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SCIENCE CHINA Materials, Volume 62 , Issue 9 : 1315-1322(2019) https://doi.org/10.1007/s40843-019-9427-5

A water-stable fcu-MOF material with exposed amino groups for the multi-functional separation of small molecules

More info
  • ReceivedFeb 25, 2019
  • AcceptedApr 2, 2019
  • PublishedApr 28, 2019

Abstract


Funded by

the National Natural Science Foundation of China(U1609219,51632008,61721005,51432001,51772268)

and Zhejiang Provincial Natural Science Foundation(LD18E020001)


Acknowledgment

This work was supported by the National Natural Science Foundation of China (U1609219, 51632008, 61721005, 51432001 and 51772268), and Zhejiang Provincial Natural Science Foundation (LD18E020001).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Jiang K designed and performed the experiments, analyzed the data, and wrote the paper; Zhang L conceived the experiments and contributed to gas sorption measurements; Xia T synthesized the MOF Eu-BDC-NH2; Yang Y and Li B analyzed the data; Cui Y and Qian G conceived the framework of this paper and revised the paper. All authors contributed to the general discussion.


Author information

Ke Jiang was born in Shandong, China. He received his double BSc degree at Hainan University and Tianjin University. He is now a PhD student in Prof. Guodong Qian’s laboratory at the School of Materials Science and Engineering, Zhejiang University. His current research focuses on the design and synthesis of metal-organic framework for biomedical application and gas separation.


Yuanjing Cui was born in Jiangsu, China. He received his BSc and PhD degrees in materials science and engineering from Zhejiang University in 1998 and 2006, respectively. Currently, he is a full professor in the School of Materials Science and Engineering at Zhejiang University. His research interest focuses on organic-inorganic hybrid photonic materials.


Guodong Qian was born in Zhejiang, China. He received his bachelor’s (1988) and master’s (1992) degrees in materials science from Zhejiang University in China. He joined the Materials Department of Zhejiang University after obtaining his PhD degree from Zhejiang University in 1997. He was promoted to associate professor, full professor and Cheung Kong professor in 1999, 2002 and 2011, respectively. His current research interests include hybrid organic-inorganic photonic functional materials and multifunctional porous materials.


Supplement

Supplementary information

Chemical stability data, thermo stability data and the performance comparison data with other MOF materials are available in the online version of the paper.


References

[1] Choudhary VR, Mayadevi S. Adsorption of methane, ethane, ethylene, and carbon dioxide on high silica pentasil zeolites and zeolite-like materials using gas chromatography pulse technique. Separation Sci Tech, 1993, 28: 2197-2209 CrossRef Google Scholar

[2] Cavenati S, Grande CA, Rodrigues AE. Removal of carbon dioxide from natural gas by vacuum pressure swing adsorption. Energy Fuels, 2006, 20: 2648-2659 CrossRef Google Scholar

[3] He Y, Zhou W, Qian G, et al. Methane storage in metal-organic frameworks. Chem Soc Rev, 2014, 43: 5657-5678 CrossRef PubMed Google Scholar

[4] Li JR, Sculley J, Zhou HC. Metal-organic frameworks for separations. Chem Rev, 2012, 112: 869-932 CrossRef PubMed Google Scholar

[5] Liang CC, Shi ZL, He CT, et al. Engineering of pore geometry for ultrahigh capacity methane storage in mesoporous metal-organic frameworks. J Am Chem Soc, 2017, 139: 13300-13303 CrossRef PubMed Google Scholar

[6] He M, Wang Y, Gao X, et al. Three ligand-originated MOF isomers: the positional effect of the methyl group on structures and selective C2H2/CH4 and CO2/CH4 adsorption properties. Dalton Trans, 2018, 47: 8983-8991 CrossRef PubMed Google Scholar

[7] Zhai QG, Bai N, Li SN, et al. Design of pore size and functionality in pillar-layered Zn-triazolate-dicarboxylate frameworks and their high CO2/CH4 and C2 hydrocarbons/CH4 selectivity. Inorg Chem, 2015, 54: 9862-9868 CrossRef PubMed Google Scholar

