One-pot selective amination of GLYcerol using ligand decorated metal NANOparticles – GLYNANO

Despite considerable efforts, the transformation of biomass products into valuable nitrogen-containing chemicals still represents an important challenge today. Yet, their demand is dramatically increasing worldwide, since amines are sought for their unique properties as corrosion inhibitors, paints and coatings, as well as in cosmetic, detergence and food industries. The GLYNANO project aims to provide a one-pot efficient and selective catalytic route upgrading glycerol into valuable bio-based amines through its direct amination with ammonia or primary amines. We target in this project the amination of the central hydroxyl group of glycerol. Keeping the two terminal-hydroxyl groups free will facilitate further chemical modifications and will confer hydrophilicity to the resulting surfactant when using a fatty amine as an aminating agent. Since the central hydroxyl of glycerol is often less reactive than the two terminal ones (statistically and sterically), the amination of glycerol at its central position is highly challenging and chemoselective catalysts are required. We will use magnetically recyclable and unsupported ligand-decorated Co-based metal nanoparticles with controlled sizes and shapes that have already shown excellent activity, chemoselectivity and recyclability for the acceptorless alcohol dehydrogenation (the first step of the direct amination of alcohols). Their catalytic performances will be adjusted through the fine control of their composition (alloying Co with Ru or Cu), size, shape and surface ligand decoration. To obtain a better understanding of the structure/selectivity relationships and to further improve our catalysts, computational investigations (e.g. adsorption of the substrate through the ligand layer, reaction mechanism) will be carried out. Based on this integrated approach combining expertise in the fields of materials chemistry, reactivity and theoretical chemistry, this project is expected to lead not only to a better understanding on the influence of the surface ligands used to stabilize metal NPs on the catalytic amination of glycerol but also to the emergence of novel catalysts and eco-efficient processes to produce selectively modified bio-sourced amines.