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.

A Quasi-Bound States in the Continuum Dielectric Metasurface-Based Antenna-Reactor Photocatalyst.

Metasurfaces are a class of two-dimensional artificial resonators, creating new opportunities for strong light-matter interactions. One type of nonradiative optical metasurface that enables substantial light concentration is based on quasi-Bound States in the Continuum (quasi-BIC). Here we report the design and fabrication of a quasi-BIC dielectric metasurface that serves as an optical frequency antenna for photocatalysis. By depositing Ni nanoparticle reactors onto the metasurface, we create an antenna-reactor photocatalyst, where the virtually lossless metasurface funnels light to drive a chemical reaction. This quasi-BIC-Ni antenna-reactor drives H2 dissociation under resonant illumination, showing strong polarization, wavelength, and optical power dependencies. Both E-field-induced electronic and photothermal heating effects drive the reaction, supported by load-dependent reactivity studies and our theoretical model. This study unlocks new opportunities for photocatalysis that employ dielectric metasurfaces for light harvesting in an antenna-reactor format.

Combined Surface-Enhanced Raman and Infrared Absorption Spectroscopies for Streamlined Chemical Detection of Polycyclic Aromatic Hydrocarbon-Derived Compounds.

Polycyclic aromatic hydrocarbons (PAHs) constitute a class of universally prevalent carcinogenic environmental contaminants. It is increasingly recognized, however, that PAHs derivatized with oxygen, sulfur, or nitrogen functional groups are frequently more dangerous than their unfunctionalized counterparts. This much larger family of chemicals─polycyclic aromatic compounds─PACs─is far less well characterized than PAHs. Using surface-enhanced Raman and IR Absorption spectroscopies (SERS + SEIRA) combined on a single substrate, along with density functional theoretical (DFT) calculations, we show that direct chemical detection and identification of PACs at sub-parts-per-billion concentration can be achieved. Focusing our studies on 9,10-anthraquinone, 5,12-tetracenequinone, 9-nitroanthracene, and 1-nitropyrene as model PAC contaminants, detection is made possible by incorporating a hydroxy-functionalized self-assembled monolayer that facilitates hydrogen bonding between analytes and the SERS + SEIRA substrate. 5,12-Tetracenequinone was detected at 0.3 ppb, and the limit of detection was determined to be 0.1 ppb using SEIRA alone. This approach is straightforwardly extendable to other families of analytes and will ultimately facilitate fieldable chemical detection of these dangerous yet largely overlooked environmental contaminants.

Identifying Surface-Enhanced Raman Spectra with a Raman Library Using Machine Learning.

Since its discovery, surface-enhanced Raman spectroscopy (SERS) has shown outstanding promise of identifying trace amounts of unknown molecules in rapid, portable formats. However, the many different types of nanoparticles or nanostructured metallic SERS substrates created over the past few decades show substantial variability in the SERS spectra they provide. These inconsistencies have even raised speculation that substrate-specific SERS spectral libraries must be compiled for practical use of this type of spectroscopy. Here, we report a machine learning (ML) algorithm that can identify chemicals by matching their SERS spectra to those of a standard Raman spectral library. We use an approach analogous to facial recognition that utilizes feature extraction in the presence of multiple nuisance variables for spectral recognition. The key element is a metric we call "Characteristic Peak Similarity" (CaPSim) that focuses on the characteristic peaks in the SERS spectra. It has the flexibility to accommodate substrate-specific variability when quantifying the degree of similarity to a Raman spectrum. Analysis shows that CaPSim substantially outperforms existing spectral matching algorithms in terms of accuracy. This ML-based approach could greatly facilitate the spectroscopic identification of molecules in fieldable SERS applications.

Chiral Plasmonic Pinwheels Exhibit Orientation-Independent Linear Differential Scattering under Asymmetric Illumination.

Plasmonic nanoantennas have considerably stronger polarization-dependent optical properties than their molecular counterparts, inspiring photonic platforms for enhancing molecular dichroism and providing fundamental insight into light-matter interactions. One such insight is that even achiral nanoparticles can yield strong optical activity when they are asymmetrically illuminated from a single oblique angle instead of evenly illuminated. This effect, called extrinsic chirality, results from the overall chirality of the experimental geometry and strongly depends on the orientation of the incident light. Although extrinsic chirality has been well-characterized, an analogous effect involving linear polarization sensitivity has not yet been discussed. In this study, we investigate the differential scattering of rotationally symmetric chiral plasmonic pinwheels when asymmetrically irradiated with linearly polarized light. Despite their high rotational symmetry, we observe substantial linear differential scattering that is maintained over all pinwheel orientations. We demonstrate that this orientation-independent linear differential scattering arises from the broken mirror and rotational symmetries of our overall experimental geometry. Our results underscore the necessity of considering both the rotational symmetry of the nanoantenna and the experimental setup, including illumination direction and angle, when performing plasmon-enhanced chiroptical characterizations. Our results demonstrate spectroscopic signatures of an effect analogous to extrinsic chirality for linear polarizations.