[8] Cui Y, Li B, He H, et al. Metal-organic frameworks as platforms for functional materials. Acc Chem Res, 2016, 49: 483-493 CrossRef PubMed Google Scholar

[9] Jiang K, Zhang L, Hu Q, et al. Indocyanine green–encapsulated nanoscale metal-organic frameworks for highly effective chemo-photothermal combination cancer therapy. Mater Today Nano, 2018, 2: 50-57 CrossRef Google Scholar

[10] Huang W, Sun H, Shangguan H, et al. Three-dimensional iron sulfide-carbon interlocked graphene composites for high-performance sodium-ion storage. Nanoscale, 2018, 10: 7851-7859 CrossRef PubMed Google Scholar

[11] Guo Y, Peng X. Mass transport through metal organic framework membranes. Sci China Mater, 2019, 62: 25-42 CrossRef Google Scholar

[12] Gong YN, Ouyang T, He CT, et al. Photoinduced water oxidation by an organic ligand incorporated into the framework of a stable metal-organic framework. Chem Sci, 2016, 7: 1070-1075 CrossRef PubMed Google Scholar

[13] Teplensky MH, Fantham M, Li P, et al. Temperature treatment of highly porous zirconium-containing metal-organic frameworks extends drug delivery release. J Am Chem Soc, 2017, 139: 7522-7532 CrossRef PubMed Google Scholar

[14] Wu H, Shen C, Xia C, et al. Versatile MOF-derived cobalt catalyst for the reductive amination. Sci China Mater, 2017, 60: 1269-1271 CrossRef Google Scholar

[15] Jiao L, Jiang HL. Metal-organic-framework-based single-atom catalysts for energy applications. Chem, 2019, 5: 786-804 CrossRef Google Scholar

[16] Fang Y, Liu W, Teat SJ, et al. A systematic approach to achieving high performance hybrid lighting phosphors with excellent thermal- and photostability. Adv Funct Mater, 2017, 27: 1603444 CrossRef Google Scholar

[17] Wang H, Xu J, Zhang DS, et al. Crystalline capsules: metal-organic frameworks locked by size-matching ligand bolts. Angew Chem Int Ed, 2015, 54: 5966-5970 CrossRef PubMed Google Scholar

[18] Zhao D, Kong C, Du H, et al. A molecular-templating strategy to polyamine-incorporated porous organic polymers for unprecedented CO2 capture and separation. Sci China Mater, 2019, 62: 448-454 CrossRef Google Scholar

[19] Sasan K, Lin Q, Mao C, et al. Open framework metal chalcogenides as efficient photocatalysts for reduction of CO2 into renewable hydrocarbon fuel. Nanoscale, 2016, 8: 10913-10916 CrossRef PubMed ADS Google Scholar

[20] Chen CX, Wei ZW, Jiang JJ, et al. Dynamic spacer installation for multirole metal-organic frameworks: a new direction toward multifunctional MOFs achieving ultrahigh methane storage working capacity. J Am Chem Soc, 2017, 139: 6034-6037 CrossRef PubMed Google Scholar

[21] Liao PQ, Huang NY, Zhang WX, et al. Controlling guest conformation for efficient purification of butadiene. Science, 2017, 356: 1193-1196 CrossRef PubMed Google Scholar

[22] Aguila B, Sun Q, Wang X, et al. Lower activation energy for catalytic reactions through host-guest cooperation within metal-organic frameworks. Angew Chem, 2018, 130: 10264-10268 CrossRef Google Scholar

[23] Yi FY, Chen D, Wu MK, et al. Chemical sensors based on metal-organic frameworks. ChemPlusChem, 2016, 81: 675-690 CrossRef Google Scholar

[24] Li B, Wen HM, Yu Y, et al. Nanospace within metal-organic frameworks for gas storage and separation. Mater Today Nano, 2018, 2: 21-49 CrossRef Google Scholar

[25] Hu TL, Wang H, Li B, et al. Microporous metal-organic framework with dual functionalities for highly efficient removal of acetylene from ethylene/acetylene mixtures. Nat Commun, 2015, 6: 7328 CrossRef PubMed ADS Google Scholar

