Imidazolium-Containing Hybrid Organic-Inorganic Materials for the Conversion of CO: 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, N physisorption, transmission electron microscopy, C and Si MAS NMR, combustion chemical analysis, X-ray photoelectron spectroscopy, and CO physisorption to assess their physicochemical and structural features, as well as the successful incorporation of imidazolium salts. Their catalytic activity in the conversion of CO 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.