Imidazolium-Containing Hybrid Organic-Inorganic Materials for the Conversion of CO₂: Unveiling the Key Role of the Ionic Template

A straightforward synthesis of a series of hybrid organic-inorganic materials (HOIMs) containing imidazolium moieties was achieved. The preparation of the imidazolium acetate precursor was performed in a single-step procedure using the Debus-Radziszewski reaction. The as-synthesized alkoxysilane was employed in combination with tetraethyl orthosilicate to generate an HOIM presenting a high specific surface area. Two different structure-directing agents (SDAs), an anionic (sodium dodecyl sulfate (SDS)) or a cationic (cetyltrimethylammonium bromide) surfactant, were used to investigate the role played by the SDA on the distribution of the imidazolium-based active sites within the silica structure. After the synthesis, the acetate ion was replaced with Cl^- and Br^- via a simple acid treatment. This procedure favors also the removal of the surfactant, thus releasing the porosity of the solids. The HOIMs synthesized were fully characterized via low-angle X-ray diffraction, N₂ physisorption, transmission electron microscopy, ¹³C and ²⁹Si MAS NMR, combustion chemical analysis, X-ray photoelectron spectroscopy, and CO₂ physisorption to assess their physicochemical and structural features, as well as the successful incorporation of imidazolium salts. Their catalytic activity in the conversion of CO₂ was tested over different epoxides to produce the corresponding cyclic carbonates. The key role of the SDS (anionic surfactant) as a templating agent was proved. The best material was stable under the selected reaction conditions, reusable over multiple cycles, and active on a series of different epoxides, thus proving its versatility.