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.

A 3D Plasmonic Antenna-Reactor for Nanoscale Thermal Hotspots and Gradients.

Plasmonic nanoantennas focus light below the diffraction limit, creating strong field enhancements, typically within a nanoscale junction. Placing a nanostructure within the junction can greatly enhance the nanostructure's innate optical absorption, resulting in intense photothermal heating that could ultimately compromise both the nanostructure and the nanoantenna. Here, we demonstrate a three-dimensional "antenna-reactor" geometry that results in large nanoscale thermal gradients, inducing large local temperature increases in the confined nanostructure reactor while minimizing the temperature increase of the surrounding antenna. The nanostructure is supported on an insulating substrate within the antenna gap, while the antenna maintains direct contact with an underlying thermal conductor. Elevated local temperatures are quantified, and high local temperature gradients that thermally reshape only the internal reactor element within each antenna-reactor structure are observed. We also show that high local temperature increases of nominally 200 °C are achievable within antenna-reactors patterned into large extended arrays. This simple strategy can facilitate standoff optical generation of high-temperature hotspots, which may be useful in applications such as small-volume, high-throughput chemical processes, where reaction efficiencies depend exponentially on local temperature.

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.

Acoustic Vibrations of Al Nanocrystals: Size, Shape, and Crystallinity Revealed by Single-Particle Transient Extinction Spectroscopy.

Acoustic vibrations in plasmonic nanoparticles, monitored by an all-optical means, have attracted significant increasing interest because they provide unique insight into the mechanical properties of these metallic nanostructures. Al nanostructures are a recently emerging alternative to noble metal nanoparticles, because their broad wavelength tunability and high natural abundance make them ideal for many potential applications. Here, we investigate the acoustic vibrations of individual Al nanocrystals using a combination of electron microscopy and single-particle transient extinction spectroscopy, made possible with a low-pulse energy, high sensitivity, and probe-wavelength-tunable, single-particle transient extinction microscope. For chemically synthesized, faceted Al nanocrystals, the observed vibration frequency scales with the inverse particle diameter. In contrast, triangularly shaped Al nanocrystals support two distinct frequencies, corresponding to their in- and out-of-plane breathing modes. Unlike ensemble measurements, which measure average properties, measuring the damping time of the acoustic vibrations for individual particles enables us to investigate variations of the quality factor on the particle-to-particle level. Surprisingly, we find a large variation in quality factors even for nanocrystals of similar size and shape. This observed heterogeneity appears to result from substantially varying degrees of nanoparticle crystallinity even for chemically synthesized nanocrystals.

Aluminum Nanocubes Have Sharp Corners.

Of the many plasmonic nanoparticle geometries that have been synthesized, nanocubes have been of particular interest for creating nanocavities, facilitating plasmon coupling, and enhancing phenomena dependent upon local electromagnetic fields. Here we report the straightforward colloidal synthesis of single-crystalline {100} terminated Al nanocubes by decomposing AlH3 with Tebbe's reagent in tetrahydrofuran. The size and shape of the Al nanocubes is controlled by the reaction time and the ratio of AlH3 to Tebbe's reagent, which, together with reaction temperature, establish kinetic control over Al nanocube growth. Al nanocubes possess strong localized field enhancements at their sharp corners and resonances highly amenable to coupling with metallic substrates. Their native oxide surface renders them extremely air stable. Chemically synthesized Al nanocubes provide an earth-abundant alternative to noble metal nanocubes for plasmonics and nanophotonics applications.

Ultrafast Electron Dynamics in Single Aluminum Nanostructures.

