Preventing Alloy Electrocatalyst Segregation in Air Using Sacrificial Passivating Overlayers.

Many alloy electrocatalysts, including intermetallics, are exceptionally sensitive to segregation in air due to the electronic dissimilarity of the constituent metals. We demonstrate that even alloys with strong cohesive energies rapidly segregate upon air exposure, completely burying the less reactive constituent metal beneath the surface. To circumvent this issue, we develop and validate a new experimental approach for bridging the pressure gap between electronic structure characterization performed under ultrahigh vacuum and electrocatalytic activity testing performed under ambient conditions. This method is based on encapsulation of the alloy surface with a sacrificial passivating overlayer of aluminum oxide. These passivating overlayers protect the underlying material from segregation in the air and can be completely and rapidly removed in an alkaline electrochemical environment under potential control. We demonstrate that alloy surfaces prepared, protected, and introduced into the electrolyte in this manner exhibit near-surface compositions consistent with those of the bulk material despite prior air exposure. We also demonstrate that this protection scheme does not alter the electrocatalytic activity of benchmark electrocatalysts. Implementation of this approach will enable reliable correlations between the electrocatalytic activity measured under ambient conditions and the near-surface electronic structure measured under ultrahigh vacuum.