Shining Light on Aluminum Nanoparticle Synthesis.

ConspectusAluminum in its nanostructured form is generating increasing interest because of its light-harvesting properties, achieved by excitation of its localized surface plasmon resonance. Compared to traditional plasmonic materials, the coinage metals Au and Ag, Al is far more earth-abundant and, therefore, more suitable for large-area applications or where cost may be an important factor. Its optical properties are far more flexible than either Au or Ag, supporting plasmon resonances that range from UV wavelengths, through the visible regime, and into the infrared region of the spectrum. However, the chemical synthesis of Al nanocrystals (NCs) of controlled size and shape has historically lagged far behind that of Au and Ag. This is partially due to the high reactivity of Al precursors, which react readily with O, HO, and many reagents used in traditional NC syntheses. The first chemical synthesis of Al NCs was demonstrated by Haber and Buhro in 1998, decomposing AlH using titanium isopropoxide (TIP), with a number of subsequent reports refining this protocol. The role of a catalyst in Al NC synthesis is, we believe, unique to this synthetic approach. In 2015, the first synthesis of size controlled Al NCs was published by our group. Since then, we have significantly advanced Al NC synthesis, postsynthetic modifications, and applications of Al nanoparticles (NPs)-NCs with additional surface modifications-in chemical sensing and photocatalysis. Colloidal Al synthesis has its unique challenges, differing markedly from the far more familiar Au and Ag syntheses, which currently appears to present a de facto barrier to broader research activity in this field.The goal of this Account is to highlight developments in controlled synthesis of Al NCs and applications of Al NPs over the last five years. We outline techniques for successful Al NC synthesis and address some of the problems that may be encountered in this synthesis. A mechanistic understanding of AlH decomposition using TIP has been developed, while new directions have been discovered for synthetic control. Facet-binding ligands, alternate Al precursors, new titanium-based reduction catalysts, even solvent composition have all been shown to control reaction products while also opening doors to future developments. A variety of postsynthetic modifications to the Al NC native oxide surface, including polymer, MOF, and transition metal island coatings have been demonstrated for applications in molecular sensing and photocatalysis. In this Account, we hope to convey that Al synthesis is more accessible than generally perceived and to encourage new synthetic development based on underlying mechanisms controlling size and shape. High selectivity in particle faceting and twinning, implementation of seeded growth principles for monodisperse samples, and the demonstration of new, practical applications of Al nanoparticles remain primary challenges in the field. As Al nanoparticle synthesis is refined and new applications emerge, colloidal Al will become an accessible and low-cost plasmonic nanomaterial complementary to Au and Ag.