Atmane Kahina Aït, Michel Carine, Piquemal Jean-Yves, Sautet Philippe, Beaunier Patricia, Giraud Marion, Sicard Mickaël, Nowak Sophie, Losno Rémi, Viau Guillaume
Université Paris Diderot, Sorbonne Paris Cité, ITODYS, CNRS UMR 7086, 15 rue J.-A. de Baïf, 75205 Paris Cedex 13, France.
Nanoscale. 2014 Mar 7;6(5):2682-92. doi: 10.1039/c3nr03686c. Epub 2014 Jan 22.
The polyol process is one of the few methods allowing the preparation of metal nanoparticles in solution. Hexagonal close packed monocrystalline Co nanorods are easily obtained in basic 1,2-butanediol at 448 K after a few minutes using a Co(II) dicarboxylate precursor. By using a combined experimental and theoretical approach, this study aims at a better understanding of the growth of anisotropic cobalt ferromagnetic nanoparticles by the polyol process. The growth of Co nanorods along the c axis of the hexagonal system was clearly evidenced by transmission electron microscopy, while the mean diameter was found to be almost constant at about 15 nm. Powder X-ray diffraction data showed that metallic cobalt was generated at the expense of a non-reduced solid lamellar intermediate phase which can be considered as a carboxylate ligand reservoir. Density functional theory calculations combined with a thermodynamic approach unambiguously showed that the main parameter governing the shape of the objects is the chemical potential of the carboxylate ligand: the crystal habit was deeply modified from rods to platelets when increasing the concentration of the ligand, i.e. its chemical potential. The approach presented in this study could be extended to a large number of particle types and growth conditions, where ligands play a key role in determining the particle shape.
