Owing to their excellent physical and electrical properties, metal–organic framework (MOF) materials with well‐defined supramolecular structures have received extensive research attention. However, the fabrication of large‐area two‐dimensional (2D) MOF films is still a significant challenge. Herein, we propose a novel electrochemical (EC) synthesis method for the preparation of large‐area Cu3(HHTP)2 MOF film on single‐crystal Cu (100) anode. The surface reaction was achieved via charge‐induced molecular assembly. The synthesized MOF film exhibited a high crystalline quality with an electrical conductivity of approximately 0.087 S cm−1, which was around 1000 times larger than the previously reported values for the same material prepared by the interface method. In addition, Cu2(MTCP), Cu3(BTPA)2, and Cu3(TPTC)2 MOF films were synthesized on Cu foil with the same strategy, which confirmed the universality of the proposed method. This controllable EC method can be effectively applied to the industrial‐scale production of 2D MOF films on Cu foil.
Covalent organic frameworks (COFs) can exhibit high specific surface area and catalytic activity, but traditional solution-based synthesis methods often lead to insoluble and infusible powders or fragile films on solution surface. Herein we report large-area –C=N– linked two-dimensional (2D) COF films with controllable thicknesses via vapor induced conversion in a chemical vapor deposition (CVD) system. The assembly process is achieved by reversible Schiff base polycondensation between PyTTA film and TPA vapor, which results in a uniform organic framework film directly on growth substrate, and is driven by π‐π stacking interactions with the aid of water and acetic acid. Wafer-scale 2D COF films with different structures have been successfully synthesized by adjusting their building blocks, suggesting its generic applicability. The carrier mobility of PyTTA-TPA COF films can reach 1.89 × 10−3 cm2 V−1 s−1. When employed as catalysts in hydrogen evolution reaction (HER), they show high electrocatalytic activity compared with metal-free COFs or even some metallic catalysts. Our results represent a versatile route for the direct construction of large-area uniform 2D COF films on substrates towards multi-functional applications of 2D π‐conjugated systems.
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