The use of two different classes of covalent organic frameworks (covalent triazine and imine linked frameworks) as supports for molecular Ni²⁺ catalysts is presented. For COFs, a large concentration of N heteroatoms, either in the form of quasi bipyridine or as diiminopyridine moieties, allows for the coordination of NiBr₂ to the scaffold of the porous polymers. When applied as catalysts in the oligomerization of ethylene under mild reaction conditions (15 bar, 50 °C), these new catalysts display an activity comparable to those of their homogeneous counterpart and a fivefold higher selectivity to C₆ ⁺ olefins. Accumulation of long chain hydrocarbons within the porosity of the COFs leads to reversible deactivation. Full activity and selectivity of the best catalysts can be recovered upon washing with dichlorobenzene.

A facile one-step method to shape covalent triazine frameworks (CTFs) for catalytic applications is reported. Phase inversion of the CTF powder by using a polyimide as a binder in a microfluidic device results in the formation of composite spheres with accessible CTF porosity and a high mechanical and thermal stability. The fabricated spheres can be used to host organometallic complexes. The obtained shaped catalysts, Ir@CTF spheres, are active and fully recyclable in the direct hydrogenation of carbon dioxide into formic acid under mild reaction conditions (20 bar and 50–90 °C) and in the dehydrogenation of formic acid.

Mixed-matrix membranes (MMMs) comprising Matrimid and a microporous azine-linked covalent organic frameworks (ACOF-1) were prepared and tested in the separation of CO₂ from an equimolar CO₂/CH₄ mixture. The COF-based MMMs show a more than doubling of the CO₂ permeability upon 16 wt % ACOF-1 loading together with a slight increase in selectivity compared to the bare polymer. These results show the potential of COFs in the preparation of MMMs.