Energy Transfer to Molecular Adsorbates by Transient Hot Electron Spillover.

Hot electron (HE) photocatalysis is one of the most intriguing fields of nanoscience, with a clear potential for technological impact. Despite much effort, the mechanisms of HE photocatalysis are not fully understood. Here we investigate a mechanism based on transient electron spillover on a molecule and subsequent energy release into vibrational modes. We use state-of-the-art real-time Time Dependent Density Functional Theory (rt-TDDFT), simulating the dynamics of a HE moving within linear chains of Ag or Au atoms, on which CO, N2, or H2O are adsorbed. We estimate the energy a HE can release into adsorbate vibrational modes and show that certain modes are selectively activated. The energy transfer strongly depends on the adsorbate, the metal, and the HE energy. Considering a cumulative effect from multiple HEs, we estimate this mechanism can transfer tenths of an eV to molecular vibrations and could play an important role in HE photocatalysis.

Computational chromatography: A machine learning strategy for demixing individual chemical components in complex mixtures.

Surface-enhanced Raman spectroscopy (SERS) holds exceptional promise as a streamlined chemical detection strategy for biological and environmental contaminants compared with current laboratory methods. Priority pollutants such as polycyclic aromatic hydrocarbons (PAHs), detectable in water and soil worldwide and known to induce multiple adverse health effects upon human exposure, are typically found in multicomponent mixtures. By combining the molecular fingerprinting capabilities of SERS with the signal separation and detection capabilities of machine learning (ML), we examine whether individual PAHs can be identified through an analysis of the SERS spectra of multicomponent PAH mixtures. We have developed an unsupervised ML method we call Characteristic Peak Extraction, a dimensionality reduction algorithm that extracts characteristic SERS peaks based on counts of detected peaks of the mixture. By analyzing the SERS spectra of two-component and four-component PAH mixtures where the concentration ratios of the various components vary, this algorithm is able to extract the spectra of each unknown component in the mixture of unknowns, which is then subsequently identified against a SERS spectral library of PAHs. Combining the molecular fingerprinting capabilities of SERS with the signal separation and detection capabilities of ML, this effort is a step toward the computational demixing of unknown chemical components occurring in complex multicomponent mixtures.

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.

Earth-abundant photocatalyst for H2 generation from NH3 with light-emitting diode illumination.

Catalysts based on platinum group metals have been a major focus of the chemical industry for decades. We show that plasmonic photocatalysis can transform a thermally unreactive, earth-abundant transition metal into a catalytically active site under illumination. Fe active sites in a Cu-Fe antenna-reactor complex achieve efficiencies very similar to Ru for the photocatalytic decomposition of ammonia under ultrafast pulsed illumination. When illuminated with light-emitting diodes rather than lasers, the photocatalytic efficiencies remain comparable, even when the scale of reaction increases by nearly three orders of magnitude. This result demonstrates the potential for highly efficient, electrically driven production of hydrogen from an ammonia carrier with earth-abundant transition metals.

Plasmonic Photocatalysis with Chemically and Spatially Specific Antenna-Dual Reactor Complexes.

Plasmonic antenna-reactor photocatalysts have been shown to convert light efficiently to chemical energy. Virtually all chemical reactions mediated by such complexes to date, however, have involved relatively simple reactions that require only a single type of reaction site. Here, we investigate a planar Al nanodisk antenna with two chemically distinct and spatially separated active sites in the form of Pd and Fe nanodisks, fabricated in 90° and 180° trimer configurations. The photocatalytic reactions H2 + D2 → 2HD and NH3 + D2 → NH2D + HD were both investigated on these nanostructured complexes. While the H2-D2 exchange reaction showed an additive behavior for the linear (180°) nanodisk complex, the NH3 + D2 reaction shows a clear synergistic effect of the position of the reactor nanodisks relative to the central Al nanodisk antenna. This study shows that light-driven chemical reactions can be performed with both chemical and spatial control of the specific reaction steps, demonstrating precisely designed antennas with multiple reactors for tailored control of chemical reactions of increasing complexity.

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.

Fast Topology Optimization for Near-Field Focusing All-Dielectric Metasurfaces Using the Discrete Dipole Approximation.

