A new class of 2D van der Waals metal–organic frameworks (MOFs) is discovered. Large‐scale synthesis of van der Waals MOF nanosheets with controlled interlayer coupling strength is realized via novel biphase growth. The discussed methods outline kinetics, manufacturing design rules, as well as introduce their vibrational (Raman), structural, and optical properties, and open new avenues toward their large‐scale production. Abstract Large‐scale synthesis of van der Waals (vdW) metal–organic framework (MOF) nanosheets with controlled crystallinity and interlayer coupling strength is one of the bottlenecks in 2D materials that has limited its successful transition to large‐scale applications. Here, scalable synthesis of mBDC (m = Zn and Cu) 2D MOFs at large scales through a biphase method is demonstrated. The results show replacing water molecules with pyridine eliminates hydrogen bond formation at metal cluster sites. This prohibits tight coupling across adjacent MOF layers and sustains controllable 2D vdW MOF growth. It is further shown that control over the growth speed, crystallinity, and thickness can be achieved by addition of a controlled amount of triethylamine and formic acid to achieve highly crystalline vdW MOF nanosheets with extraordinarily high aspect ratio. The described synthesis route can easily be scaled up for large‐scale production either by deposition onto desired substrates or in crystalline layered powder form. Owing to its large lateral size, vdW nature, and high crystallinity, it is possible to perform atomic force microscopy, Kelvin probe force microscopy, and Raman measurements on the 2D MOFs. The results not only establish their vibrational properties and layer‐dependent responses but also show striking differences from other 2D inorganic materials.

Published in: "Advanced Materials".