Oppositely Charged Nanoparticles Precipitate Not Only at the Point of Overall Electroneutrality

Precipitation of oppositely charged entities is a common phenomenon in nature and laboratories. Precipitation and crystallization of oppositely charged ions are well-studied and understood processes in chemistry. However, much less is known about the precipitation properties of oppositely charged nanoparticles. Recently, it was demonstrated that oppositely charged gold nanoparticles (AuNPs), also called nanoions, decorated with positively or negatively charged thiol groups precipitate only at the point of electroneutrality of the sample (i.e., the charges on the particles are balanced). Here we demonstrate that the precipitation of oppositely AuNPs can occur not only at the point of electroneutrality. The width of the precipitation window depends on the size and concentration of the nanoparticles. This behavior can be explained by the aggregation of partially stabilized clusters reaching the critical size for their sedimentation in the gravitational field.