A series of palladium-based catalysts were synthesized by grafting a silylated imidazolium ionic liquid onto two types of silica supports: mesoporous SBA-15 and commercial silica. The ionic liquid served as both a stabilizing matrix and anchoring platform for palladium ions, introduced via aqueous impregnation. The influence of support activation temperature, reduction treatment, and textural properties on catalytic performance was systematically studied. Catalysts were tested in the aqueous-phase hydrogenation of CO₂ to formic acid under mild conditions (40 bar H₂/CO₂, room temperature). SBA-15-based catalysts showed superior performance, achieving up to 50 mol HCOOH ·mol⁻¹ Pd ·h −1 — over three times higher than the flash silica counterpart. High support surface area and pore volume enabled greater ionic liquid loading and palladium dispersion, as confirmed by TEM, SEM-EDX and ICP analyses. Pre-reduction with NaBH₄ eliminated induction periods in the kinetic profile and further enhanced activity, whereas no such improvement was observed for flash silica, likely due to palladium aggregation. These findings demonstrate that combining mesoporous supports with covalently anchored ionic liquids enables the design of efficient, water-compatible CO₂ hydrogenation catalysts under mild conditions. • Imidazolium ionic liquid grafted onto silica enables stable Pd heterogeneous catalysts. • SBA-15 textural properties enhance ionic liquid loading and Pd dispersion. • SBA-15–supported catalysts show > 3 × higher activity than flash silica analogues. • Up to 205 µmol formic acid obtained from CO₂ hydrogenation under mild conditions. • NaBH₄ pre-reduction removes induction period and boosts activity for SBA-15 systems.
Cuesta-Álvaro et al. (Fri,) studied this question.