Silica-supported Fe/Fe–O nanoparticles for the catalytic hydrogenation of nitriles to amines in the presence of aluminium additives

• Published in: Nature catalysis Vol. 5; no. 1; pp. 20 - 29
• Main Authors: Chandrashekhar, Vishwas G., Senthamarai, Thirusangumurugan, Kadam, Ravishankar G., Malina, Ondřej, Kašlík, Josef, Zbořil, Radek, Gawande, Manoj B., Jagadeesh, Rajenahally V., Beller, Matthias
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01-01-2022
• Subjects: 639/301/357/354; 639/638/77/887; 639/638/77/888; Catalysis; Chemistry; Chemistry and Materials Science
• ISSN: 2520-1158; 2520-1158
• DOI: 10.1038/s41929-021-00722-x

The hydrogenation of nitriles to amines represents an important and frequently used industrial process due to the broad applicability of the resulting products in chemistry and life sciences. Despite the existing portfolio of catalysts reported for the hydrogenation of nitriles, the development of iron-based heterogeneous catalysts for this process is still a challenge. Here, we show that the impregnation and pyrolysis of iron(II) acetate on commercial silica produces a reusable Fe/Fe–O@SiO
2
catalyst with a well-defined structure comprising the fayalite phase at the Si–Fe interface and α-Fe nanoparticles, covered by an ultrathin amorphous iron(III) oxide layer, growing from the silica matrix. These Fe/Fe–O core–shell nanoparticles, in the presence of catalytic amounts of aluminium additives, promote the hydrogenation of all kinds of nitriles, including structurally challenging and functionally diverse aromatic, heterocyclic, aliphatic and fatty nitriles, to produce primary amines under scalable and industrially viable conditions.
Nitriles can be hydrogenated with a variety of precious metal catalysts, yet there is a lack of heterogeneous systems based on affordable metals such as iron. Here, the authors report a silica-supported Fe/Fe–O core–shell catalyst with the ability to hydrogenate nitriles in the presence of aluminium additives.