Tailoring the aluminum nanocrystal surface oxide for all-aluminum-based antenna-reactor plasmonic photocatalysts.

Aluminum nanocrystals (AlNCs) are of increasing interest as sustainable, earth-abundant nanoparticles for visible wavelength plasmonics and as versatile nanoantennas for energy-efficient plasmonic photocatalysis. Here, we show that annealing AlNCs under various gases and thermal conditions induces substantial, systematic changes in their surface oxide, modifying crystalline phase, surface morphology, density, and defect type and concentration. Tailoring the surface oxide properties enables AlNCs to function as all-aluminum-based antenna-reactor plasmonic photocatalysts, with the modified surface oxides providing varying reactivities and selectivities for several chemical reactions.

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.

d-Band Hole Dynamics in Gold Nanoparticles Measured with Time-Resolved Emission Upconversion Microscopy.

The performance of photocatalysts and photovoltaic devices can be enhanced by energetic charge carriers produced from plasmon decay, and the lifetime of these energetic carriers greatly affects overall efficiencies. Although hot electron lifetimes in plasmonic gold nanoparticles have been investigated, hot hole lifetimes have not been as thoroughly studied in plasmonic systems. Here, we demonstrate time-resolved emission upconversion microscopy and use it to resolve the lifetime and energy-dependent cooling of d-band holes formed in gold nanoparticles by plasmon excitation and by following plasmon decay into interband and then intraband electron-hole pairs.

Designing structures that maximize spatially averaged surface-enhanced Raman spectra.

We present a general framework for inverse design of nanopatterned surfaces that maximize spatially averaged surface-enhanced Raman (SERS) spectra from molecules distributed randomly throughout a material or fluid, building upon a recently proposed trace formulation for optimizing incoherent emission. This leads to radically different designs than optimizing SERS emission at a single known location, as we illustrate using several 2D design problems addressing effects of hot-spot density, angular selectivity, and nonlinear damage. We obtain optimized structures that perform about 4 × better than coating with optimized spheres or bowtie structures and about 20 × better when the nonlinear damage effects are included.

Selective Photodetoxification of a Sulfur Mustard Simulant Using Plasmonic Aluminum Nanoparticles.

Plasmonic nanostructures have attracted increasing interest in the fields of photochemistry and photocatalysis for their ability to enhance reactivity and tune reaction selectivity, a benefit of their strong interactions with light and their multiple energy decay mechanisms. Here we introduce the use of earth-abundant plasmonic aluminum nanoparticles as a promising renewable detoxifier of the sulfur mustard simulant 2-chloroethylethylsulfide through gas phase photodecomposition. Analysis of the decomposition products indicates that C-S bond breaking is facilitated under illumination, while C-Cl breaking and HCl elimination are favored under thermocatalytic (dark) conditions. This difference in reaction pathways illuminates the potential of plasmonic nanoparticles to tailor reaction selectivity toward less hazardous products in the detoxification of chemical warfare agents. Moreover, the photocatalytic activity of the Al nanoparticles can be regenerated almost completely after the reaction concludes through a simple surface treatment.

A high-efficiency regime for gas-phase terahertz lasers.

We present both an innovative theoretical model and an experimental validation of a molecular gas optically pumped far-infrared (OPFIR) laser at 0.25 THz that exhibits 10× greater efficiency (39% of the Manley-Rowe limit) and 1,000× smaller volume than comparable commercial lasers. Unlike previous OPFIR-laser models involving only a few energy levels that failed even qualitatively to match experiments at high pressures, our ab initio theory matches experiments quantitatively, within experimental uncertainties with no free parameters, by accurately capturing the interplay of millions of degrees of freedom in the laser. We show that previous OPFIR lasers were inefficient simply by being too large and that high powers favor high pressures and small cavities. We believe that these results will revive interest in OPFIR laser as a powerful and compact source of terahertz radiation.

Light-Induced Thermal Gradients in Ruthenium Catalysts Significantly Enhance Ammonia Production.

Industrial scale catalytic chemical synthesis demands both high reaction rates and high product yields. In exothermic chemical reactions, these conflicting objectives require a complex balance of optimized catalysts, high temperatures, high pressures, and multiple recycling steps, as in the energy-intensive Haber-Bosch process for ammonia synthesis. Here we report that illumination of a conventional ruthenium-based catalyst produces ammonia with high reaction rates and high conversion yields. Indeed, using continuous wave light-emitting diodes that simulate concentrated solar illumination, ammonia is copiously produced without any external heating or elevated pressures. The possibility of nonthermal plasmonic effects are excluded by carefully comparing the catalytic activity under direct and indirect illumination. Instead, thermal gradients, created and controlled by photothermal heating of the illuminated catalyst surface, are shown to be responsible for the high reaction rates and conversion yields. This nonisothermal environment enhances both by balancing the conflicting requirements of kinetics and thermodynamics, heralding the use of optically controlled thermal gradients as a universal, scalable strategy for the catalysis of many exothermic chemical reactions.

Plasmon-Enhanced Catalysis: Distinguishing Thermal and Nonthermal Effects.

