Gold Deposition at a Free-Standing Liquid/Liquid Interface, Evidence for the Formation of Au(I) by Microfocus X-ray Spectroscopy (μXRF and μXAFS) and Cyclic Voltammetry

Electrochemical gold nucleation and nanoparticle growth at a liquid/liquid interface were examined in situ by combined X-ray fluorescence (XRF) mapping with a microfocus X-ray beam and X-ray absorption fine structure (XAFS) spectroscopy. Gold deposition was achieved by reduction of [AuCl4]− with tri-p-tolylamine at a water/1,2-dichlorobenzene interface using a windowless liquid/liquid interface system formed from the contact of aqueous and organic phase droplets. The combination of XRF and XAFS, with a spatial resolution of approximately 70 μm, provided chemical speciation information near the interface under gold deposition conditions. Analysis of the X-ray absorption near-edge structure (XANES) reveals evidence for the presence of Au(I) species as a reduction intermediate, concomitant with a buildup of metallic gold at the interface. Cyclic voltammetry indicates the presence of two ion transfer peaks at the liquid/liquid interface, which are assigned to the transfer of [AuCl4]− and [AuCl2]−. Finally ex situ TEM analysis shows that the resultant nanoparticles have an average size between 3 and 4 nm. In line with this particle size, the XAFS indicates bulk-like structure.