Spontaneous Hetero-attachment of Single-Component Colloidal Precursors for the Synthesis of Asymmetric Au–Ag(2)X (X = S, Se) Heterodimers

[Image: see text] Finding simple, easily controlled, and flexible synthetic routes for the preparation of ternary and hybrid nanostructured semiconductors is always highly desirable, especially to fulfill the requirements for mass production to enable application to many fields such as optoelectronics, thermoelectricity, and catalysis. Moreover, understanding the underlying reaction mechanisms is equally important, offering a starting point for its extrapolation from one system to another. In this work, we developed a new and more straightforward colloidal synthetic way to form hybrid Au–Ag(2)X (X = S, Se) nanoparticles under mild conditions through the reaction of Au and Ag(2)X nanostructured precursors in solution. At the solid–solid interface between metallic domains and the binary chalcogenide domains, a small fraction of a ternary AuAg(3)X(2) phase was observed to have grown as a consequence of a solid-state electrochemical reaction, as confirmed by computational studies. Thus, the formation of stable ternary phases drives the selective hetero-attachment of Au and Ag(2)X nanoparticles in solution, consolidates the interface between their domains, and stabilizes the whole hybrid Au–Ag(2)X systems.