In plasmon-enhanced heterogeneous catalysis, illumination accelerates reaction rates by generating hot carriers and hot surfaces in the constituent nanostructured metals. In order to understand how photogenerated carriers enhance the nonthermal reaction rate, the effects of photothermal heating and thermal gradients in the catalyst bed must be confidently and quantitatively characterized. This is a challenging task considering the conflating effects of light absorption, heat transport, and reaction energetics. Here, we introduce a methodology to distinguish the thermal and nonthermal contributions from plasmon-enhanced catalysts, demonstrated by illuminated rhodium nanoparticles on oxide supports to catalyze the CO2 methanation reaction. By simultaneously measuring the total reaction rate and the temperature gradient of the catalyst bed, the effective thermal reaction rate may be extracted. The residual nonthermal rate of the plasmon-enhanced reaction is found to grow with a superlinear dependence on illumination intensity, and its apparent quantum efficiency reaches ∼46% on a Rh/TiO2 catalyst at a surface temperature of 350 °C. Heat and light are shown to work synergistically in these reactions: the higher the temperature, the higher the overall nonthermal efficiency in plasmon-enhanced catalysis.

Compressive sensing and adaptive sampling applied to millimeter wave inverse synthetic aperture imaging.

In order to improve speed and efficiency over traditional scanning methods, a Bayesian compressive sensing algorithm using adaptive spatial sampling is developed for single detector millimeter wave synthetic aperture imaging. The application of this algorithm is compared to random sampling to demonstrate that the adaptive algorithm converges faster for simple targets and generates more reliable reconstructions for complex targets.

Wide bandwidth, millimeter-resolution inverse synthetic aperture radar imaging.

The combination of wide bandwidth W-band inverse synthetic aperture radar imagery and high-fidelity numerical simulations has been used to identify distinguishing signatures from simple metallic and dielectric targets. Targets are located with millimeter-scale accuracy using super-resolution techniques. Radon transform reconstructions of the returns from rotated targets approached the image quality of the complete data set in a fraction of the time by sampling as few as 10 angles. The limitations of shooting-and-bouncing ray simulations at high frequencies are illustrated through a critical comparison of their predictions with the measured data and the method of moments simulations, indicating the importance of accurately capturing the obfuscating role played by multipath interference in complex targets.

Aluminum Nanocrystals as a Plasmonic Photocatalyst for Hydrogen Dissociation.

Hydrogen dissociation is a critical step in many hydrogenation reactions central to industrial chemical production and pollutant removal. This step typically utilizes the favorable band structure of precious metal catalysts like platinum and palladium to achieve high efficiency under mild conditions. Here we demonstrate that aluminum nanocrystals (Al NCs), when illuminated, can be used as a photocatalyst for hydrogen dissociation at room temperature and atmospheric pressure, despite the high activation barrier toward hydrogen adsorption and dissociation. We show that hot electron transfer from Al NCs to the antibonding orbitals of hydrogen molecules facilitates their dissociation. Hot electrons generated from surface plasmon decay and from direct photoexcitation of the interband transitions of Al both contribute to this process. Our results pave the way for the use of aluminum, an earth-abundant, nonprecious metal, for photocatalysis.

How an oxide shell affects the ultraviolet plasmonic behavior of Ga, Mg, and Al nanostructures.

The ultraviolet (UV) range presents new challenges for plasmonics, with interesting applications ranging from engineering to biology. In previous research, gallium, aluminum, and magnesium were found to be very promising UV plasmonic metals. However, a native oxide shell surrounds nanostructures of these metals that affects their plasmonic response. Here, through a nanoparticle-oxide core-shell model, we present a detailed electromagnetic analysis of how oxidation alters the UV-plasmonic response of spherical or hemisphere-on-substrate nanostructures made of those metals by analyzing the spectral evolution of two parameters: the absorption efficiency (far-field analysis) and the enhancement of the local intensity averaged over the nanoparticle surface (near-field analysis).

Photoluminescence Mechanism and Photocatalytic Activity of Organic-Inorganic Hybrid Materials Formed by Sequential Vapor Infiltration.

Organic-inorganic hybrid materials formed by sequential vapor infiltration (SVI) of trimethylaluminum into polyester fibers are demonstrated, and the photoluminescence of the fibers is evaluated using a combined UV-vis and photoluminescence excitation (PLE) spectroscopy approach. The optical activity of the modified fibers depends on infiltration thermal processing conditions and is attributed to the reaction mechanisms taking place at different temperatures. At low temperatures a single excitation band and dual emission bands are observed, while, at high temperatures, two distinct absorption bands and one emission band are observed, suggesting that the physical and chemical structure of the resulting hybrid material depends on the SVI temperature. Along with enhancing the photoluminescence intensity of the PET fibers, the internal quantum efficiency also increased to 5-fold from ∼4-5% to ∼24%. SVI processing also improved the photocatalytic activity of the fibers, as demonstrated by photodeposition of Ag and Au metal particles out of an aqueous metal salt solution onto fiber surfaces via UVA light exposure. Toward applications in flexible electronics, well-defined patterning of the metallic materials is achieved by using light masking and focused laser rastering approaches.