[26] Haldar R, Inukai M, Horike S, et al. 113Cd nuclear magnetic resonance as a probe of structural dynamics in a flexible porous framework showing selective O2/N2 and CO2/N2 adsorption. Inorg Chem, 2016, 55: 4166-4172 CrossRef PubMed Google Scholar

[27] Lin RB, Li L, Wu H, et al. Optimized separation of acetylene from carbon dioxide and ethylene in a microporous material. J Am Chem Soc, 2017, 139: 8022-8028 CrossRef PubMed Google Scholar

[28] He H, Sun Q, Gao W, et al. A stable metal-organic framework featuring a local buffer environment for carbon dioxide fixation. Angew Chem Int Ed, 2018, 57: 4657-4662 CrossRef PubMed Google Scholar

[29] Zhang Z, Yao ZZ, Xiang S, et al. Perspective of microporous metal-organic frameworks for CO2 capture and separation. Energy Sci, 2014, 7: 2868-2899 CrossRef Google Scholar

[30] Lu W, Wei Z, Gu ZY, et al. Tuning the structure and function of metal-organic frameworks via linker design. Chem Soc Rev, 2014, 43: 5561-5593 CrossRef PubMed Google Scholar

[31] Bai Y, Dou Y, Xie LH, et al. Zr-based metal-organic frameworks: design, synthesis, structure, and applications. Chem Soc Rev, 2016, 45: 2327-2367 CrossRef PubMed Google Scholar

[32] Zhang L, Jiang K, Zhang J, et al. Low-cost and high-performance microporous metal-organic framework for separation of acetylene from carbon dioxide. ACS Sustain Chem Eng, 2019, 7: 1667-1672 CrossRef Google Scholar

[33] Chang Z, Yang DH, Xu J, et al. Flexible metal-organic frameworks: recent advances and potential applications. Adv Mater, 2015, 27: 5432-5441 CrossRef PubMed Google Scholar

[34] Wang X, Chi C, Zhang K, et al. Reversed thermo-switchable molecular sieving membranes composed of two-dimensional metal-organic nanosheets for gas separation. Nat Commun, 2017, 8: 14460 CrossRef PubMed ADS Google Scholar

[35] Rodenas T, Luz I, Prieto G, et al. Metal-organic framework nanosheets in polymer composite materials for gas separation. Nat Mater, 2014, 14: 48-55 CrossRef PubMed ADS Google Scholar

[36] Matsumoto M, Kitaoka T. Ultraselective gas separation by nanoporous metal−organic frameworks embedded in gas-barrier nanocellulose films. Adv Mater, 2016, 28: 1765-1769 CrossRef PubMed Google Scholar

[37] Zhang L, Jiang K, Li L, et al. Efficient separation of C2H2 from C2H2/CO2 mixtures in an acid–base resistant metal-organic framework. Chem Commun, 2018, 54: 4846-4849 CrossRef PubMed Google Scholar

[38] Deng H, Doonan CJ, Furukawa H, et al. Multiple functional groups of varying ratios in metal-organic frameworks. Science, 2010, 327: 846-850 CrossRef PubMed ADS Google Scholar

[39] Wen HM, Wang H, Li B, et al. A microporous metal-organic framework with lewis basic nitrogen sites for high C2H2 storage and significantly enhanced C2H2/CO2 separation at ambient conditions. Inorg Chem, 2016, 55: 7214-7218 CrossRef PubMed Google Scholar

[40] Yang L, Cui X, Zhang Z, et al. An asymmetric anion‐pillared metal-organic framework as a multisite adsorbent enables simultaneous removal of propyne and propadiene from propylene. Angew Chem, 2018, 130: 13329-13333 CrossRef Google Scholar

[41] Chui SSY, Lo SMF, Charmant JPH, et al. A chemically functionalizable nanoporous material [Cu3(TMA)2(H2O)3]n. Science, 1999, 283: 1148-1150 CrossRef ADS Google Scholar

[42] Kaye SS, Dailly A, Yaghi OM, et al. Impact of preparation and handling on the hydrogen storage properties of Zn4O(1,4-benzenedicarboxylate)3 (MOF-5). J Am Chem Soc, 2007, 129: 14176-14177 CrossRef PubMed Google Scholar

