Galvanic Replacement-Driven Transformations of Atomically Intermixed Bimetallic Colloidal Nanocrystals: Effects of Compositional Stoichiometry and Structural Ordering.

Galvanic replacement reactions dictated by deliberately designed nanoparticulate templates have emerged as a robust and versatile approach that controllably transforms solid monometallic nanocrystals into a diverse set of architecturally more sophisticated multimetallic hollow nanostructures. The galvanic atomic exchange at the nanoparticle/liquid interfaces induces a series of intriguing structure-transforming processes that interplay over multiple time and length scales. Using colloidal Au-Cu alloy and intermetallic nanoparticles as structurally and compositionally fine-tunable bimetallic sacrificial templates, we show that atomically intermixed bimetallic nanocrystals undergo galvanic replacement-driven structural transformations remarkably more complicated than those of their monometallic counterparts. We interpret the versatile structure-transforming behaviors of the bimetallic nanocrystals in the context of a unified mechanistic picture that rigorously interprets the interplay of three key structure-evolutionary pathways: dealloying, Kirkendall diffusion, and Ostwald ripening. By deliberately tuning the compositional stoichiometry and atomic-level structural ordering of the Au-Cu bimetallic nanocrystals, we have been able to fine-maneuver the relative rates of dealloying and Kirkendall diffusion with respect to that of Ostwald ripening through which an entire family of architecturally distinct complex nanostructures are created in a selective and controllable manner upon galvanic replacement reactions. The insights gained from our systematic comparative studies form a central knowledge framework that allows us to fully understand how multiple classic effects and processes interplay within the confinement by a colloidal nanocrystal to synergistically guide the structural transformations of complex nanostructures at both the atomic and nanoparticulate levels.