The large-scale preparation of monolayer two-dimensional (2D) material remains a great challenge, which hinders its real-world applications. Herein, we report a novel layered metal–organic framework (MOF), IPM-1, which was synthesized from a cage-like organic linker, with extremely weak interlaminar interaction. When subjected to external disturbance, IPM-1 degenerated into an intermediate state between the crystalline and amorphous phase, in which the layers retain the in-plane two-dimensional periodic structure but are misaligned in the third dimension, leading to the loss of apparent porosity and crystallinity. This amorphous IPM-1 is readily exfoliated at gram scale into crystalline 2D nanosheets with a thickness of 1.15 nm, excellent thickness homogeneity, lateral size up to 10 μm, and restored microporosity. IPM-1 nanosheets exhibit high chemical stability and catalytic activity in the oxidation of alcohol, combining the advantages of both homogeneous and heterogeneous catalyst. This work underscores that MOFs without apparent crystallinity can be ideal precursors for the successful preparation of 2D crystalline monolayer nanosheets.

单层二维（2D）材料的大规模制备仍然是一个巨大的挑战，阻碍了其实际应用。在此，我们报告了一种新型层状金属有机框架（MOF）， IPM-1，它是由笼状有机连接体合成的，具有极弱的层间相互作用。当受到外界干扰时， IPM-1退化为晶相和非晶相之间的中间状态，其中各层保持面内二维周期性结构，但在三维上错位，导致表观孔隙率和结晶度的损失。这种无定形 IPM-1 很容易在克级剥离成晶体 2D 纳米片，厚度为 1.15 nm，具有出色的厚度均匀性，横向尺寸高达 10 μm，并恢复了微孔性。 IPM-1纳米片在乙醇氧化中表现出很高的化学稳定性和催化活性，结合了均相和非均相催化剂的优点。这项工作强调，没有明显结晶度的 MOF 可以成为成功制备二维结晶单层纳米片的理想前体。