Hierarchical Silica Composites for Enhanced Water Adsorption at Low Humidity

To combat water scarcity in remote areas around the world, adsorption-based atmospheric water harvesting (AWH) has been proposed as a technology that can be used alongside existing water production capabilities. However, commonly used adsorbents either have low water adsorption loadings or are difficult to regenerate. In this work, we developed two novel hierarchical silica-salt composites that both exhibit high water adsorption loadings under dry and humid conditions. The total water vapor loading, kinetics, and heats of water adsorption for both silica-salt composites were investigated. As hierarchical silicas have tunable pores and large pore volumes, these materials serve as effective host matrixes for the hygroscopic salt LiCl. Our results suggest that hierarchical pores play a significant role in water adsorption: micropores and some smaller mesopores act as "storage" sites for hygroscopic salt, whereas larger mesopores and macropores increase the accessibility of water vapor into the silica. Using this mix of pores, we achieved greater than 0.4 g H₂O/g composite at 10% RH and 27 °C. Additionally, we found that the salt-impregnated silica and bare silica had the same heat of adsorption: 80-90 kJ/mol. The results suggest that the H-bond interactions are similar for both systems and that the primary mechanism at play here is water cluster adsorption/desorption. Despite the similar energies, the LiCl-containing materials exhibited considerably slower kinetics than bare silica materials. Of equal importance to the adsorption capacity and kinetics of these composites is their mechanical stability. To assess their mechanical stability, high-energy ball milling of silica was conducted to create more uniform particle sizes. However, reduced particle sizes came at a cost─the BET surface areas and pore volumes were drastically decreased after more than 1 h of ball milling. Findings from this study suggest that short-term ball milling may be a viable large-scale option to reduce particle size in silica materials without sacrificing significant performance.