Single-Site Iridium Picolinamide Catalyst Immobilized onto Silica for the Hydrogenation of CO₂ and the Dehydrogenation of Formic Acid

The development of an efficient heterogeneous catalyst for storing H₂ into CO₂ and releasing it from the produced formic acid, when needed, is a crucial target for overcoming some intrinsic criticalities of green hydrogen exploitation, such as high flammability, low density, and handling. Herein, we report an efficient heterogeneous catalyst for both reactions prepared by immobilizing a molecular iridium organometallic catalyst onto a high-surface mesoporous silica, through a sol–gel methodology. The presence of tailored single-metal catalytic sites, derived by a suitable choice of ligands with desired steric and electronic characteristics, in combination with optimized support features, makes the immobilized catalyst highly active. Furthermore, the information derived from multinuclear DNP-enhanced NMR spectroscopy, elemental analysis, and Ir L₃-edge XAS indicates the formation of cationic iridium sites. It is quite remarkable to note that the immobilized catalyst shows essentially the same catalytic activity as its molecular analogue in the hydrogenation of CO₂. In the reverse reaction of HCOOH dehydrogenation, it is approximately twice less active but has no induction period.