Silver Nanocubes: From Serendipity to Mechanistic Understanding, Rational Synthesis, and Niche Applications

[Image: see text] Silver has long been interwoven into human history, and its uses have evolved from currency and jewelry to medicine, information technology, catalysis, and electronics. Within the last century, the development of nanomaterials has further solidified the importance of this element. Despite this long history, there was essentially no mechanistic understanding or experimental control of silver nanocrystal synthesis until about two decades ago. Here we aim to provide an account of the history and development of the colloidal synthesis of silver nanocubes, as well as some of their major applications. We begin with a description of the first accidental synthesis of silver nanocubes that spurred subsequent investigations into each of the individual components of the protocol, revealing piece by piece parts of the mechanistic puzzle. This is followed by a discussion of the various obstacles inherent to the original method alongside mechanistic details developed to optimize the synthetic protocol. Finally, we discuss a range of applications enabled by the plasmonic and catalytic properties of silver nanocubes, including localized surface plasmon resonance, surface-enhanced Raman scattering, metamaterials, and ethylene epoxidation, as well as further derivatization and development of size, shape, composition, and related properties.