2D compounds exfoliated from weakly bonded bulk materials with van der Waals (vdW) interaction are easily accessible. However, the strong internal ionic/covalent bonding of most inorganic crystal frameworks greatly hinders 2D material exfoliation. Herein, we first proposed a radical/strain‐synergistic strategy to exfoliate non‐vdW interacting pseudo‐layered phosphate framework. Specifically, hydroxyl radicals (•OH) distort the covalent bond irreversibly, meanwhile, H2O molecules as solvents, further accelerating interlayered ionic bond breakage but mechanical expansion. The innovative 2D laminar NASICON‐type Na3V2(PO4)2O2F crystal, exfoliated by •OH/H2O synergistic strategy, exhibits enhanced sodium‐ion storage capacity, high‐rate performance (85.7 mA h g‐1 at 20 C), cyclic life (2300 cycles), and ion migration rates, compared with the bulk framework. Importantly, this chemical/physical dual driving technique realized the effective exfoliation for strongly coupled pseudo‐layered frameworks, which accelerates 2D functional material development.

中文翻译：

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自由基/应变协同过程衍生的共价伪层状磷酸酯框架的二维剥离化学


通过范德华 (vdW) 相互作用从弱键合块状材料中剥离的二维化合物很容易获得。然而，大多数无机晶体框架的强内部离子/共价键极大地阻碍了二维材料的剥离。在此，我们首先提出了一种自由基/应变协同策略来剥离非 vdW 相互作用的伪层状磷酸盐框架。具体来说，羟基自由基(·OH)不可逆地扭曲共价键，同时H2O分子作为溶剂，进一步加速层间离子键断裂但机械膨胀。创新的二维层状 NASICON 型 Na3V2(PO4)2O2F 晶体，通过·OH/H2O 协同策略剥离，具有增强的钠离子存储容量、高倍率性能（20 C 时为 85.7 mA h g-1）、循环寿命（2300周期）和离子迁移率，与本体框架相比。重要的是，这种化学/物理双重驱动技术实现了强耦合赝层状框架的有效剥离，从而加速了二维功能材料的开发。