[43] Xue DX, Belmabkhout Y, Shekhah O, et al. Tunable rare earth fcu-MOF platform: access to adsorption kinetics driven gas/vapor separations via pore size contraction. J Am Chem Soc, 2015, 137: 5034-5040 CrossRef PubMed Google Scholar

[44] Yi P, Huang H, Peng Y, et al. A series of europium-based metal organic frameworks with tuned intrinsic luminescence properties and detection capacities. RSC Adv, 2016, 6: 111934-111941 CrossRef Google Scholar

[45] Chen F, Wang Y, Bai D, et al. Selective adsorption of C2H2 and CO2 from CH4 in an isoreticular series of MOFs constructed from unsymmetrical diisophthalate linkers and the effect of alkoxy group functionalization on gas adsorption. J Mater Chem A, 2018, 6: 3471-3478 CrossRef Google Scholar

[46] Zhang L, Jiang K, Li Y, et al. Microporous metal-organic framework with exposed amino functional group for high acetylene storage and excellent C2H2/CO2 and C2H2/CH4 separations. Cryst Growth Des, 2017, 17: 2319-2322 CrossRef Google Scholar

[47] Pang J, Jiang F, Wu M, et al. A porous metal-organic framework with ultrahigh acetylene uptake capacity under ambient conditions. Nat Commun, 2015, 6: 7575 CrossRef PubMed ADS Google Scholar

[48] Zhang Z, Xiang S, Hong K, et al. Triple framework interpenetration and immobilization of open metal sites within a microporous mixed metal-organic framework for highly selective gas adsorption. Inorg Chem, 2012, 51: 4947-4953 CrossRef PubMed Google Scholar

[49] Alawisi H, Li B, He Y, et al. A microporous metal-organic framework constructed from a new tetracarboxylic acid for selective gas separation. Cryst Growth Des, 2014, 14: 2522-2526 CrossRef Google Scholar

[50] Chen Z, Xiang S, Arman HD, et al. Three-dimensional pillar-layered copper(II) metal-organic framework with immobilized functional OH groups on pore surfaces for highly selective CO2/CH4 and C2H2/CH4 gas sorption at room temperature. Inorg Chem, 2011, 50: 3442-3446 CrossRef PubMed Google Scholar

[51] Cai J, Yu J, Xu H, et al. A doubly interpenetrated metal-organic framework with open metal sites and suitable pore sizes for highly selective separation of small hydrocarbons at room temperature. Cryst Growth Des, 2013, 13: 2094-2097 CrossRef Google Scholar

[52] Huang Y, Lin Z, Fu H, et al. Porous anionic indium-organic framework with enhanced gas and vapor adsorption and separation ability. ChemSusChem, 2014, 7: 2647-2653 CrossRef PubMed Google Scholar

[53] Ma JX, Guo J, Wang H, et al. Microporous lanthanide metal-organic framework constructed from lanthanide metalloligand for selective separation of C2H2/CO2 and C2H2/CH4 at room temperature. Inorg Chem, 2017, 56: 7145-7150 CrossRef PubMed Google Scholar

[54] Guo ZJ, Yu J, Zhang YZ, et al. Water-stable In(III)-based metal-organic frameworks with rod-shaped secondary building units: single-crystal to single-crystal transformation and selective sorption of C2H2 over CO2 and CH4. Inorg Chem, 2017, 56: 2188-2197 CrossRef PubMed Google Scholar

[55] Chen Y, Wu H, Liu Z, et al. Liquid-assisted mechanochemical synthesis of copper based MOF-505 for the separation of CO2 over CH4 or N2. Ind Eng Chem Res, 2018, 57: 703-709 CrossRef Google Scholar

[56] Chen Y, Wu H, Lv D, et al. An ultramicroporous nickel-based metal-organic framework for adsorption separation of CO2 over N2 or CH4. Energy Fuels, 2018, 32: 8676-8682 CrossRef Google Scholar

[57] Lu Z, Bai J, Hang C, et al. The utilization of amide groups to expand and functionalize metal-organic frameworks simultaneously. Chem Eur J, 2016, 22: 6277-6285 CrossRef PubMed Google Scholar

