Reversible Voltage-Induced Assembly of Au Nanoparticles at Liquid|Liquid Interfaces

The voltage-induced assembly of mercaptosuccinic acid-stabilized Au nanoparticles of 1.5 ± 0.4 nm diameter is investigated at the polarizable water|1,2-dichloroethane interface. Admittance measurements and quasi-elastic laser scattering (QELS) studies reveal that the surface concentration of the nanoparticle at the liquid|liquid boundary is reversibly controlled by the applied bias potential. The electrochemical and optical measurements provide no evidence of irreversible aggregation or deposition of the particles at the interface. Analysis of the electrocapillary curves constructed from the dependence of the frequency of the capillary waves on the applied potential and bulk particle concentration indicates that the maximum particle surface density is 3.8 × 1013cm-2, which corresponds to 67% of a square closed-pack arrangement. This system provides a unique example of reversible assembly of nanostructures at interfaces, in which the density can be effectively tuned by the applied potential bias.