Understanding Digestive Ripening of Ligand-Stabilized, Charged Metal Nanoparticles

Most syntheses of thiolate-protected metal nanoparticles (NPs) include a thermochemical step in which the as-prepared, polydisperse NPs are transformed to a narrower size distribution in a poorly understood process known as digestive ripening (DR). Previous theoretical approaches considered either surface and electrostatic contributions or surface and ligand-binding contributions. We show that the three contributions are needed to obtain theoretical predictions in agreement with experimental observations. Although statistical thermodynamics does not clarify mechanistic details, it certainly provides valuable insights on the DR process. Remarkably, a relatively simple theory with no fitting parameters satisfactorily explains the roles of the metal:ligand ratio, the NP charge, the relative permittivity of the solvent, the ripening temperature, the binding energy, and the ligand chain length.