Mechanochemical synthesis of Au, Pd, Ru and Re nanoparticles with lignin as a bio-based reducing agent and stabilizing matrix.

A versatile, low-energy and solvent-free method to access nanoparticles (NPs) of four different transition metals, based on a bottom-up mechanochemical procedure involving milling of inorganic precursors, is presented. Lignin, a biomass waste, was used effectively as a reducing agent, for the first time in a mechanochemical context, to access MNPs where M = Au, Pd, Ru, Re. A series of metal precursors was used for this reaction and their nature was shown to be integral in determining whether NPs became incorporated within the organic lignin matrix, M@lignin, or not. Specifically, organometallic precursors resulted in extensive encapsulation of the NPs, as well as improved control over their size and shape, while ionic precursors afforded matrix-free NPs. The resulting NP-containing composites were characterized through Fourier-transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and powder X-ray diffraction (PXRD). This mechanochemical grinding method for accessing M@lignin (M = Au, Pd, Ru and Re) is significantly more sustainable than the traditional solvent batch syntheses of metal NPs because it relies on the use of a biomass-based polymer, it is highly atom economical, it eliminates the need for solvents and it reduces drastically the energy input.