Self-Epitaxial Hetero-Nanolayers and Surface Atom Reconstruction in Electrocatalytic Nickel Phosphides

Surface atomic, compositional, and electronic structures play decisive roles in governing the performance of catalysts during electrochemical reactions. Nevertheless, for efficient and cheap transition-metal phosphides used for water splitting, such atomic-scale structural information is largely missing. Despite much effort being made so far, there is still a long way to go for establishing a precise structure-activity relationship. Here, in combination with electron-beam bombardment and compositional analysis, our atomic-scale transmission electron microscopy study on Ni₅P₄ nanosheets, with a preferential (001) orientation, directly reveals the coverage of a self-epitaxial Ni₂P nanolayer on the phosphide surface. Apart from the presence of nickel vacancies in the Ni₅P₄ phase, our quantum-mechanical image simulations also suggest the existence of an additional NiP (0 < x < 0.5) nanolayer, characteristic of complex surface atom reconstruction, on the outermost surface of the phosphides. The surface chemical gradient and the core-shell scenario, probably responsible for the passivated catalytic activity, provide a novel insight to understand the catalytic performance of transition-metal catalysts used for electrochemical energy conversion.