4.7 Article

Two Solvent-Induced In(III)-Based Metal-Organic Frameworks with Controllable Topology Performing High-Efficiency Separation of C2H2/CH4 and CO2/CH4

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INORGANIC CHEMISTRY
卷 61, 期 29, 页码 11057-11065

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AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.2c00694

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资金

  1. National Natural Science Foundation of China [52102189]
  2. Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Zhejiang Normal University [KLMEACM202001]
  3. Open Research Fund of Key Laboratory of the Ministry of Education for Advanced Catalysis Materials

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In this study, a plausible strategy involving solvent-induced effects and the flexibility of the ligand conformation was used to develop two new metal-organic frameworks (MOFs). One of the MOFs showed a large channel, which was not suitable for fine gas separation. The other MOF had a suitable micropore structure for confinement of small gas molecules, showing high selectivity in C2H2/CH4 and CO2/CH4 separation.
For pure acetylene manufacturing and natural gas purification, the development of porous materials displaying highly selective C2H2/CH4 and CO2/CH4 separation is greatly important but remains a major challenge. In this work, a plausible strategy involving solvent-induced effects and using the flexibility of the ligand conformation to make two In(III) metal-organic frameworks (MOFs) is developed, showing topological diversity and different stability. The X-shaped tetracarboxylic ligand H(4)TPTA ([1,1':3',1 ''-terpheny1]-4,4',4 '',6'-tetracarboxylic acid) was selected to construct two new heteroid In MOFs, namely, {[CH3NH3]-[In(TPTA)]center dot 2(NMF)} (MOF 1) and {[In-2(TPTA)(OH)(2)]center dot 2(H2O)center dot(DMF)} (MOF 2). MOF 1 is a (4, 4)-connected net showing a pts topology with a large channel that is not conducive to fine gas separation. By contrast, with the reduction of SBU from uninucleated In to an {In-OH-In}(n) chain, MOF 2 has a (4, 6)-connected net with the fsc topology with an similar to 5 angstrom suitable micropore to confine matching small gas. The permanent porosity of MOF 2 leads to the preferential adsorption of C2H2 over CO2 with superior C2H2/CH4 (332.3) and CO2/CH4 (31.2) separation selectivities. Meanwhile, the cycling dynamic breakthrough experiments showed that the high-purity C2H2 (>99.8%) capture capacities of MOF 2 were >1.92 mmol g(-1) from a binary C2H2/CH4 mixture, and its separation factor reached 10.

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