This review summarizes the recent progress in preparations, functionalities and applications of composites of metal–organic frameworks (MOFs) and carbon-based materials.

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This work aims to study the features of CH4 and N2 adsorption inside 1D micro-channels and develop the best suitable MOF candidates for the adsorptive separation of CH4 against N2. For this purpose, four MOFs ([Ni3(HCOO)6], [Cu(INA)2], Al-BDC and Ni-MOF-74) with similar network topology and single 1D micro-channel have been systematically investigated via structure characterization and selective gas adsorption and separation. The selected MOFs are classified into three groups. Thereinto, Ni-MOF-74, with coordinatively unsaturated metal sites, is considered as strong polar adsorbent, whilst Al-BDC is treated as moderate polar adsorbent owing to the polar linkers. However, [Ni3(HCOO)6] and [Cu(INA)2] are regarded as apolar (weak polarity) adsorbents because of lack of any polar functional groups inside the frameworks. The adsorption potential of CH4 follows the trend Ni-MOF-74 > [Ni3(HCOO)6]> [Cu(INA)2] > Al-BDC, while Ni-MOF-74 > Al-BDC > [Ni3(HCOO)6] > [Cu(INA)2] for the potential of N2. This implies that pore size and electrostatic interactions have different contributions to the CH4 or N2-MOFs interactions, resulting in excellent CH4/N2 selectivity more than 6 on [Ni3(HCOO)6] and [Cu(INA)2].

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Eight new d 10 metal-organic coordination polymers, [Zn(mip)(bpa)] n (1), [Zn(mip)were prepared through hydrothermal reactions of H 2 mip or H 2 tbip (H 2 mip = 5-methylisophthalic acid and H 2 tbip = 5-tert-butylisophthalic acid) with different pyridyl-containing ligands (bpa = 1,2-bis(4-pyridyl)ethane, bpp = 1,3-bis(4-pyridyl)propane, dpe = 1,2-di(4-pyridyl)ethene and bipy = 4,4 0 -bipyridine), respectively. Except for complexes 2 and 6, all the other six compounds were reported for the first time. These complexes were structurally characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Complex 1 is a 3-fold interpenetrating three-dimensional (3D) network with CdSO 4 topology constructed from alternately left-handed and right-handed helical channels. Complexes 2 and 3 are 4fold interpenetrated diamondoid-like networks. Polymers 4 and 5 are isostructural, showing 2-fold 3D interpenetrating R-Po networks constructed from binuclear zinc nodes. Complex 6 possesses a two-dimensional (2D) corrugated network. Complex 7 has a one-dimensional (1D) tube-like chain along the a direction and is further linked by hydrogen bonding and π-π stacking interactions to form a 3D supramolecular network. Complex 8 features a 2D layer and further forms a 3D supramolecular framework by hydrogen bonding. These results show that the influence of steric hindrance of an organic ligand on the structures of d 10 coordination polymers is realized through changing the substituted groups of the dicarboxylate derivatives. Furthermore, thermal stabilities and photoluminescent properties of the complexes were also studied in the solid state.

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The adsorptive separation selectivities of CH4/N2were successfully improved from 4.0–4.8 to 7.0–7.5viasynthesis optimization of ultra-microporous [Ni3(HCOO)6] frameworks.