Birnessite is a layered MnO 2 mineral capable of intercalating nanometric water films in its bulk. With its variable distributions of Mn oxidation states (Mn IV , Mn III , and Mn II ), cationic vacancies, and interlayer cationic populations, birnessite plays key roles in catalysis, energy storage solutions, and environmental (geo)chemistry. We here report the molecular controls driving the nanoscale intercalation of water in potassium-exchanged birnessite nanoparticles. From microgravimetry, vibrational spectroscopy, and X-ray diffraction, we find that birnessite intercalates no more than one monolayer of water per interlayer when exposed to water vapor at 25 °C, even near the dew point. Molecular dynamics showed that a single monolayer is an energetically favorable hydration state that consists of 1.33 water molecules per unit cell. This monolayer is stabilized by concerted potassium–water and direct water–birnessite interactions, and involves negligible water–water interactions. Using our composite adsorption–condensation–intercalation model, we predicted humidity-dependent water loadings in terms of water intercalated in the internal and adsorbed at external basal faces, the proportions of which vary with particle size. The model also accounts for additional populations condensed on and between particles. By describing the nanoscale hydration of birnessite, our work secures a path for understanding the water-driven catalytic chemistry that this important layered manganese oxide mineral can host in natural and technological settings.

Sorption isotherm models have traditionally served as an invaluable tool to characterize synthesized and natural mineral particles. However, for particles susceptible to substantial hydration, such as the swelling smectite clay minerals and other layered minerals displaying intercalation of discrete water monolayers, traditional isotherm models inadequately describe the total water uptake as a result of the change in available surface sites and area during the hydration process. With the goal of deconvoluting the water uptake behavior of swelling smectite minerals, this research presents a novel composite isotherm model that describes water uptake by surface adsorption, condensation, and stepwise intercalation. A set of eight montmorillonite samples ion-exchanged with different countercations (Li+, Na+, K+, Cs+, Mg2+, Ca2+, Sr2+, and Cu2+) were used to develop this model, which was based on gravimetric uptake measurements and X-ray diffraction data of basal spacings obtained from relative humidity conditions up to 98% relative humidity.

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