Switchable Binding Energy of Ionic Compounds and Application in Customizable Ligand Exchange for Colloid Nanocrystals

The ability to engineer the surface ligands or adsorbed molecules on colloid nanocrystals (NCs) is important for various applications, as the physical and chemical properties are strongly affected by the surface chemistry. Here, we develop a facile and generalized ionic compound-mediated ligand-exchange strategy based on density functional theory calculations, in which the ionic compounds possess switchable bonding energy when they transfer between the ionized state and the non-ionized state, hence catalyzing the ligand-exchange process. By using an organic acid as the intermediate ligand, ligands such as oleylamine, butylamine, polyvinylpyrrolidone, and poly(vinyl alcohol) can be freely exchanged on the surface of Au NCs. Benefiting from this unique ligand-exchange strategy, the ligands with strong bonding energy can be replaced by weak ones, which is hard to realize in traditional ligand-exchange processes. The ionic compound-mediated ligand exchange is further utilized to improve the catalytic properties of Au NCs, facilitate the loading of nanoparticles on substrates, and tailor the growth of colloid NCs. These results indicate that the mechanism of switchable bonding energy can be significantly expanded to manipulate the surface property and functionalization of NCs that have applications in a wide range of chemical and biomedical fields.

Automated summary

This study presents an efficient and generalized ionic compound-mediated ligand exchange strategy for engineering the surface ligands on colloidal nanocrystals, which significantly influences the physical and chemical properties. By utilizing this strategy, ligands with strong bonding energy can be replaced by weak ones, facilitating the improvement of Au NCs' catalytic properties and functionalization.