Intrinsic Water Transport in Moisture-Capturing Hydrogels.

Moisture-capturing hydrogels have emerged as attractive sorbent materials capable of converting ambient humidity into liquid water. Recent works have demonstrated exceptional water capture capabilities of hydrogels while simultaneously exploring different strategies to accelerate water capture and release. However, on the material level, an understanding of the intrinsic transport properties of moisture-capturing hydrogels is currently missing, which hinders their rational design. In this work, we combine absorption and desorption experiments of macroscopic hydrogel samples in pure vapor with models of water diffusion in the hydrogels to demonstrate the first measurements of the intrinsic water diffusion coefficient in hydrogel-salt composites. Based on these insights, we pattern hydrogels with micropores to significantly decrease the required absorption and desorption times by 19% and 72%, respectively, while reducing the total water capacity of the hydrogel by only 4%. Thereby, we provide an effective strategy toward hydrogel material optimization, with a particular significance in pure-vapor environments.

Extreme Water Uptake of Hygroscopic Hydrogels through Maximized Swelling-Induced Salt Loading.

Hygroscopic hydrogels are emerging as scalable and low-cost sorbents for atmospheric water harvesting, dehumidification, passive cooling, and thermal energy storage. However, devices using these materials still exhibit insufficient performance, partly due to the limited water vapor uptake of the hydrogels. Here, the swelling dynamics of hydrogels in aqueous lithiumchloride solutions, the implications on hydrogel salt loading, and the resulting vapor uptake of the synthesized hydrogel-salt composites are characterized. By tuning the salt concentration of the swelling solutions and the cross-linking properties of the gels, hygroscopic hydrogels with extremely high salt loadings are synthesized, which enable unprecedented water uptakes of 1.79 and 3.86 gg-1 at relative humidity (RH) of 30% and 70%, respectively. At 30% RH, this exceeds previously reported water uptakes of metal-organic frameworks by over 100% and of hydrogels by 15%, bringing the uptake within 93% of the fundamental limit of hygroscopic salts while avoiding leakage problems common in salt solutions. By modeling the salt-vapor equilibria, the maximum leakage-free RH is elucidated as a function of hydrogel uptake and swelling ratio. These insights guide the design of hydrogels with exceptional hygroscopicity that enable sorption-based devices to tackle water scarcity and the global energy crisis.

Unusual Temperature Dependence of Water Sorption in Semicrystalline Hydrogels.

Water vapor sorption is a ubiquitous phenomenon in nature and plays an important role in various applications, including humidity regulation, energy storage, thermal management, and water harvesting. In particular, capturing moisture at elevated temperatures is highly desirable to prevent dehydration and to enlarge the tunability of water uptake. However, owing to the thermodynamic limit of conventional materials, sorbents inevitably tend to capture less water vapor at higher temperatures, impeding their broad applications. Here, an inverse temperature dependence of water sorption in poly(ethylene glycol) (PEG) hydrogels, where their water uptake can be doubled with increasing temperature from 25 to 50 °C, is reported. With mechanistic modeling of water-polymer interactions, this unusual water sorption is attributed to the first-order phase transformation of PEG structures, and the key parameters for a more generalized strategy in materials development are identified. This work elucidates a new regime of water sorption with an unusual temperature dependence, enabling a promising engineering space for harnessing moisture and heat.