The impact of defects and crystal size on negative gas adsorption in DUT-49 analyzed by in situ 129Xe NMR spectroscopy.
2020-03-11T05:16:39Z (GMT) by
The origin of crystal size-dependent adsorption behavior of flexible metal-organic frameworks is increasingly studied. In this contribution, we probe the solid-fluid interactions of DUT-49 crystals of different size by in situ 129Xe NMR spectroscopy at 200 K. With decreasing size of the crystals, the average solid-fluid interactions are found to decrease reflected by a decrease in chemical shift of adsorbed xenon from 230 to 200 ppm explaining the lack of adsorption-induced transitions for smaller crystals. However, recent studies propose that these results can also originate from the presence of lattice defects. To investigate the influence of defects on the adsorption behavior of DUT-49 we synthesized a series of samples with tailored defect concentrations and characterized them by in situ 129Xe NMR. In comparison to the results obtained for crystals with different size we find pronounced changes of the adsorption behavior and influence of the chemical shift only for very high concentrations of defects, which further emphasizes the important role of particle size phenomena.