Graphene and MOF Assembly: Enhanced Fabrication and Functional Derivative via MOF Amorphization

Abstract The integration of graphene and metal–organic frameworks (MOFs) has numerous implications across various domains, but fabricating such assemblies is often complicated and time‐consuming. Herein, a one‐step preparation of graphene‐MOF assembly is presented by directly impregnating vertical graphene (VG) arrays into the zeolitic imidazolate framework (ZIF) precursors under ambient conditions. This approach can effectively assemble multiple ZIFs, including ZIF‐7, ZIF‐8, and ZIF‐67, resulting in their uniform dispersion on the VG with adjustable sizes and shapes. Hydrogen defects on the VG surface are critical in inducing such high‐efficiency ZIF assembly, acting as the reactive sites to interact with the ZIF precursors and facilitate their crystallisation. The versatility of VG‐ZIF‐67 assembly is further demonstrated by exploring the process of MOF amorphization. Surprisingly, this process leads to an amorphous thin‐film coating formed on VG (named VG‐IL‐amZIF‐67), which preserves the short‐range molecular bonds of crystalline ZIF‐67 while sacrificing the long‐range order. Such a unique film‐on‐graphene architecture maintains the essential characteristics and functionalities of ZIF‐67 within a disordered arrangement, making it well‐suited for electrocatalysis. In electrochemical oxygen reduction, VG‐IL‐amZIF‐67 exhibits exceptional activity, selectivity, and stability to produce H 2 O 2 in acid media.