Atomistic Insight into Adsorption, Mobility, and Vibration of Water in Ion-Exchanged Zeolite-like Metal−Organic Frameworks

The adsorption, mobility, and vibration of water in ion-exchanged rho-zeolite-like metal−organic frameworks (ZMOFs) are investigated using atomistic simulations. Because of the high affinity for the ionic framework and nonframework ions, water is strongly adsorbed in rho-ZMOFs with a three-step adsorption mechanism. At low pressures, water is preferentially adsorbed onto Na⁺ ions, particularly at site II; with increasing pressure, adsorption occurs near the framework and finally in the large cage. Upon water adsorption, Na⁺ ions are observed to redistribute from site I to site II and gradually hydrated with increasing pressure. In Li-, Na-, and Cs-exchanged rho-ZMOFs, the adsorption capacity and isosteric heat decrease with increasing ionic radius attributed to the reduced electrostatic interaction and free volume. The mobility of water in Na-rho-ZMOF increases at low pressures but decreases upon approaching saturation. With sufficient amount of water present, the mobility of Na⁺ ions is promoted. The vibrational spectra of water in Na-rho-ZMOF exhibit distinct bands for librational motion, bending, and stretching. The librational motion has a frequency higher than bulk water due to confinement. With increasing loading and hence stronger coordinative attraction, the bending frequency shows a blue shift. Symmetric and asymmetric modes are observed in the stretching as a consequence of the strong water−ion interaction. This study provides a fundamental microscopic insight into the static and dynamic properties of water in charged ZMOFs and reveals the subtle interplay between water and nonframework ions.