Particle size dependence of the charging of Au nanoparticles immobilized on a modified ITO electrode

Citrate-stabilized gold nanoparticles (Au-NPs) of a nearly spherical shape with four different diameters (3.7, 11.0, 21.7, and 40.8 nm) were immobilized on a 4-aminobutylsiloxane monolayer-modified indium-tin oxide (ITO) electrode. From the results of coulometric measurements using potential step sequences, the number of electrons per particle to be transferred to attain a new equilibrium state after applying a potential step was found to increase in proportion to the square of the diameter. The double layer integral capacitance of the Au-NP surface per unit area in the potential range from −0.4 to 0.6 V (Ag/AgCl/sat’d KCl) is ca. 70 μF cm−2, being independent of the particle size. The differential capacitance of the Au-NP surface is a function of the potential with a maximum at 0.32 V, while the function is again independent of the particle size. The kinetics of the charging was discussed using the analysis of the potential step transient current. The potential-dependent shift of the plasmon absorption band obtained by constant-potential and potential-modulated transmission–absorption spectroscopic measurements revealed that a smaller Au-NP exhibits a greater blue-shift of the plasmon band when applying more negative potentials, being in line with the Mie–Drude theory.