Oxidation of highly unstable <4 nm diameter gold nanoparticles 850 mV negative of the bulk oxidation potential

Here we describe the oxidation of <4 nm diameter Au nanoparticles (NPs) attached to indium tin oxide-coated glass electrodes in Br(-) and Cl(-) solution. Borohydride reduction of AuCl(4)(-) in the presence of hexanethiol or trisodium citrate (15 min) led to Au NPs <4 nm in diameter. After electrochemical and ozone removal of the hexanthiolate ligands from the thiol-coated Au NPs, Au oxidation peaks appeared in the range 0-400 mV vs Ag/AgCl (1 M KCl), which is 850-450 mV negative of the bulk Au oxidation peak near 850 mV. The oxidation potential of citrate-coated Au NPs is in the 300-500 mV range and those of 4 and 12 nm diameter Au NPs in the 660-780 mV range. The large negative shift in potential agrees with theory for NPs in the 1-2 nm diameter range. The oxidation potential of Au in Cl(-) solution is positive of that in Br(-) solution, but the difference decreases dramatically as the NP size decreases, showing less dependence on the halide for smaller NPs.