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Issue 48, 2014
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Gas adsorption properties of highly porous metal–organic frameworks containing functionalized naphthalene dicarboxylate linkers

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Abstract

Three functionalized metal–organic frameworks (MOFs), MOF-205-NH2, MOF-205-NO2, and MOF-205-OBn, formulated as Zn4O(BTB)4/3(L), where BTB is benzene-1,3,5-tribenzoate and L is 1-aminonaphthalene-3,7-dicarboxylate (NDC-NH2), 1-nitronaphthalene-3,7-dicarboxylate (NDC-NO2) or 1,5-dibenzyloxy-2,6-naphthalenedicarboxylate (NDC-(OBn)2), were synthesized and their gas (H2, CO2, or CH4) adsorption properties were compared to those of the un-functionalized, parent MOF-205. Ordered structural models for MOF-205 and its derivatives were built based on the crystal structures and were subsequently used for predicting porosity properties. Although the Brunauer–Emmett–Teller (BET) surface areas of the three MOF-205 derivatives were reduced (MOF-205, 4460; MOF-205-NH2, 4330; MOF-205-NO2, 3980; MOF-205-OBn, 3470 m2 g−1), all three derivatives were shown to have enhanced H2 adsorption capacities at 77 K and CO2 uptakes at 253, 273, and 298 K respectively at 1 bar in comparison with MOF-205. The results indicate the following trend in H2 adsorption: MOF-205 < MOF-205-NO2 < MOF-205-NH2 < MOF-205-OBn. MOF-205-OBn showed good ideal adsorbed solution theory (IAST) selectivity values of 6.5 for CO2/N2 (15/85 in v/v) and 2.7 for CO2/CH4 (50/50 in v/v) at 298 K. Despite the large reduction (−22%) in the surface area, MOF-205-OBn displayed comparable total volumetric CO2 (at 48 bar) and CH4 (at 35 bar) storage capacities with those of MOF-205 at 298 K: MOF-205-OBn, 305 (CO2) and 112 (CH4) cm3 cm−3, and for MOF-205, 307 (CO2) and 120 (CH4) cm3 cm−3, respectively.

Graphical abstract: Gas adsorption properties of highly porous metal–organic frameworks containing functionalized naphthalene dicarboxylate linkers

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Publication details

The article was received on 28 Jul 2014, accepted on 02 Oct 2014 and first published on 06 Oct 2014


Article type: Paper
DOI: 10.1039/C4DT02300E
Citation: Dalton Trans., 2014,43, 18017-18024
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    Gas adsorption properties of highly porous metal–organic frameworks containing functionalized naphthalene dicarboxylate linkers

    J. Sim, H. Yim, N. Ko, S. B. Choi, Y. Oh, H. J. Park, S. Park and J. Kim, Dalton Trans., 2014, 43, 18017
    DOI: 10.1039/C4DT02300E

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