Rhodium nanoparticles for ultraviolet plasmonics.

The nonoxidizing catalytic noble metal rhodium is introduced for ultraviolet plasmonics. Planar tripods of 8 nm Rh nanoparticles, synthesized by a modified polyol reduction method, have a calculated local surface plasmon resonance near 330 nm. By attaching p-aminothiophenol, local field-enhanced Raman spectra and accelerated photodamage were observed under near-resonant ultraviolet illumination, while charge transfer simultaneously increased fluorescence for up to 13 min. The combined local field enhancement and charge transfer demonstrate essential steps toward plasmonically enhanced ultraviolet photocatalysis.

Aluminum nanocrystals.

We demonstrate the facile synthesis of high purity aluminum nanocrystals over a range of controlled sizes from 70 to 220 nm diameter with size control achieved through a simple modification of solvent ratios in the reaction solution. The monodisperse, icosahedral, and trigonal bipyramidal nanocrystals are air-stable for weeks, due to the formation of a 2-4 nm thick passivating oxide layer on their surfaces. We show that the nanocrystals support size-dependent ultraviolet and visible plasmon modes, providing a far more sustainable alternative to gold and silver nanoparticles currently in widespread use.

Adaptive millimeter-wave synthetic aperture imaging for compressive sampling of sparse scenes.

We apply adaptive sensing techniques to the problem of locating sparse metallic scatterers using high-resolution, frequency modulated continuous wave W-band RADAR. Using a single detector, a frequency stepped source, and a lateral translation stage, inverse synthetic aperture RADAR reconstruction techniques are used to search for one or two wire scatterers within a specified range, while an adaptive algorithm determined successive sampling locations. The two-dimensional location of each scatterer is thereby identified with sub-wavelength accuracy in as few as 1/4 the number of lateral steps required for a simple raster scan. The implications of applying this approach to more complex scattering geometries are explored in light of the various assumptions made.

Optical characterization of electron-phonon interactions at the saddle point in graphene.

The role of many-body interactions is experimentally and theoretically investigated near the saddle point absorption peak of graphene. The time and energy-resolved differential optical transmission measurements reveal the dominant role played by electron-acoustic phonon coupling in band structure renormalization. Using a Born approximation for electron-phonon coupling and experimental estimates of the dynamic lattice temperature, we compute the differential transmission line shape. Comparing the numerical and experimental line shapes, we deduce the effective acoustic deformation potential to be Deff(ac)≃5 eV. This value is in accord with recent theoretical predictions but differs from those extracted using electrical transport measurements.

Ultraviolet nanoplasmonics: a demonstration of surface-enhanced Raman spectroscopy, fluorescence, and photodegradation using gallium nanoparticles.

Self-assembled arrays of hemispherical gallium nanoparticles deposited by molecular beam epitaxy on a sapphire support are explored as a new type of substrate for ultraviolet plasmonics. Spin-casting a 5 nm film of crystal violet upon these nanoparticles permitted the demonstration of surface-enhanced Raman spectra, fluorescence, and degradation following excitation by a HeCd laser operating at 325 nm. Measured local Raman enhancement factors exceeding 10(7) demonstrate the potential of gallium nanoparticle arrays for plasmonically enhanced ultraviolet detection and remediation.

Aluminum plasmonic nanoantennas.

The use of aluminum for plasmonic nanostructures opens up new possibilities, such as access to short-wavelength regions of the spectrum, complementary metal-oxide-semiconductor (CMOS) compatibility, and the possibility of low-cost, sustainable, mass-producible plasmonic materials. Here we examine the properties of individual Al nanorod antennas with cathodoluminescence (CL). This approach allows us to image the local density of optical states (LDOS) of Al nanorod antennas with a spatial resolution less than 20 nm and to identify the radiative modes of these nanostructures across the visible and into the UV spectral range. The results, which agree well with finite difference time domain (FDTD) simulations, lay the groundwork for precise Al plasmonic nanostructure design for a variety of applications.

Controlling product selectivity in hybrid gas/liquid reactors using gas conditions, voltage, and temperature.

For the conversion of CO2 into fuels and chemical feedstocks, hybrid gas/liquid-fed electrochemical flow reactors provide advantages in selectivity and production rates over traditional liquid phase reactors. However, fundamental questions remain about how to optimize conditions to produce desired products. Using an alkaline electrolyte to suppress hydrogen formation and a gas diffusion electrode catalyst composed of copper nanoparticles on carbon nanospikes, we investigate how hydrocarbon product selectivity in the CO2 reduction reaction in hybrid reactors depends on three experimentally controllable parameters: (1) supply of dry or humidified CO2 gas, (2) applied potential, and (3) electrolyte temperature. Changing from dry to humidified CO2 dramatically alters product selectivity from C2 products ethanol and acetic acid to ethylene and C1 products formic acid and methane. Water vapor evidently influences product selectivity of reactions that occur on the gas-facing side of the catalyst by adding a source of protons that alters reaction pathways and intermediates.