Reduced-Dimensionality Al Nanocrystals: Nanowires, Nanobars, and Nanomoustaches.

Aluminum nanocrystals created by catalyst-driven colloidal synthesis support excellent plasmonic properties, due to their high level of elemental purity, monocrystallinity, and controlled size and shape. Reduction in the rate of nanocrystal growth enables the synthesis of highly anisotropic Al nanowires, nanobars, and singly twinned "nanomoustaches". Electron energy loss spectroscopy was used to study the plasmonic properties of these nanocrystals, spanning the broad energy range needed to map their plasmonic modes. The coupling between these nanocrystals and other plasmonic metal nanostructures, specifically Ag nanocubes and Au films of controlled nanoscale thickness, was investigated. Al nanocrystals show excellent long-term stability under atmospheric conditions, providing a practical alternative to coinage metal-based nanowires in assembled nanoscale devices.

Facet Tunability of Aluminum Nanocrystals.

Aluminum nanocrystals (Al NCs) with a well-defined size and shape combine unique plasmonic properties with high earth abundance, potentially ideal for applications where sustainability and cost are important factors. It has recently been shown that single-crystal Al {100} nanocubes can be synthesized by the decomposition of AlH3 with Tebbe's reagent, a titanium(IV) catalyst with two cyclopentadienyl ligands. By systematically modifying the catalyst molecular structure, control of the NC growth morphology is observed spectroscopically, as the catalyst stabilizes the {100} NC facets. By varying the catalyst concentration, Al NC faceted growth is tunable from {100} faceted nanocubes to {111} faceted octahedra. This study provides direct insight into the role of catalyst molecular structure in controlling Al NC morphology.

Plasmon-Generated Solvated Electrons for Chemical Transformations.

Methods for generating solvated electrons─free electrons in solution─have focused primarily on alkali metal ionization or high-energy electrons or photons. Here we report the generation of solvated electrons by exciting the plasmon resonance of Al nanocrystals suspended in solution with visible light. Two chemical reactions were performed: a radical-addition reaction with the spin-trap 2-methyl-2-nitrosopropane, and a model cyclization reaction with the radical clock 6-bromohex-1-ene. A quantum efficiency of at least ∼1.1% for plasmon absorbed photon to solvated electron generation can be inferred from the measured radical clock reaction concentration. This study demonstrates a simple way to generate solvated electrons for driving reductive organic chemical reactions in a quantifiable and controlled manner.

Al@TiO2 Core-Shell Nanoparticles for Plasmonic Photocatalysis.

Plasmon-induced photocatalysis is a topic of rapidly increasing interest, due to its potential for substantially lowering reaction barriers and temperatures and for increasing the selectivity of chemical reactions. Of particular interest for plasmonic photocatalysis are antenna-reactor nanoparticles and nanostructures, which combine the strong light-coupling of plasmonic nanostructures with reactors that enhance chemical specificity. Here, we introduce Al@TiO2 core-shell nanoparticles, combining earth-abundant Al nanocrystalline cores with TiO2 layers of tunable thickness. We show that these nanoparticles are active photocatalysts for the hot electron-mediated H2 dissociation reaction as well as for hot hole-mediated methanol dehydration. The wavelength dependence of the reaction rates suggests that the photocatalytic mechanism is plasmonic hot carrier generation with subsequent transfer of the hot carriers into the TiO2 layer. The Al@TiO2 antenna-reactor provides an earth-abundant solution for the future design of visible-light-driven plasmonic photocatalysts.

UV-Resonant Al Nanocrystals: Synthesis, Silica Coating, and Broadband Photothermal Response.

The field of plasmonics has largely been inspired by the properties of Au and Ag nanoparticles, leading to applications in sensing, photocatalysis, nanomedicine, and solar water treatment. Recently the quest for new plasmonic materials has focused on earth-abundant elements, where aluminum is a sustainable, low-cost potential alternative. Here we report the chemical synthesis of sub-50 nm diameter Al nanocrystals with a plasmon-resonant absorption in the UV region of the spectrum. We observe a transition from a UV-resonant response, that is, a colorless solution, to a broadband absorptive response, that is, a completely black solution, as the nanocrystal concentration is increased. The strong absorptive interband transition in Al provides the dominant mechanism responsible for this effect. We developed a robust method to functionalize Al nanocrystals with silica to increase their stability in H2O from hours to weeks enabling us to observe efficient broadband photothermal heating with these nanoparticles.

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 O2, H2O, and many reagents used in traditional NC syntheses. The first chemical synthesis of Al NCs was demonstrated by Haber and Buhro in 1998, decomposing AlH3 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 AlH3 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.