Self‐Polycondensation Flux Synthesis of Ultrastable Olefin‐Linked Covalent Organic Frameworks for Electrocatalysis

Creating new functional materials that efficiently support noble metal catalysts is important and in high demand. Herein, we develop a self‐polycondensation flux synthesis strategy that can produce olefin‐linked covalent organic framework (COF) platforms with high crystallinity and porosity as the supports of Pd nanoparticles for electrocatalytic nitrogen reduction reaction (ENRR). A series of "two in one" monomers integrating aldehyde and methyl reactive groups are rationally designed to afford COFs with square‐shaped pores and ultrahigh chemical stability (e.g., strong acid or alkali environments for >1 month). Functionalizing Fluorine significantly boosts the hydrophobicity of fluoro‐functionalized COFs, which can inhibit the competing hydrogen evolution reaction (HER) and enhance ENRR performances. The COFs loading Pd nanoparticles show high NH3 production yields up to 90.0 ± 2.6 μg·h−1·mgcat.−1 and the faradaic efficiency of 44% at −0.2 V versus reversible hydrogen electrode, the best comprehensive performance among all reported COFs. Meanwhile, the catalysts are easy to recover and recycle, as demonstrated by their use for 15 cycles and 17 hours, with good performance retention. This work not only provides a new synthesis strategy for olefin‐linked COFs, but also paves a new avenue for the design of highly efficient ENRR catalysts.