Tailoring Surface Opening of Hollow Nanocubes and Their Application as Nanocargo Carriers

[Image: see text] Hollow nanoparticles (NPs) are of broad interest for biomedical, optical, and catalytic applications due to their unique geometry-related physicochemical properties. The ability to engineer hollow structures with surface openings is particularly attractive since emergent properties are promised by the design of shell porosity and encapsulation of guest materials. However, it still remains challenging to precisely control the opening of the hollow structure, in terms of shape, size, and location. Here, we report a facile one-step strategy to synthesize a hollow nanostructure with well-defined cubic-shape openings at the corners, by regulating nanoscale galvanic replacement processes with specific surface-capping agents. The final product is a single-crystalline AuAg alloy which morphologically features three “belts” orthogonally wrapping around a virtual cube, denoted by nanowrapper. We demonstrate a structural tunability of our synthetic method for tailoring nanowrapper and the corresponding tuning of its plasmonic band from the visible to near-infrared (NIR) range. Advanced electron tomography techniques provide unambiguous three-dimensional (3D) visualizations to reveal an unconventional transformation pathway of sharp-cornered Ag nanocube to nanowrapper and correlate its structure with measured and computed spectroscopic properties. Importantly, we find that the surfactant, i.e., cetylpyridinium chloride (CPC), is crucial for the openings to be localized at the corners of the hollow cube and be tailored to a cubic shape in our one-step process. Furthermore, such a well-defined hollow architecture also allows a guest nano-object to be contained within, while the large openings at corners enable controlled loading/release of nanoscale cargo, a DNA-coated particle, using change of ionic conditions. This work expands our understanding of surface engineering in nanoscale galvanic replacement reactions and opens new ways toward the shape control of hollow NPs.