In situ visualization of loading-dependent water effects in a stable metal–organic framework

Competitive water adsorption can have a significant impact on metal–organic framework performance properties, ranging from occupying active sites in catalytic reactions to co-adsorbing at the most favourable adsorption sites in gas separation and storage applications. In this study, we investigate, for a metal–organic framework that is stable after moisture exposure, what are the reversible, loading-dependent structural changes that occur during water adsorption. Herein, a combination of in situ synchrotron powder and single-crystal diffraction, infrared spectroscopy and molecular modelling analysis was used to understand the important role of loading-dependent water effects in a water stable metal–organic framework. Through this analysis, insights into changes in crystallographic lattice parameters, water siting information and water-induced defect structure as a response to water loading were obtained. This work shows that, even in stable metal–organic frameworks that maintain their porosity and crystallinity after moisture exposure, important molecular-level structural changes can still occur during water adsorption due to guest–host interactions such as water-induced bond rearrangements.