Two-dimensional (2D) membranes with lamina nanofluidic channels hold great promise for ion selective transport. However, the complex nanosheets preparation process and undesirable ion sieving ability of 2D channels in aqueous environment hindered the further application of 2D membranes. Herein, we designed and constructed 2D vermiculite-based nanofluidic membranes with ultrafast lithium ion-selective transport channels through interlayer chemical modification-to introduce sulfonated polyvinyl alcohol (SPVA). As for salt concentration of 0.2 M, the optimal VmMS-1 membrane with stable and sub-nanometer ion selective channels exhibited high Li⁺ permeation rate up to ∼1.3 mol m⁻² h⁻¹ driven by concentration gradient difference, while the selectivity of Li⁺/Mg²⁺, Li⁺/Na⁺, and Li⁺/K⁺ reached 23.8, 14.9, 19.1, respectively. Self-confinement ion recognition (SCIR) mechanism was proposed to describe the superior lithium ion-selective transport process in 2D confined channels. Self-confinement interlayer channel could manipulate the water-shell layer of ions and sulfonic acid groups could effectively recognize lithium ion to accelerate them transport. This study provides a new vermiculite membrane design insight based on SCIR mechanism that is expected to achieve high lithium extraction, as well as providing a new insight of membrane design for other 2D materials.

具有层纳米流体通道的二维 (2D) 膜在离子选择性传输方面具有广阔的前景。然而，复杂的纳米片制备过程和二维通道在水环境中离子筛分能力不佳阻碍了二维膜的进一步应用。在此，我们设计并构建了基于二维蛭石的纳米流体膜，具有超快的锂离子选择性传输通道，通过层间化学修饰引入磺化聚乙烯醇（SPVA）。对于0.2 M的盐浓度，具有稳定的亚纳米离子选择性通道的最佳VmMS-1膜表现出高达~1.3 mol m ⁻²  h ^{−1的高Li +渗透速率}在浓度梯度差驱动下，Li ⁺ /Mg ²⁺、Li ⁺ /Na ⁺、Li ⁺ /K ^{+的选择性}分别达到23.8、14.9、19.1。提出了自约束离子识别（SCIR）机制来描述二维受限通道中优异的锂离子选择性传输过程。自约束层间通道可以操纵离子的水壳层，磺酸基可以有效识别锂离子，加速其传输。该研究提供了基于SCIR机制的蛭石膜设计新见解，有望实现高锂提取率，也为其他膜设计提供新见解。2D 材料。