Subnanometer Ion Channel Anion Exchange Membranes Having a Rigid Benzimidazole Structure for Selective Anion Separation

Ion-conductive polymers having a well-defined phase-separated structure show the potential application of separating mono- and bivalent ion separation. In this work, three side-chain-type poly(arylene ether sulfone)-based anion exchange membranes (AEMs) have been fabricated to investigate the effect of the stiffness of the polymer backbone within AEMs on the Cl-/NO3- and Cl-/SO42- separation performance. Our investigations via small-angle X-ray scattering (SAXS), positron annihilation, and differential scanning calorimetry (DSC) demonstrate that the as-prepared AEM with a rigid benzimidazole structure in the backbone bears subnanometer ion channels resulting from the arrangement of the rigid polymer backbone. In particular, SAXS results demonstrate that the rigid benzimidazole-containing AEM in the wet state has an ion cluster size of 0.548 nm, which is smaller than that of an AEM with alkyl segments in the backbone (0.760 nm). Thus, in the electrodialysis (ED) process, the former exhibits a superior capacity of separating Cl-/SO42- ions relative to latter. Nevertheless, the benzimidazole-containing AEM shows an inability to separate the Cl-/NO3- ions, which is possibly due to the similar ion size of the two. The higher rotational energy barrier (4.3 X 10(-3) Hartree) of benzimidazole units and the smaller polymer matrix free-volume (0.636%) in the AEM significantly contribute to the construction of smaller ion channels. As a result, it is believed that the rigid benzimidazole structure of this kind is a benefit to the construction of stable subnanometer ion channels in the AEM that can selectively separate ions with different sizes.

Automated summary

Ion-conductive polymers with well-defined phase-separated structure have the potential application of separating mono- and bivalent ions. In this study, three anion exchange membranes based on side-chain-type poly(arylene ether sulfone) with different backbone stiffness were fabricated to investigate their separation performance of Cl-/NO3- and Cl-/SO42- ions. The results showed that the membrane with a rigid benzimidazole structure in the backbone had smaller ion channels and exhibited superior performance in separating Cl-/SO42- ions. However, it failed to separate Cl-/NO3- ions, possibly due to the similar ion size. The higher rotational energy barrier and smaller polymer matrix free-volume contributed to the construction of smaller ion channels.