Aluminum nanostructures are a promising alternative material to noble metal nanostructures for several photonic and catalytic applications, but their ultrafast electron dynamics remain elusive. Here, we combine single-particle transient extinction spectroscopy and parameter-free first-principles calculations to investigate the non-equilibrium carrier dynamics in aluminum nanostructures. Unlike gold nanostructures, we find the sub-picosecond optical response of lithographically fabricated aluminum nanodisks to be more sensitive to the lattice temperature than the electron temperature. We assign the rise in the transient transmission to electron-phonon coupling with a pump-power-independent lifetime of 500 ± 100 fs and theoretically confirm this strong electron-phonon coupling behavior. We also measure electron-phonon lifetimes in chemically synthesized aluminum nanocrystals and find them to be even longer (1.0 ± 0.1 ps) than for the nanodisks. We also observe a rise and decay in the transient transmissions with amplitudes that scale with the surface-to-volume ratio of the aluminum nanodisks, implying a possible hot carrier trapping and detrapping at the native oxide shell-metal core interface.

Polydopamine-Stabilized Aluminum Nanocrystals: Aqueous Stability and Benzo[a]pyrene Detection.

Aluminum nanocrystals have emerged as an earth-abundant material for plasmonics applications. Al nanocrystals readily oxidize in aqueous-based solutions, however, transforming into highly stratified γ-AlOOH nanoparticles with a 700% increase in surface area in a matter of minutes. Here we show that by functionalizing Al nanocrystals with the bioinspired polymer polydopamine, their stability in aqueous media is dramatically increased, maintaining their integrity in aqueous solution for over 2 weeks with no discernible structural changes. Polydopamine functionalization also provides a molecular capture layer that enables the capture of polycyclic aromatic hydrocarbon pollutants in H2O samples and their detection by surface-enhanced Raman spectroscopy, when polydopamine-stabilized Al nanocrystal aggregates are used as substrates. This approach was used to detect a prime carcinogenic H2O pollutant, benzo[a]pyrene with a sensitivity in the sub part-per-billion range.

Ligand-Dependent Colloidal Stability Controls the Growth of Aluminum Nanocrystals.

The precise size- and shape-controlled synthesis of monodisperse Al nanocrystals remains an open challenge, limiting their utility for numerous applications that would take advantage of their size and shape-dependent optical properties. Here we pursue a molecular-level understanding of the formation of Al nanocrystals by titanium(IV) isopropoxide-catalyzed decomposition of AlH3 in Lewis base solvents. As determined by electron paramagnetic resonance spectroscopy of intermediates, the reaction begins with the formation of Ti3+-AlH3 complexes. Proton nuclear magnetic resonance spectroscopy indicates isopropoxy ligands are removed from Ti by Al, producing aluminum(III) isopropoxide and low-valent Ti3+ catalysts. These Ti3+ species catalyze elimination of H2 from AlH3 inducing the polymerization of AlH3 into colloidally unstable low-valent aluminum hydride clusters. These clusters coalesce and grow while expelling H2 to form colloidally stable Al nanocrystals. The colloidal stability of the Al nanocrystals and their size is determined by the molecular structure and density of coordinating atoms in the reaction, which is controlled by choice of solvent composition.

Transition-Metal Decorated Aluminum Nanocrystals.

Recently, aluminum has been established as an earth-abundant alternative to gold and silver for plasmonic applications. Particularly, aluminum nanocrystals have shown to be promising plasmonic photocatalysts, especially when coupled with catalytic metals or oxides into "antenna-reactor" heterostructures. Here, a simple polyol synthesis is presented as a flexible route to produce aluminum nanocrystals decorated with eight varieties of size-tunable transition-metal nanoparticle islands, many of which have precedence as heterogeneous catalysts. High-resolution and three-dimensional structural analysis using scanning transmission electron microscopy and electron tomography shows that abundant nanoparticle island decoration in the catalytically relevant few-nanometer size range can be achieved, with many islands spaced closely to their neighbors. When coupled with the Al nanocrystal plasmonic antenna, these small decorating islands will experience increased light absorption and strong hot-spot generation. This combination makes transition-metal decorated aluminum nanocrystals a promising material platform to develop plasmonic photocatalysis, surface-enhanced spectroscopies, and quantum plasmonics.