Fabrication of a hierarchically structured HKUST-1 by a mixed-ligand approach

A novel hierarchically structured HKUST-1 has been synthesized under hydrothermal synthesis conditions using a mixed ligand strategy, in which benzene-1,3,5-tricarboxylic acid was partially replaced by benzoic acid. The formation of the crystalline HKUST-1 material containing mesoporosity was characterized by a complementary combination of X-ray powder diffraction, Fourier transform infrared spectroscopy, N-2 adsorption-desorption isotherms, scanning electron microscopy, transmission electron microscopy and thermogravimetric analysis. These analyses indicated that incorporation of a certain amount of benzoic acid in the crystal lattice of HKUST-1 preserved its crystal structure. The benzoic acid ligand could be seen as defect sites that two carboxylate groups of one linker molecule are missing, leading to a distorted paddle-wheel unit, which induced the formation of an intra-crystalline mesoporous structure in HKUST-1. The hierarchically structured HKUST-1 combines the dual merits of two different pore structures, enabling it has maximum structural function in a limited space due to the enhanced diffusion through mesoporous channels. The presented method opens the door for the preparation of a variety of hierarchically structured MOFs.