The influence of halides on the initial selective dissolution of Cu3Au (1 1 1)

Abstract

We report an electrochemical in situ X-ray diffraction (XRD) and ex situ atomic force microscopy (AFM) study on the influence of the halide additives bromide and iodide in comparison to chloride in 0.1M H2SO4 solution on the selective dissolution of Cu3Au (111). Our results suggest that the addition of these halides have a pronounced effect on the dealloying process and lead to peculiar changes in the resulting surface morphologies. For an additive of bromide we observed (similar to an earlier study with chloride) a sequence of specific Au surface layers with an initial ultra-thin stacking-inverted Au-rich layer, subsequent pure Au islands, and finally substrate oriented nanometer-scale ligaments (nanoporosity). These structures occur with a negative shift in the transformation potentials compared to pure sulfuric acid solution. With an additive of iodide no stable passive Au film is formed and a porous surface was observed at relatively short times and low potentials. A precipitation of copper iodide (CuI) visible in the ex situ AFM images leads to the formation of surface porosity with bimodal length scales.