Role of Semiconductive Property on Selective Cementation Mechanism of Iron Oxides to Gold in Galvanic Interaction with Zero-Valent Aluminum from Gold–Copper Ammoniacal Thiosulfate Solutions

Abstract

Iron oxides (hematite, Fe2O3, and magnetite, Fe3O4), previously used as electron mediators in the galvanic system with zero-valent aluminum (ZVAl), have been shown to recover Au upon cementation in Au–Cu ammoniacal thiosulfate media selectively, and this warrants further investigation. This research is focused on investigating the role of the semiconductive properties of metal oxides by performing a cementation experiment by mixing 0.15 g of electron mediators (Fe3O4, Fe2O3, TiO2 (anatase and rutile)) and 0.15 g of zero-valent aluminum powder as an electron donor in various electrochemical experiments. The results revealed that upon the cementation experiment, synthetic Fe2O3 and Fe3O4 were consistently able to selectively recover Au at around 90% and Cu at around 20%. Compared to activated carbon (AC), TiO2, in anatase and rutile forms, obtained selective recovery of gold, but the recovery was utterly insignificant compared to that of iron oxides, obtaining an average of 93% Au and 63% Cu recovery. The electrochemical and surface analysis supports the results obtained upon the cementation process, where TiO2, upon cyclic voltammetry (CV), obtained two reduction peaks centered at −1.0 V and −0.5 V assigned to reducing Au and Cu ions, respectively. Furthermore, various electrochemical impedance spectroscopic analyses revealed that the flat band potential obtained in the Mott–Schottky plot is around −1.0 V and −0.2 V for iron oxides and titanium oxides, respectively, suggesting that the electrons travel from semiconductor interface to electrolyte interface, and electrons are accessible only to Au ions in the electrolyte interface (reduction band edge around −1.0 V). The determination of this selective cementation mechanism is one of a kind. It has been proposed that the semiconductive properties of Fe2O3, Fe3O4, and, by configuring their relative energy band diagram, the travel of electrons from the iron oxide–electrolyte interface facilitate the selective cementation towards Au(S2O3)23+ ions in gold–copper ammoniacal thiosulfate solutions.