Modular Synthesis of Anisotropic, Multinary, and Heterostructured Nanoshells

Abstract

Here, we report the synthesis of multinary, heterostructured, and octahedral nanoshells with tunable structures. The synthesis leverages a unique combination of widely used post-synthetic modifications, including galvanic replacement, facet selective growth and etching, as well as cation exchange (CE) reactions. We start by using octahedral Au nanoparticles, converting these to PtAu nanoframes, and then depositing Se windows onto that framework. The subsequent reaction of Se with Cu+/2+ ions yields a hollow, metal–semiconductor hybrid PtAu@Cu2–x Se structure with observable plasmonic features from the Cu2–x Se component. We then show that these Cu2–x Se domains can undergo CE and metal deposition reactions using Ag and Pd to yield both quinary and senary nanoshells with control over the identity, composition, and spatial arrangement of the domains. Taken together, these experiments yield a new class of complex, hollow, metal–semiconductor hybrid particles. More broadly, these results demonstrate remarkable modularity of the constituent reactions and indicate that these structures, as well as even more diverse and complex structures, are likely accessible by retrosynthetic design.

Influence of Surface Chemistry on Metal Deposition Outcomes in Copper Selenide-Based Nanoheterostructure Synthesis

“…There is a large and growing interest in the creation of metal–semiconductor hybrid nanomaterials because of their unique properties and applications including in photocatalysis, − optoelectronics, , and biological imaging/diagnostics. − To efficiently match structure with function, there has been sustained interest in establishing synthetic methods for precise control of their morphology. − A particularly successful approach for tuning these heterostructures has been postsynthetic modification of starting nanoparticle (NP) substrates. − There are several advantages to postsynthetic modification strategies for tuning nanoheterostructure morphology including the improved ability to tailor interfaces within the structure such as interface size, composition, number, and/or extent (e.g., gradient). Strategies such as cation/anion exchange and galvanic replacement have led to remarkably complex structures, ,,,− with both established and still studied new physical and chemical behaviors of interest. − …”

Design of Pb1−xSrxF2 hollow crystals with gas–solution interfacial reactions

“…For example, a dissolution–regrowth strategy was used to obtain cobalt squarate cages via the ultrasonic treatment. 10 Authors 11 converted the octahedral Au nanoparticles into nanoshells with tunable structures using galvanic replacement, facet-selective growth and etching. Ion exchange is also used as a simple route for the synthesis of hollow structures.…”