화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.142, No.21, 9827-9833, 2020
Sulfonated Sub-1-nm Metal-Organic Framework Channels with Ultrahigh Proton Selectivity
Biological proton channels are sub-1-nm protein pores with ultrahigh proton (H+) selectivity over other ions. Inspired by biological proton channels, developing artificial proton channels with biological-level selectivity is of fundamental significance for separation science. Herein we report synthetic proton channels fabrication based on sulfonated metalorganic frameworks (MOFs), UiO-66-X, X = SAG, NH-SAG, (NH-SAG)(2) (SAG: sulfonic acid groups), which have sub-1-nm windows and a high density of sulfonic acid groups mimicking natural proton channels. The ion conductance of UiO-66-X channels follows the sequence: H+ >> K+ > Na+ > Li+, and the sulfonated UiO-66 derivative channels show proton selectivity much higher than that of the pristine UiO-66 channels. Particularly, the UiO-66-(NH-SAG)(2) channels exhibit ultrahigh proton selectivities, H+/Li+ up to similar to 100, H+/Na+ of similar to 80, and H+/K+ of similar to 70, which are similar to 3 times of that of UiO-66-NH-SAG channels, and similar to 15 times of that of UiO-66@SAG channels. The ultrahigh proton selectivity in the sulfonated sub-1-nm MOF channels is mainly attributed to the narrow window-cavity pore structure functionalized with nanoconfined high-density sulfonic acid groups that facilitate fast proton transport and simultaneously exclude other cations. Our work opens an avenue to develop functional MOF channels for selective ion conduction and efficient ion separation.