Water Adsorption in Soft and Heterogeneous Nanopores

ConspectusLiquids under confinement differ in behavior from their bulk counterparts and can acquire properties that are specific to the confined phase and linked to the nature and structure of the host matrix. While confined liquid water is not a new topic of research, the past few years have seen a series of intriguing novel features for water inside nanoscale pores. These unusual properties arise from the very specific nature of nanoporous materials, termed "soft porous crystals"; they combine large-scale flexibility with a heterogeneous internal surface. This creates a rich diversity of behavior for the adsorbed water, and the combination of different experimental characterization techniques along with computational chemistry at various scales is necessary to understand the phenomena observed and their microscopic origins. The range of systems of interest span the whole chemical range, from the inorganic (zeolites, imogolites) to the organic (microporous carbons, graphene, and its derivatives), and even encompass the hybrid organic-inorganic systems (such as metal-organic frameworks).The combination of large scale flexibility with the strong physisorption (or even chemisorption) of water can lead to unusual properties (belonging to the "metamaterials" category) and to novel phenomena. One striking example is the recent elucidation of the mechanism of negative hydration expansion in ZrW₂O₈, by which adsorption of ∼10 wt % water in the inorganic nonporous framework leads to large shrinkage of its volume. Another eye-catching case is the occurrence of multiple water adsorption-driven structural transitions in the MIL-53 family of materials: the specific interactions between water guest molecules and the host framework create behavior that has not been observed with any other adsorbate. Both are counterintuitive phenomena that have been elucidated by a combination of experimental in situ techniques and molecular simulation.Another important direction of research is the shift in the systems and phenomena studied, from physical adsorption toward studies of reactivity, hydrothermal stability, and the effect of confinement on aqueous phases more complex than pure water. There have been examples of water adsorption in highly flexible metal-organic frameworks being able to compete with the materials' coordination bonds, thereby limiting its hydrothermal stability, while tweaking the functional groups of the same framework can lead to increased stability while retaining the flexibility of the material. However, this additional complexity and tunability in the macroscopic behavior can occur from changes in the confined fluid rather than the material. Very recent studies have shown that aqueous solutions of high concentration (such as LiCl up to 20 mol L^-1) confined in flexible nanoporous materials can have specific properties different from pure water and not entirely explained by osmotic effects. There, the strong ordering of the confined electrolyte competes with the structural flexibility of the framework to create an entirely new behavior for the {host, guest} system.