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Cathodic protection (CP) was introduced two centuries ago and since has foundwidespread application in protecting structures such as pipelines, offshoreinstallations, and bridges from corrosion. Despite its extensive use, thefundamental working mechanism of CP remains debated, particularly for metals inporous media such as soil. Here, we offer resolution to the long-standingdebate by employing in-situ and ex-situ characterisation techniques coupledwith electrochemical measurements to characterise the spatio-temporal changesoccurring at the steel-electrolyte interface. We show that upon CP, theinterfacial electrolyte undergoes alkalinisation and deoxygenation, and thatdepending on polarisation conditions, an iron oxide film can simultaneouslyform on the steel surface. We further demonstrate that these changes ininterfacial electrolyte chemistry and steel surface state result in alteredanodic and cathodic reactions and their kinetics. We propose a mechanism of CPthat integrates the long debated theories, based on both concentration andactivation polarisation, complimentarily. Implications of this coherentscientific understanding for enhancing corrosion protection technologies andthe safe, economic, and environmental-friendly operation of criticalsteel-based infrastructures are discussed.

Mechanism of cathodic protection of iron and steel in porous media