Interface Dynamics in Ag-Cu₃P Nanoparticle Heterostructures

Earth-abundant transition metal phosphides are promising materials for energy-related applications. Specifically, copper(I) phosphide is such a material and shows excellent photocatalytic activity. Currently, there are substantial research efforts to synthesize well-defined metal-semiconductor nanoparticle heterostructures to enhance the photocatalytic performance by an efficient separation of charge carriers. The involved crystal facets and heterointerfaces have a major impact on the efficiency of a heterostructured photocatalyst, which points out the importance of synthesizing potential photocatalysts in a controlled manner and characterizing their structural and morphological properties in detail. In this study, we investigated the interface dynamics occurring around the synthesis of Ag-Cu₃P nanoparticle heterostructures by a chemical reaction between Ag-Cu nanoparticle heterostructures and phosphine in an environmental transmission electron microscope. The major product of the Cu-Cu₃P phase transformation using Ag-Cu nanoparticle heterostructures with a defined interface as a template preserved the initially present Ag{111} facet of the heterointerface. After the complete transformation, corner truncation of the faceted Cu₃P phase led to a physical transformation of the nanoparticle heterostructure. In some cases, the structural rearrangement toward an energetically more favorable heterointerface has been observed and analyzed in detail at the atomic level. The herein-reported results will help better understand dynamic processes in Ag-Cu₃P nanoparticle heterostructures and enable facet-engineered surface and heterointerface design to tailor their physical properties.