Revealing the Reaction Pathway of Anodic Hydrogen Evolution at Magnesium Surfaces in Aqueous Electrolytes

Aqueous metal corrosion is a major economic concern in modern society. A phenomenon that has puzzled generations of scientists in this field is the so-called anomalous hydrogen evolution: the violent dissolution of magnesium under electron-deficient (anodic) conditions, accompanied by strong hydrogen evolution and a key mechanism hampering Mg technology. Experimental studies have indicated the presence of univalent Mg⁺ in solution, but these findings have been largely ignored because they defy our common chemical understanding and evaded direct experimental observation. Using recent advances in the <i>ab initio</i> description of solid-liquid electrochemical interfaces under controlled potential conditions, we describe the full reaction path of Mg atom dissolution from a kinked Mg surface under anodic conditions. Our study reveals the formation of a solvated [Mg²⁺(OH)^-]⁺ ion complex, challenging the conventional assumption of Mg²⁺ ion formation. This insight provides an intuitive explanation for the postulated presence of (Coulombically) univalent Mg⁺ ions, and the absence of protective oxide/hydroxide layers normally formed under anodic/oxidizing conditions. The discovery of this unexpected and unconventional reaction mechanism is crucial for identifying new strategies for corrosion prevention and can be transferred to other metals.