Nanochemistry and biotechnology

Composites of 3d metals and N-containing carboneous nanoparticles for catalytic hydrogenation, amination and cyclization processes
Kolotilov S. V.1, Asaula V. M.1,  Buryanov V. V.2, Sotnik S. A.1,2, 
Pariiska O. O.1, Volochnyuk D. M.2,3, Ryabukhin S. V.2,4
1 L.V.Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine. Prospect Nauki, 31, Kyiv, 03028, Ukraine. 
E-mail: s.v.kolotilov@gmail.com
2 Enamine Ltd, 78 Chervonotkatska str., Kyiv 02660, Ukraine
3 Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Murmanska str., 5, Kyiv, 02000, Ukraine 
4 National Taras Shevchenko University of Kyiv, 60 Volodymyrska str., Kyiv, 01033, Ukraine

Composites of 3d metal nanoparticles and nanostructured carboneous (or graphene-like) species can be an alternative to the catalysts based on noble metals for many organic processes, used for preparation of active pharmaceutical ingredients, compounds for agrochemistry etc. Catalytic activity of such composites can be comparable with the activity of Pd or Pt-based systems, however the former are much more attractive because of the lower cost.
A series of composites containing Co, Ni or Cu nanoparticles and N-doped carboneous particles was prepared by thermolysis of the coordination compounds deposited on silica or alumina carriers. The composites were characterized by TEM, SEM, Raman spectroscopy. Then influence of the thermolysis conditions on the composites' structure was studied.
Co and Ni-containing composites were catalytically active in hydrogenation of heterocyclic compounds, such as substituted quinolines and furfural. While hydrogenation of quinoline derivatives led to corresponding 1,2,3,4-tetrahydroquinolines, hydrogenation of furfural resulted in formation of more complex mixtures of products. Reaction of benzaldehyde with aliphatic amines at presence of Co-containing composites allowed to obtain benzylamines via reductive amination. Cu-containing composites showed high catalytic activity in oxidative cyclization of propargylamine and cyclic ketones leading to fused pyridines.