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.

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 Å cavities connected by ca. 6 Å triangular 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.

Graphene-based laminate membranes have been theoretically predicted to selectively transport ethanol from ethanol-water solution while blocking water. Here, we report robust angstromchannel graphene membranes (ACGMs) fabricated by intercalating carbon sheets derived from chitosan into thermally-reduced graphene oxide (GO) sheets. ACGMs with robust and continuous slitshaped pores (an average pore size of 3.9 Å) were 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.

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...

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