Using Helium Pycnometry to Study the Apparent Densities of Metal–Organic Frameworks

When investigating the gas storage capacities of metal-organic frameworks, volumetric values are often reported based on crystallographic densities. Although it is widely accepted that Langmuir and BET surface areas of a given MOF can vary depending on the exact synthetic conditions used to prepare the materials, it is rare that deviations in density from the optimal crystallographic density are considered. The actual (apparent) densities of these materials are highly variable depending on the presence of defects, impurities, or multiple phases that arise during synthesis. The apparent density of specific samples, which represent an experimentally determined crystallographic density, can be measured with helium pycnometry where the skeletal density measured via pycnometry is easily converted to an apparent density. In the work reported here, apparent density was measured for 46 samples across a series of different structure types where experimentally measured density was consistently lower than crystallographic density, up to 30% in some cases. Subsequently, use of this technique allows for quantification of densities for those materials whose structures have not been crystallographically determined.