[58] Safarifard V, Rodríguez-Hermida S, Guillerm V, et al. Influence of the amide groups in the CO2/N2 selectivity of a series of isoreticular, interpenetrated metal-organic frameworks. Cryst Growth Des, 2016, 16: 6016-6023 CrossRef Google Scholar

[59] Liu B, Smit B. Molecular simulation studies of separation of CO2/N2, CO2/CH4, and CH4/N2 by ZIFs. J Phys Chem C, 2010, 114: 8515-8522 CrossRef Google Scholar

[60] Liang L, Liu C, Jiang F, et al. Carbon dioxide capture and conversion by an acid-base resistant metal-organic framework. Nat Commun, 2017, 8: 1233 CrossRef PubMed ADS Google Scholar

[61] Liao PQ, Chen XW, Liu SY, et al. Putting an ultrahigh concentration of amine groups into a metal-organic framework for CO2 capture at low pressures. Chem Sci, 2016, 7: 6528-6533 CrossRef PubMed Google Scholar

[62] McDonald TM, D’Alessandro DM, Krishna R, et al. Enhanced carbon dioxide capture upon incorporation of N,Nʹ-dimethylethylenediamine in the metal-organic framework CuBTTri. Chem Sci, 2011, 2: 2022-2028 CrossRef Google Scholar

  • Figure 1

    The optical microscopy image (a) and FE-SEM image of compound 1 (b), displaying the homogeneous polyhedral morphology with a particle size of around 50 µm.

  • Figure 2

    X-ray single crystal structure of compound 1 indicating that, (a) the 12-connected Eu6O4(OH)4(CO2)12 molecular building block (MBB) and the 2-connected linker (2-aminoterephthalic acid); (b) the bigger octahedral cage constructed from 6 MBBs and 12 ligands with a diameter of around 7.8 Å, while the smaller tetrahedral cage constructed from 4 MBBs and 6 ligands with a diameter of around 4.0 Å, and the 3D framework is viewed from a, b or c axes (C, white; O, red; Eu, cambridge blue; N, purple; H, green).

  • Figure 3

    N2 sorption isotherms and pore size distribution of compound 1 at 77 K. Closed symbols, adsorption; open symbols, desorption.

  • Figure 4

    Single-component adsorption isotherms of compound 1 for C2-hydrocarbons and CH4 at 273 (a) and 298 K (b); single-component adsorption isotherms of compound 1 for CO2 and N2 at 273 (c) and 298 K (d).

  • Figure 5

    IAST calculations of compound 1 for C2/CH4 selectivity at 273 (a) and 298 K (b); IAST calculations of compound 1 for CO2/N2 selectivity (c); the isosteric heats of gases in compound 1 (d); comparison of reported MOF materials for C2H2/CH4 selectivity (e); comparison of reported MOF materials for CO2 uptake and CO2/N2 selectivity (f).

  • Table 1   Important physical parameters of the selected gas adsorbates

    Adsorbate

    Kinetic diameter (Å)

    Polarizability (1025 cm−3)

    N2

    3.64–3.80

    17.403

    CO2

    3.3

    29.11

    CH4

    3.758

    25.93

    C2H2

    3.3

    33.3–39.3

    C2H4

    4.163

    42.52

    C2H6

    4.443

    44.3–44.7

  • Table 2   The gas sorption, selectivity and of compound

    Adsorbate

    C2H2

    C2H4

    C2H6

    CH4

    CO2

    N2

    Uptake capacity at 273 K and 1.0 bar (cm3 cm−3)

    143.6

    94.9

    86.6

    22.6

    126.4

    4.5

    Uptake capacity at 298 K and 1.0 bar (cm3 cm−3)

    113.1

    76.8

    71.9

    17.9

    92.6

    3.7

    Si/CH4 or Si/N2 at 273 K

    107.7

    47.3

    39.7

    /

    474.1

    /

    Si/CH4 or Si/N2 at 298 K

    33.4

    30.5

    22.3

    /

    151.7

    /

    Qst (kJ mmol−1)

    34.5

    32.8

    34.0

    16.1

    18.3

    13.0

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