Different Pore Structures. Carbon 2013, 57, 239-274. (12) Mota, J. P.; Martins, D.; Lopes, D.; Catarino, I.; Bonfait, G. Structural Transitions in the MIL-53 (Al) Metal–Organic Framework upon Cryogenic Hydrogen Adsorption. J. Phys. Chem. C 2017, 121, 24252-24263.


12

Page 13 of 17 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


(13) Fitzgerald, S. A.; Shinbrough, K.; Rigdon, K. H.; Rowsell, J. L. C.; Kapelewski, M. T.; Pang, S. H.; Lawler, K. V.; Forster, P. M. Temperature-Programmed Desorption for Isotope Separation in Nanoporous Materials. J. Phys. Chem. C 2018, 122, 1995-2001. (14) Niimura, S.; Fujimori, T.; Minami, D.; Hattori, Y.; Abrams, L.; Corbin, D.; Hata, K.; Kaneko, K. Dynamic Quantum Molecular Sieving Separation of D2 from H2–D2 Mixture with Nanoporous Materials. J. Am. Chem. Soc. 2012, 134, 18483-18486. (15) Yang, Q.; Liu, D. Zhong, C.; Li, J. Development of Computational Methodologies for Metal–Organic Frameworks and Their Application in Gas Separations. Chem. Rev. 2013, 113, 8261-8323. (16) Tanaka, H.; Noguchi, D.; Yuzawa, A.; Kodaira, T.; Kanoh, H.; Kaneko, K. Quantum Effects on Hydrogen Isotopes Adsorption in Nanopores. J. Low Temp. Phys. 2009, 157, 352-373. (17) Stock, N.; Biswas, S. Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites. Chem. Rev. 2012, 112, 933-969. (18) Han, G.; Wang, K.; Peng, Y.; Zhang, Y.; Huang, H.; Zhong, C. Enhancing Higher Hydrocarbons Capture for Natural Gas Upgrading by Tuning van der Waals Interactions in fcuType Zr-MOFs. Ind. Eng. Chem. Res. 2017, 56, 14633-14641. (19) Huang, H.; Li, J.; Wang, K.; Han, T.; Tong, M.; Li, L.; Xue, Y.; Yang, Q.; Liu, D.; Zhong, C. An in Situ Self-Assembly Template Strategy for the Preparation of Hierarchical-Pore MetalOrganic Frameworks. Nat. Commun. 2015, 6, 8847-8855.


13


Page 14 of 17

(20) Gagnon, K. J.; Perry, H. P.; Clearfield, A. Conventional and Unconventional Metal– Organic Frameworks Based on Phosphonate Ligands: MOFs and UMOFs. Chem. Rev. 2012, 112, 1034-1054. (21) Wang, Z.; Tanabe, K. K.; Cohen, S. M. Tuning Hydrogen Sorption Properties of Metal– Organic Frameworks by Postsynthetic Covalent Modification. Chem. Eur. J. 2010, 16, 212-217. (22) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The Chemistry and Applications of Metal-Organic Frameworks. Science 2013, 341, 1230444. (23) Schoedel, A.; Li, M.; Li, D.; O'Keeffe, M.; Yaghi, O. M. Structures of Metal–Organic Frameworks with Rod Secondary Building Units. Chem. Rev. 2016, 116, 12466-12535. (24) Altintas, C.; Avci, G.; Daglar, H.; Nemati Vesali Azar, A.; Velioglu, S.; Erucar, I.; Keskin, S. A Database for CO2 Separation Performances of MOFs based on Computational Materials Screening. ACS Appl. Mater. Interfaces 2018, 10, 17257-17268. (25) Zhang, N.; Yuan, L.; Guo, W.; Luo, S.; Chai, Z.; Shi, W. Extending the Use of Highly Porous and Functionalized MOFs to Th(IV) Capture. ACS Appl. Mater. Interfaces 2017, 9, 25216-25224. (26) Liu, D.; Wang, W.; Mi, J.; Zhong, C.; Yang, Q.; Wu, D. Quantum Sieving in Metal– Organic Frameworks: A Computational Study. Ind. Eng. Chem. Res. 2012, 51, 434-442. (27) Hu, S.; Gopinadhan, K.; Rakowski, A.; Neek-Amal, M.; Heine, T.; Grigorieva, I. V.; Haigh, S. J.; Peeters, F. M.; Geim, A. K.; Lozada-Hidalgo, M. Transport of Hydrogen Isotopes through Interlayer Spacing in van der Waals Crystals. Nat. Nanotechnol. 2018, 13, 468-472.


