Electrochemical Studies of Capping Agent Adsorption Provide Insight into the Formation of Anisotropic Gold Nanocrystals

The ability of the 4-dimethylaminopyridine (DMAP) to stabilize and control the formation of anisotropic gold nanocrystals produced via the borohydride reduction of gold(III) salts is reported here. Electrochemical measurements of DMAP electrosorption on different low-index single crystal and polycrystalline electrodes is provided and shows a propensity for DMAP to preferentially adsorb on {100} facets. Measuring the electrochemical potential during nanocrystal formation shows that experimental conditions can easily be manipulated so that the growth of nanoseeds occurs at potentials that support preferential DMAP adsorption on {100} surfaces giving rise to highly anisotropic nanocrystals (nanorods, bipyramids, and nanopods). Nanopods with nearly 50 nm arm lengths are shown to form and produce a surface plasmon mode that extends well into the near IR (λ(max) ≈ 1350 nm). Evidence is provided of the slow, partial reduction of tetrachloroaurate to a DMAP stabilized Au(I) species. Shape control is achieved simply by varying the length of time, τ, that DMAP is allowed to partially reduce the Au(III) ions prior to the addition of the strong reducing agent, NaBH(4). Thus the role of DMAP in producing anisotropic particle shapes is shown to be multifunctional. A mechanism accounting for the dependence of particle shape on τ is provided.