Synthetic azobenzene-containing metal-organic framework ion channels toward efficient light-gated ion transport at the subnanoscale.

Artificial nanochannels with diverse responsive properties have been widely developed to replicate the smart gating functionalities of biological ion channels. However, in these traditional nanochannels, common responsive molecules are usually too small to efficiently block the large channels under the closed states, leading to weak gating performances. Herein, we report carboxylated azobenzene-coordinated metal-organic-framework (AZO-MOF) ion channels with impressive light-gating properties. The AZO-MOF ion channels were synthesized by the confined growth of AZO-MOFs, composed of light-responsive AZO-containing ligands, non-responsive ligands and metal clusters, into ion-track-etched polymer nanochannels. The AZO-MOF ion channels with an appropriate number of AZO ligands showed a well-maintained crystalline and three-dimensional porous structure, including nanoscale cavities and subnanoscale windows for LiCl conduction. Meanwhile, the AZO-containing ligands bend and stretch upon light irradiation to open and close the pathways, thus gating the ion flux through the AZO-MOF ion channels with high on-off ratios up to 40.2, which is ∼2.3-30 times those of AZO-encapsulated MOF ion channels and AZO-modified nanochannels. This work suggests ways to achieve subnanoscaled gating of ion transport by angstrom-porous MOFs coordinated by stimuli-responsive ligands.

Selective Permeation of Water through Angstrom-Channel Graphene Membranes for Bioethanol Concentration.

Graphene-based laminate membranes have been theoretically predicted to selectively transport ethanol from ethanol-water solution while blocking water. Here, robust angstrom-channel graphene membranes (ACGMs) fabricated by intercalating carbon sheets derived from chitosan into thermally reduced graphene oxide (GO) sheets are reported. ACGMs with robust and continuous slit-shaped pores (an average pore size of 3.9 Å) are investigated for the dehydration of ethanol. Surprisingly, only water permeates through ACGMs in the presence of aqueous ethanol solution. For the water-ethanol mixture containing 90 wt% ethanol, water can selectively permeate through ACGMs with a water flux of 63.8 ± 3.2 kg m-2 h-1 at 20 °C and 389.1 ± 19.4 kg m-2 h-1 at 60 °C, which are over two orders of magnitude higher than those of conventional pervaporation membranes. This means that ACGMs can effectively operate at room temperature. Moreover, the ethanol can be fast concentrated to high purity (up to 99.9 wt%). Therefore, ACGMs are very promising for production of bioethanol with high efficiency, thus improving its process sustainability.

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 metal-organic 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 ∼100, H+/Na+ of ∼80, and H+/K+ of ∼70, which are ∼3 times of that of UiO-66-NH-SAG channels, and ∼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.

Efficient Gating of Ion Transport in Three-Dimensional Metal-Organic Framework Sub-Nanochannels with Confined Light-Responsive Azobenzene Molecules.

1D nanochannels modified with responsive molecules are fabricated to replicate gating functionalities of biological ion channels, but gating effects are usually weak because small molecular gates cannot efficiently block the large channels in the closed states. Now, 3D metal-organic framework (MOF) sub-nanochannels (SNCs) confined with azobenzene (AZO) molecules achieve efficient light-gating functionalities. The 3D MOFSNCs consisting of a MOF UiO66 with ca. 9-12 Šcavities connected by ca. 6 Štriangular windows work as angstrom-scale ion channels, while confined AZO within the MOF cavities function as light-driven molecular gates to efficiently regulate the ion flux. The AZO-MOFSNCs show good cyclic gating performance and high on-off ratios up to 17.8, an order of magnitude higher than ratios observed in conventional 1D AZO-modified nanochannels (1.3-1.5). This work provides a strategy to develop highly efficient switchable ion channels based on 3D porous MOFs and small responsive molecules.