Single-Crystal Electrochemistry Reveals Why Metal Nanowires Grow

Shape-control is used to tune the properties of metal nanostructures in applications ranging from catalysts to touch screens, but the origins of anisotropic growth of metal nanocrystals in solution are unknown. We show single-crystal electrochemistry can test hypotheses for why nanostructures form and predict conditions for anisotropic growth by quantifying the degree to which different species cause facet-selective metal deposition. Electrochemical measurements show disruption of alkylamine monolayers by chloride ions causes facet-selective Cu deposition. An intermediate range of chloride concentrations maximizes facet-selective Cu deposition on single crystals and produces the highest aspect ratio nanowires in a solution-phase synthesis. DFT calculations similarly show an intermediate monolayer coverage of chloride displaces the alkylamine capping agent from the ends but not the sides of a nanowire, facilitating anisotropic growth.