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

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 H₂O₂ in acid media.