Using an efficient implementation of the discrete dipole approximation and topology optimization, we design all-dielectric metasurfaces capable of focusing light into intense deep subwavelength hotspots. The light focusing of these metasurfaces far outweighs conventional lenses and can provide dramatic enhancements of processes that depend superlinearly on light intensity, such as light-powered membrane distillation and photocatalysis. Our approach can easily be generalized to optimize metasurfaces for other functionalities, such as nonlinear optics or photothermal conversion.

Gd2O3-mesoporous silica/gold nanoshells: A potential dual T1/T2 contrast agent for MRI-guided localized near-IR photothermal therapy.

A promising clinical trial utilizing gold-silica core-shell nanostructures coated with polyethylene glycol (PEG) has been reported for near-infrared (NIR) photothermal therapy (PTT) of prostate cancer. The next critical step for PTT is the visualization of therapeutically relevant nanoshell (NS) concentrations at the tumor site. Here we report the synthesis of PEGylated Gd2O3-mesoporous silica/gold core/shell NSs (Gd2O3-MS NSs) with NIR photothermal properties that also supply sufficient MRI contrast to be visualized at therapeutic doses (≥108 NSs per milliliter). The nanoparticles have r1 relaxivities more than three times larger than those of conventional T1 contrast agents, requiring less concentration of Gd3+ to observe an equivalent signal enhancement in T1-weighted MR images. Furthermore, Gd2O3-MS NS nanoparticles have r2 relaxivities comparable to those of existing T2 contrast agents, observed in agarose phantoms. This highly unusual combination of simultaneous T1 and T2 contrast allows for MRI enhancement through different approaches. As a rudimentary example, we demonstrate T1/T2 ratio MR images with sixfold contrast signal enhancement relative to its T1 MRI and induced temperature increases of 20 to 55 °C under clinical illumination conditions. These nanoparticles facilitate MRI-guided PTT while providing real-time temperature feedback through thermal MRI mapping.

A Dual Catalyst Strategy for Controlling Aluminum Nanocrystal Growth.

The synthesis of Al nanocrystals (Al NCs) is a rapidly expanding field, but there are few strategies for size and morphology control. Here we introduce a dual catalyst approach for the synthesis of Al NCs to control both NC size and shape. By using one catalyst that nucleates growth more rapidly than a second catalyst whose ligands affect NC morphology during growth, one can obtain both size and shape control of the resulting Al NCs. The combination of the two catalysts (1) titanium isopropoxide (TIP), for rapid nucleation, and (2) Tebbe's reagent, for specific facet-promoting growth, yields {100}-faceted Al NCs with tunable diameters between 35 and 65 nm. This dual-catalyst strategy could dramatically expand the possible outcomes for Al NC growth, opening the door to new controlled morphologies and a deeper understanding of earth-abundant plasmonic nanocrystal synthesis.

Towards scalable plasmonic Fano-resonant metasurfaces for colorimetric sensing.

Transitioning plasmonic metasurfaces into practical, low-cost applications requires meta-atom designs that focus on ease of manufacturability and a robustness with respect to structural imperfections and nonideal substrates. It also requires the use of inexpensive, earth-abundant metals such as Al for plasmonic properties. In this study, we focus on combining two aspects of plasmonic metasurfaces-visible coloration and Fano resonances-in a morphology amenable to scalable manufacturing. The resulting plasmonic metasurface is a candidate for reflective colorimetric sensing. We examine the potential of this metasurface for reflective strain sensing, where the periodicity of the meta-atoms could ultimately be modified by a potential flexion, and for localized surface plasmon resonance refractive index sensing. This study evaluates the potential of streamlined meta-atom design combined with low-cost metallization for inexpensive sensor readout based on human optical perception.

Vacuum ultraviolet nonlinear metalens.

Vacuum ultraviolet (VUV) light plays an essential role across science and technology, from molecular spectroscopy to nanolithography and biomedical procedures. Realizing nanoscale devices for VUV light generation and control is critical for next-generation VUV sources and systems, but the scarcity of low-loss VUV materials creates a substantial challenge. We demonstrate a metalens that both generates-by second-harmonic generation-and simultaneously focuses the generated VUV light. The metalens consists of 150-nm-thick zinc oxide (ZnO) nanoresonators that convert 394 nm (~3.15 eV) light into focused 197-nm (~6.29 eV) radiation, producing a spot 1.7 µm in diameter with a 21-fold power density enhancement as compared to the wavefront at the metalens surface. The reported metalens is ultracompact and phase-matching free, allowing substantial streamlining of VUV system design and facilitating more advanced applications. This work provides a useful platform for developing low-loss VUV components and increasing the accessibility of the VUV regime.

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.