Small Rotations, Big Effects: Lessons from Water Adsorption in NU-1000

In this study, the adsorption mechanism of water in the metal–organic framework NU-1000 was investigated using molecular simulations. The simulations predict a significant impact of small changes in terminal aquo ligand orientation on the shape and pressure of the condensation step in the water adsorption isotherm. The analysis revealed that the rotational mobility of aquo ligands, often neglected in computational studies, can shift the condensation step by up to 20% in the relative humidity scale. By examining adsorption modes and interaction sites, it was demonstrated that configurational changes in the Zr6O8 node affect water adsorption significantly and can change the nature of the interactions from hydrophobic to hydrophilic. We propose a robust approach to account for these changes in simulations, achieving good agreement with experimental results. This work underscores the necessity of considering local, molecular flexibility in water adsorption simulations to avoid mischaracterization of MOFs’ water adsorption properties.