Interface Dynamics in Ag–Cu₃P Nanoparticle Heterostructures

Abstract

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.

Insights into the Synthesis Mechanisms of Ag-Cu3P-GaP Multicomponent Nanoparticles

“…It is worth mentioning that the selected Ag-Cu 3 P nanoparticle’s interface was formed by Ag{110} and Cu 3 P­{110} facets. Recently, we reported Ag-Cu nanoparticles with Ag{111}/Cu{111} interfaces acting as templates stabilizing Ag-Cu 3 P nanoparticles with interfaces formed by Ag{111} and Cu 3 P­{100} facets after initiating the chemical reaction via the supply of PH 3 . Under certain conditions, such a nanoparticle had the potential to rearrange into an Ag-Cu 3 P nanoparticle with the thermodynamically more favorable interface formed by Ag{110} and Cu 3 P­{110} facets.…”

“…The adapted synthesis procedure, lacking the pretreatment under an H 2 atmosphere, could have led to supplying PH 3 to Ag-Cu nanoparticles with rough heterointerfaces . That circumstance could have caused the formation of the thermodynamically more favorable Ag{110}/Cu 3 P­{110} interface in the Ag-Cu 3 P nanoparticle presented in Figure .…”

Creation of Gases with Interplanetary Oxygen Concentration at Atmospheric Pressure by Nanoparticle Aerosol Scavengers: Implications for Metal Processing from nm to mm Range

“…Recently, nanoscience research has intensively focused on the creation of defined multicomponent nanoparticles − such as core–shell particles, as well as so-called “high-entropy-alloys” (HEAs) with unique properties. Especially for the synthesis of tailored core–shell particles, oxygen would act disruptively, as the pure metallic character of the produced particles would vanish.…”

Probing Chemical-Composition-Induced Heterostructures and Interfaces in Lead Halide Perovskites

“…With the advance in synthetic strategies, different heterostructured materials are regularly produced. These heterostructured materials includes metal–metal (Au/Ag, Ag/Cu 3 P, and Ag/Cu) metal–semiconductor (Au/PbS, Au/CdSe, and Au/CdS), and semiconductor–semiconductor (CdS/ZnSe, CdSe/CdS, and CdS/CdTe) materials as shown in Figure (a–d). Furthermore, the semiconductor–semiconductor heterostructure can be classified as type-I (high band gap shell on top of a low band gap core or vice versa) and type-II (band position are offset such that in the valence band maxima (VBM)/conduction band minima (CBM) of one semiconductor lies between the band gap region of the other semiconductor) heterostructures as shown in Figure (e,f).…”

“…HRTEM images of (a) a metal–metal heterostructure in a Ag–Cu nanoparticle (reproduced with permission from ref , copyright 2021 American Chemical Society), (b) a metal–semiconductor heterostructure in Au–CdS NCs (reproduced with permission from ref , copyright 2008 American Chemical Society), (c) a semiconductor CdS nanoparticle with a radius of 2.4 nm, and (d) a semiconductor–semiconductor CdS/ZnSe core/shell heterostructure with a radius of 3.4 nm, indicating a 1.0 nm shell width (reproduced with permission from ref , copyright 2007 Springer Nature). The CdS/ZnSe interface is imperceptible in the HRTEM due to the small difference in electron-scattering cross sections of CdS and ZnSe.…”