Chitosan as a Bio-Based Ligand for the Production of Hydrogenation Catalysts

Bio-based polymers are attracting increasing interest as alternatives to harmful and environmentally concerning non-biodegradable fossil-based products. In particular, bio-based polymers may be employed as ligands for the preparation of metal nanoparticles (M(0)NPs). In this study, chitosan (CS) was used for the stabilization of Ru(0) and Rh(0) metal nanoparticles (MNPs), prepared by simply mixing RhCl3 x 3H2O or RuCl3 with an aqueous solution of CS, followed by NaBH4 reduction. The formation of M(0)NPs-CS was confirmed by Fourier Transform Infrared Spectroscopy (FT-IR), Differential Scanning Calorimetry (DSC), Thermal Gravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), Energy-Dispersive X-ray Analysis (EDX), Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD). Their size was estimated to be below 40 nm for Rh(0)-CS and 10nm for Ru(0)-CS by SEM analysis. M(0)NPs-CS were employed for the hydrogenation of (E)-cinnamic aldehyde and levulinic acid. Easy recovery by liquid-liquid extraction made it possible to separate the catalyst from the reaction products. Recycling experiments demonstrated that M(0)NPs-CS were highly efficient up to four times in the best hydrogenation conditions. The data found in this study show that CS is an excellent ligand for the stabilization of Rh(0) and Ru(0) nanoparticles, allowing the production of some of the most efficient, selective and recyclable hydrogenation catalysts known in the literature.