Silica‐Grafted Isonicotinamide to Boost Catalytic Activity of Cobalt Nanoparticles in Hydrogenation and Reductive Amination Reactions

The functionalization of silica supports with isonicotinamide (NIC) facilitated the stabilization of small (3.5 nm), spherical cobalt nanoparticles (CoNPs) used in catalytic hydrogenation. Various silica matrices, including amorphous, mesoporous, and non‐porous ones, were synthesized and post‐grafted with NIC to serve as ligands for stabilizing CoNPs. Comprehensive characterization techniques were employed to fully analyze the prepared materials, which were then utilized in the catalytic hydrogenation of acetophenone, serving as a benchmark reaction to assess the impact of different silica supports on catalysis. The porosity and surface nature of the silica matrices played crucial roles in anchoring the amide ligand, and the presence of the ligand was essential for stabilizing the nanoparticles. Among the catalysts tested, CoNPs@SBA‐15/NIC exhibited the highest catalytic activity and demonstrated excellent performance in the hydrogenation of alkenes, nitriles, ketones, and quinoline under relatively mild conditions. No significant alteration in catalyst morphology or leaching of metal was observed after the reaction. Notably, this catalytic system achieved turnover numbers comparable to those of homogeneous cobalt catalysts. Additionally, one‐pot tandem reductive amination reactions starting from aldehydes and involving both amines and nitrobenzene yielded secondary and tertiary amines in good yields, highlighting the robustness and versatility of the catalyst. The functionalization of silica supports with isonicotinamide (NIC) facilitated the stabilization of small cobalt nanoparticles (CoNPs) for catalytic hydrogenation. Various silica matrices (mesoporous, amorphous and non‐porous) were synthesized and post‐grafted with NIC. Comprehensive characterization showed that CoNPs@SBA‐15/NIC exhibited the highest catalytic activity, demonstrating excellent performance and robustness in hydrogenation reactions of different functional groups and tandem reductive amination.