Syntheses, Structures, and Gas Adsorption Properties of Two Novel Cadmium–Sodium Organic Frameworks with 1,3,5-Benzenetricarboxylate Ligands

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Abstract

Solvothermal reactions of Cd(CH3COO)2·2H2O and NaOH with 1,3,5-benzenetricarboxylic acid (H3BTC) in a mixture of H2O/DMA (DMA = N,N?-dimethylacetamide) gave rise to two novel 3D porous metal?organic frameworks (MOFs), [Cd3Na6(BTC)4(H2O)12]·H2O (1) and [Cd3Na2(BTC)3(H2O)3]·[H2N(CH3)2]·H2O (2), which were characterized by single crystal and variable temperature powder X-ray diffraction (VTPXRD), IR spectroscopy, elemental analyses, inductively coupled plasma measurements, and coupled thermogravimetric?mass spectrometric analyses. Compound 1 crystallizes in the tetragonal space group P42/n and could be described as a 2-fold interpenetrated net having a boracite (bor) topology, bridged by {Na3O12} trimers. Compound 2 crystallizes in the monoclinic space group Cc with 1D channels distributed in an unusual honeycomb fashion along the b-axis. {Na2O10} dimers, (CH3)2NH2+ ions, and guest water are located in these channels. TG-MS and VTPXRD studies revealed that 1 had a high thermal stability up to 340 °C under air, and 2 was stable up to 310 °C. The gas-adsorption investigation disclosed that compound 1 exhibited H2 uptake of 1.11 wt % at 77 K and 1.0 bar, with a high adsorption heat (8.4 kJ mol?1).

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