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–/SO4
2– 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–/SO4
2– 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 ×
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.