Activation behavior for ion permeation in ion-exchange membranes: Role of ion dehydration in selective transport
Journal of Membrane Science 2019, 580, 316-326
Razi Epsztein, Evyatar Shaulsky, Mohan Qin, and Menachem Elimelech
The abstract reads as follows: We explored the mechanisms governing the selectivity of anion- and cation-exchange membranes for the transport of four monovalent anions (i.e., fluoride, chloride, bromide, and nitrate) and four monovalent cations (i.e., sodium, potassium, cesium, and ammonium), respectively. Our ion adsorption and transport tests with mixed ion solutions reveal that an ion with larger ionic radius and lower hydration energy is more favorably adsorbed onto the ion-exchange membrane but diffuses more slowly through the polymer matrix compared to an ion with smaller ionic radius and higher hydration energy. Individual anion (as sodium salt) or cation (as chloride salt) permeation tests at different temperatures were performed to evaluate the activation behavior of ion transport through the ion-exchange membranes by calculating the energy barrier and pre-exponential factor (i.e., the ion flux when the energy barrier is negligible) for ion transport from an Arrhenius-type equation. Our results show that an ion with smaller ionic radius and higher hydration energy experiences higher energy barrier (e.g., fluoride, 10.3 kcal mol−1) and possesses higher pre-exponential factor compared to an ion with larger ionic radius and lower hydration energy (e.g., bromide, 4.6 kcal mol−1). This correlation corroborates our main hypothesis that the activation behavior observed for ion transport is a result of ion dehydration at the water-membrane interface. Our proposed ion selectivity mechanism elucidates how ion dehydration governs the extent of ion permeation into the membrane and the subsequent transport through the charged polymer matrix. Future membrane design that promotes dehydration of target ions is challenging but can result in unprecedented ion selectivity.
This research was supported by CENT, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award No. DE-SC001911.