Dynamic Insights into the Growth Mechanisms of 2D Covalent Organic Frameworks on Graphene Surfaces.

Producing high-quality two-dimensional (2D) covalent organic frameworks (COFs) is crucial for industrial applications. However, this remains significantly challenging with current synthetic techniques. A deep understanding of the intermolecular interactions, reaction temperature, and oligomers is essential to facilitate the growth of highly crystalline COF films. Herein, molecular dynamics simulations were employed to explore the growth of 2D COFs from monomer assemblies on graphene. Our results showed that chain growth reactions dominated the COF surface growth and that van der Waals (vdW) interactions were important in enhancing the crystallinity through monomer preorganization. Moreover, appropriately tuning the reaction temperature improved the COF crystallinity and minimized the effects of amorphous oligomers. Additionally, the strength of the interface between the COF and the graphene substrate indicated that the adhesion force was proportional to the crystallinity of the COF. This work reveals the mechanisms for nucleation and growth of COFs on surfaces and provides theoretical guidance for fabricating high-quality 2D polymer-based crystalline nanomaterials.

High-Strength Polycrystalline Covalent Organic Framework with Abnormal Thermal Transport Insensitive to Grain Boundary.

Grain boundaries (GBs) in two-dimensional (2D) covalent organic frameworks (COFs) unavoidably form during the fabrication process, playing pivotal roles in the physical characteristics of COFs. Herein, molecular dynamics simulations were employed to elucidate the fracture failure and thermal transport mechanisms of polycrystalline COFs (p-COFs). The results revealed that the tilt angle of GBs significantly influences out-of-plane wrinkles and residual stress in monolayer p-COFs. The tensile strength of p-COFs can be enhanced and weakened with the tilt angle, which exhibits an inverse relationship with the defect density. The crack always originates from weaker heptagon rings during uniaxial tension. Notably, the thermal transport in p-COFs is insensitive to the GBs due to the variation of minor polymer chain length at defects, which is abnormal for other 2D crystalline materials. This study contributes insights into the impact of GBs in p-COFs and offers theoretical guidance for structural design and practical applications of advanced COFs.