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(28) Contescu, C. I.; Zhang, H.; Olsen, R. J.; Mamontov, E.; Morris, J. R.; Gallego, N. C. Isotope Effect on Adsorbed Quantum Phases: Diffusion of and in Nanoporous Carbon. Phys. Rev. Lett. 2013, 110, 236102. (29) Oh, H.; Kalidindi, S. B.; Um, Y.; Bureekaew, S.; Schmid, R.; Fischerand, R. A.; Hirscher, M. A Cryogenically Flexible Covalent Organic Framework for Efficient Hydrogen Isotope Separation by Quantum Sieving. Angew. Chem. Int. Ed. 2013, 52, 13219-13222. (30) Mondelo-Martell, M.; Huarte-Larrañaga, F. Diffusion of H2 and D2 Confined in SingleWalled Carbon Nanotubes: Quantum Dynamics and Confinement Effects. J. Phys. Chem. A 2016, 120, 6501-6512. (31) Oh, H.; Savchenko, I.; Mavrandonakis, A.; Heine, T.; Hirscher. M. Highly Effective Hydrogen Isotope Separation in Nanoporous Metal–Organic Frameworks with Open Metal Sites: Direct Measurement and Theoretical Analysis. ACS Nano, 2014, 8, 761-770. (32) Uemura, K.; Maeda, A.; Maji, T. K.; Kanoo, P.; Kita, H. Syntheses, Crystal Structures and Adsorption Properties of Ultramicroporous Coordination Polymers Constructed from Hexafluorosilicate Ions and Pyrazine. Eur. J. Inorg. Chem. 2009, 2009, 2329-2337. (33) 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, 8084. (34) Elsaidi, S. K.; Mohamed, M. H.; Schaef, H. T.; Kumar, A.; Lusi, M.; Pham, T.; Forrest, K. A.; Space, B.; Xu, W. Q.; Halder, G. J.; Liu, J.; Zaworotko, M. J.; Thallapally, P. K.


15


Page 16 of 17

Hydrophobic Pillared Square Grids for Selective Removal of CO2 from Simulated Flue Gas. Chem. Commun. 2015, 51, 15530-15533. (35) Brammer, L.; Bruton, E. A.; Sherwood, P. Understanding the Behavior of Halogens as Hydrogen Bond Acceptors. Cryst. Growth Des. 2001, 1, 277-290. (36) Chen, B.; Zhao, X.; Putkham, A.; Hong, K.; Lobkovsky, E. B.; Hurtado, E. J.; Fletcher, A. J.; Thomas, K. M. Surface Interactions and Quantum Kinetic Molecular Sieving for H2 and D2 Adsorption on a Mixed Metal−Organic Framework Material. J. Am. Chem. Soc. 2008, 130, 6411-6423. (37) Hattori, Y.; Tanaka, H.; Okino, F.; Touhara, H.; Nakahigashi, Y.; Utsumi, S.; Kanoh, H.; Kaneko, K. Quantum Sieving Effect of Modified Activated Carbon Fibers on H2 and D2 Adsorption at 20 K. J. Phys. Chem. B 2006, 110, 9764-9767. (38) Oh, H.; Park, K. S.; Kalidindi, S. B.; Fischerc, R. A.; Hirscher, M. Quantum Cryo-Sieving for Hydrogen Isotope Separation in Microporous Frameworks: An Experimental Study on the Correlation between Effective Quantum Sieving and Pore Size. J. Mater. Chem. A 2013, 1, 32443248. (39) Kagita, H.; Ohba, T.; Fujimori, T.; Tanaka, H.; Hata, K.; Taira, S.-I.; Kanoh, H.; Minami, D.; Hattori, Y.; Itoh, T.; Masu, H.; Endo, M.; Kaneko, K. Quantum Molecular Sieving Effects of H2 and D2 on Bundled and Nonbundled Single-Walled Carbon Nanotubes. J. Phys. Chem. C 2012, 116, 20918-20922.


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Screening of Metal-Organic Frameworks for Highly Effective Hydrogen

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