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In this paper, a facile route is reported for the synthesis of MIL-53(Al) particles with different sizes and morphologies via the addition of various ratios of an esterified ligand to realize the deferred release of the ligand. Detailed proof indicates that the hydrolysis and deferred release of the ligand play a crucial role in modulating the morphology and size of the obtained MIL-53 nanoparticles without disrupting the original structure and framework of MIL-53. A possible mechanism for the growth of MIL-53 crystals with different exposed facets is proposed based on the structure of MIL-53 and BFDH (Bravais, Friedel, Donnay and Harker) theory. In addition, the influence of the crystal morphologies or exposed surfaces on the breathing effect and gas adsorption performance was evaluated using N2 and CO2 adsorption, and the as-prepared MIL-53 particles showed different adsorption isotherms and adsorption behavior under the same conditions. The MIL-53 particles synthesized using an appropriate amount of an esterified ligand could present an enhanced surface area when compared to that of bulk MIL-53, and the breathing effect during CO2 adsorption was moderate, while excessive amounts of the esterified ligand resulted in a decrease in the porosity and the formation of boehmite. Based on the experiment, the discrepancy in the breathing effect is mainly attributed to the stability of the narrow pore form with different exposed facets, but not the decreased particle size. [ABSTRACT FROM AUTHOR]

In this paper, an efficient method to fabricate Al-based metal organic framework (Al-MOF) MIL-96 crystals with controllable size and morphology, by mixing other forms of reactants to replace the coordination modulators or capping agents, is presented. The size and morphology of the MIL-96 crystals can be selectively varied by simply altering the ratio of dual reactants via their hydrolysis reaction. All the samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA) and nitrogen sorption. Then based on the BFDH theory, a mechanism for the impact of hydrolysis of reactants on the crystal size and morphology is presented and discussed. We also evaluated the performance of these MOFs as sorbents for capturing CO2, and they all show enhanced adsorption properties compared with the bulk material, displaying high adsorption capacities on CO2 at atmospheric pressure and ambient temperature. [ABSTRACT FROM AUTHOR]