Thermodynamic and electrochemical study on the mechanism of formation of Ag(OH)4− in alkaline media

•Sensitive electrochemical techniques were used to evidence the formation of Ag(III).•The required potential for the generation of Ag(III) was found by using UV–vis to monitor species being formed.•A mechanism for the production of Ag(III) in the form of Ag(OH)4− is proposed. A mechanism based on electrochemical, spectrophotometric and scanning electron microscopy (SEM) data in alkaline media is proposed for the generation of Ag(III) in the form of Ag(OH)4−. The formation of Ag(III) from Ag0 is a rather complex multistep process that involves several steps. The presence of soluble Ag(I) species as Ag(OH)2− is of paramount importance for the production of soluble Ag(OH)4−, whose decomposition time is shown to exceed 8h.