Carboxylate‐Functionalized Zeolitic Imidazolate Framework Enables Catalytic N‐Formylation Using Ambient CO₂

Abstract Catalytic upgrading of CO₂ into value‐added chemicals to build the excess carbon cycle is of great significance. In this work, carboxylate‐functionalized zeolitic imidazolate framework (F‐ZIF‐90) with good crystallinity and porosity is constructed from ZIF‐90 and employed as a robust heterogeneous catalyst to boost the reductive N‐functionalization of various amines with CO₂ to furnish N‐formyl compounds (up to 99% yield) in the presence of PhSiH₃ under an ambient environment. The imidazole carboxylate species (COO^‐) can not only activate hydrosilane and CO₂ to form the key intermediate formoxysliane but also activate amines to participate in the N‐formylation reaction to obtain the target product. Moreover, it can enhance the catalyst capture and exchange ability toward ambient CO₂. The powerful adsorption capacity of the F‐ZIF‐90 catalyst toward CO₂ is conducive to elevating CO₂ concentration around the active species. Theoretical calculations show that the carboxylate‐mediated conversion path undergoes the transition state of hydrosilane activation with a relatively lower energy barrier (ΔG = 26.9 kcal mol^–1). F‐ZIF‐90 exhibits good thermochemical stability with no obvious activity attenuation after repeated use 5 times. This strategy opens a new avenue based on ZIFs to develop heterogeneous catalysts for reductive upgrading of CO₂.