The bifunctional mechanism that involves adsorbed hydroxide in the alkaline hydrogen oxidation and evolution reactions, important in hydrogen fuel cells and water electrolysers, is hotly debated.... Show moreThe bifunctional mechanism that involves adsorbed hydroxide in the alkaline hydrogen oxidation and evolution reactions, important in hydrogen fuel cells and water electrolysers, is hotly debated. Hydroxide binding has been suggested to impact activity, but the exact role of adsorbed hydroxide in the reaction mechanism is unknown. Here, by selectively decorating steps on a Pt single crystal with other metal atoms, we show that the rate of alkaline hydrogen evolution exhibits a volcano-type relationship with the hydroxide binding strength. We find that Pt decorated with Ru at the step edge is 65 times more active for the hydrogen evolution reaction (HER) than is the bare Pt step. Simulations of electrochemical water dissociation show that the activation energy correlates with the OH* adsorption strength, even when the adsorbed hydroxide is not a product, which leads to a simulated volcano curve that matches the experimental curve. This work not only illustrates the alkaline HER mechanism but also provides a goal for catalyst design in targeting an optimum hydroxide binding strength to yield the highest rate for the alkaline HER. A three-dimensional (H and OH adsorbed species) HER activity volcano and the implications for hydrogen oxidation are discussed.The appropriate descriptors for a catalyst's hydrogen evolution activity in alkaline electrolyte are debated. Combining simulations and single-crystal studies of metal-decorated Pt surfaces, McCrum and Koper show that activity exhibits a volcano-type relationship with the hydroxide binding strength of the catalyst, providing a target for catalyst design. Show less
