Migration: A Neglected Potential Contribution of HCl-Oxidized Au(0)

In this study, the typical oxidation process of Au/C catalysts exposed to HCl is presented. Although the process violates the standard electrode potentials, the “oxidized” tendency of Au(0) species is analyzed. This oxidation behavior can only be triggered over the Au/C sample within residual cationic Au species, and terminated over the completely metallic Au(0)/C sample. This study demonstrates that the presence of surface chlorination species cannot facilitate the oxidation of Au(0) and Au(I) when the sample is treated with HCl alone, which excludes the oxidation paths of: Au(0) → Au(III) and Au(I) → Au(III). The reported “HCl-oxidized Au(0)” behavior is partially caused by the migration of Au(III) species in the carbon bulk-phase, which occurs outside the XPS detection limit region and into the detection limit rather than the “HCl-oxidized Au(0)” itself. The mechanism of driving the bulk-phase Au(III) migrated from the steady destabilized state to the carbon surface is then studied. This study demonstrates that the migration of Au cannot be neglected behind the curious oxidation phenomenon by HCl, which provides a new perspective for the oxidation of other noble metals by HCl.