Rich-N highly branched COF loaded with imidazolyl ionic liquids for highly efficient catalysis of CO2 conversion under atmospheric pressure

The highly loaded ionic active centers and carbon dioxide (CO2) affinity sites play pivotal roles in catalyzing the gas-solid-liquid three-phase reaction in CO2 cycloaddition. In this study, a kind of rich-N highly branched Covalent organic framework loaded with imidazolyl ionic liquids (DhaTat-COF-IL) was synthesized through a nucleophilic substitution reaction, which bridged the highly loaded imidazolyl ionic liquids (Im-IL) active centers (20.72 %) and strong CO2-philic sites, efficiently promoting the in-situ of CO2 conversion at catalyst interface. The rich-N highly branched Covalent organic framework (DhaTat-COF) benefits from its abundant CO2-philic groups (imine and triazine groups) and microporous properties, exhibiting excellent CO2 enrichment capacity, designed as a porous crystalline material for anchoring high active Im-IL. The resultant DhaTat-COF-IL achieved a quantitative yield of 95 % (selectivity > 99 %) in converting epichlorohydrin (ECH) under ambient pressure at 80 ℃, with a turnover frequency (TOF) value reaching 1582 h⁻¹ at 120 ℃. Additionally, yields of ≥ 94 % were obtained for various terminal-substituted epoxides. Density Functional Theory (DFT) analysis reveals a synergistic effect between −CH and Br− in the DhaTat-COF-IL during catalytic cycling. This work provides valuable insights into the targeted design and performance optimization of Im-IL-grafted COF-based catalysts, emphasizing high efficiency and sustainability in CO₂ conversion. [Display omitted] •High specific surface area DhaTat-COF and highly loaded Im-IL active centers were integrated into DhaTat-COF-IL catalyst successfully.•The synergistic effects between DhaTat-COF (CO2 affinity) and Im-IL (active site) play a crucial role at the catalyst interface.•The DhaTat-COF-IL could convert various terminal-substituted epoxides with yields of ≥ 94 % under ambient pressure at 80 °C.