ABSTRACT
The electrochemical stability window of water is known to vary with the type and concentration of dissolved salts. However, the underlying influence of ions on the thermodynamic stability of aqueous solutions has not been fully understood. Here, we investigated the electrolytic behaviors of aqueous electrolytes as a function of different ions. Our findings indicate that ions with high ionic potentials, i.e., charge density, promote the formation of their respective hydration structures, enhancing electrolytic reactions via an inductive effect, particularly for small cations. Conversely, ions with lower ionic potentials increase the proportion of free water molecules-those not engaged in hydration shells or hydrogen-bonding networks-leading to greater electrolytic stability. Furthermore, we observe that the chemical environment created by bulky ions with lower ionic potentials impedes electrolytic reactions by frustrating the solvation of protons and hydroxide ions, the products of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. We found that the solvation of protons plays a more substantial role than that of hydroxide, which explains a greater shift for OER than for HER, a puzzle that cannot be rationalized by the notion of varying O-H bond strengths of water. These insights will help the design of aqueous systems.
ABSTRACT
Passive daytime radiative cooling (PDRC) involves spontaneously cooling a surface by reflecting sunlight and radiating heat to the cold outer space. Current PDRC designs are promising alternatives to electrical cooling but are either inefficient or have limited applicability. We present a simple, inexpensive, and scalable phase inversion-based method for fabricating hierarchically porous poly(vinylidene fluoride-co-hexafluoropropene) [P(VdF-HFP)HP] coatings with excellent PDRC capability. High, substrate-independent hemispherical solar reflectances (0.96 ± 0.03) and long-wave infrared emittances (0.97 ± 0.02) allow for subambient temperature drops of ~6°C and cooling powers of ~96 watts per square meter (W m-2) under solar intensities of 890 and 750 W m-2, respectively. The performance equals or surpasses those of state-of-the-art PDRC designs, and the technique offers a paint-like simplicity.
