In recent years, studies on porous coordination polymers (PCPs) have been rapidly developed owing to their varied framework structures, high stability, tailored pore structures, high surface areas and specific properties. In addition, it was found that the properties of PCPs nano/micromaterials depend on their crystal morphology and size, therefore, controlled synthesis of PCP nano/micromaterials with specific morphology and size is an attractive research area. We focus our attention on crystal engineering, structure and property of PCPs as well as their nano/micromaterials with multi-carboxylate and/or imidazole-containing organic ligands such as benzene-1,3, 5-tricarboxylic acid (H3BTC), 4,4',4''-benzene-1,3,5-triyl-tribenzoic acid (H3BTB) and 1,4-di(1H-imidazol-4- yl)benzene (H2L) were used to react with metal salts to give PCPs nano/micromaterials with controllable morphology and size under different reaction conditions. The nano/micromaterials were characterized by powder X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and so on. The formation mechanism of PCPs nano/micromaterials and the influence of crystal shape and size on their properties were investigated. For example, a facile and convenient method was used for synthesis of [Cu3(BTB)2] (MOF-14) microcrystals with definite shapes and crystal facets controlled by reaction medium at room temperature. The amount of sodium acetate was found to play a crucial role in the shape evolution of MOF-14 from rhombic dodecahedron to truncated rhombic dodecahedron and cube with truncated edges and then to cube. In addition, the addition of base could accelerate the formation rate of crystal growth and increase the supersaturation of crystal growth, and thus result in the formation of MOF-14 cube crystals with high-energy crystal facets. Gas adsorption properties of MOF-14 with different shapes were studied and the results reveal that the PCP microcrystals display excellent and morphology dependent sorption property.

Synthesis and property of porous coordination polymer nano/micromaterials

251st National Meeting (2016)

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