William K. Lewis

Carbon Quantum Dots and Applications in Photocatalytic Energy Conversion

Quantum dots (QDs) generally refer to nanoscale particles of conventional semiconductors that are subject to the quantum-confinement effect, though other nanomaterials of similar optical and redox properties are also named as QDs even in the absence of strictly defined quantum confinement. Among such nanomaterials that have attracted tremendous recent interest are carbon dots, which are small carbon nanoparticles with some form of surface passivation, and graphene quantum dots in various configurations. In this article, we highlight these carbon-based QDs by focusing on their syntheses, on their photoexcited state properties and redox processes, and on their applications as photocatalysts in visible-light carbon dioxide reduction and in water-splitting, as well as on their mechanistic similarities and differences.

Spontaneous Hydrogen Generation from Organic-Capped Al Nanoparticles and Water

The development of technologies that would lead toward the adoption of a hydrogen economy requires readily available, safe, and environmentally friendly access to hydrogen. This can be achieved using the aluminum-water reaction; however, the protective nature and stability of aluminum oxide is a clear detriment to its application. Here, we demonstrate the spontaneous generation of hydrogen gas from ordinary room-temperature tap water when combined with aluminum-oleic acid core-shell nanoparticles obtained via sonochemistry. The reaction is found to be near-complete (>95% yield hydrogen) with a tunable rate from 6.4x10(-4) to 0.01 g of H2/s/g of Al and to yield an environmentally benign byproduct. The potential of these nanoparticles as a source of hydrogen gas for power generation is demonstrated using a simple fuel cell with an applied load.

Ionization and fragmentation of isomeric van der Waals complexes embedded in helium nanodroplets

The ionization and charge transfer processes, which occur when a doped helium droplet undergoes electron impact, are studied for droplets doped with van der Waals complexes with various structures and electrostatic moments. The mass spectra of the two isomers of hydrogen cyanide complexed with either cyanoacetylene or acetylene in helium droplets were obtained using optically selected mass spectrometry, and show that the structure of the complex has a large effect on the fragmentation pattern. The resulting fragmentation pattern is consistent with an ionization process in which charge steering strongly influences the site of initial ionization. The observed dissociation products may also be subject to caging by the helium matrix.

Formation of cold ion-neutral clusters using superfluid helium nanodroplets.

A strategy for forming and detecting cold ion-neutral clusters using superfluid helium nanodroplets is described. Sodium cations generated via thermionic emission are directed toward a beam of helium droplets that can also pick up neutral molecules and form a cluster with the captured Na(+). The composition of the clusters is determined by mass spectrometric analysis following a desolvation step. It is shown that the polar molecules H(2)O and HCN are picked up and form ion-neutral clusters with sizes and relative abundances that are in good agreement with those predicted by the statistics used to describe neutral cluster formation in helium droplets. [Na(H(2)O)(n)](+) clusters containing six to 43 water molecules were observed, a size range of sodiated water clusters difficult to access in the gas phase. Clusters containing N(2) were in lower abundance than expected, suggesting that the desolvation process heats the clusters sufficiently to dissociate those containing nonpolar molecules.

Confirmation of the metastability of HF (v=1) in helium nanodroplets.

Infrared laser spectroscopy is reported for HF in helium nanodroplets. The purpose of the present study is to resolve a discrepancy in the literature, namely, between the previous optothermal study, which indicates the HF does not vibrationally relax in the droplets, with an earlier mass spectrometer experiment which showed laser induced depletion. The resolution of this issue is that the depletion signal arises from the pickup of another molecule after an infrared photon has been absorbed by the HF monomer. In the case of pickup of an N2 molecule, the formation of the N2-HF (v=1) complex then facilitates vibrational relaxation, causing the laser induced depletion. Simulations of this effect provide quantitative agreement with the observed behavior.

A threshold-based approach to calorimetry in helium droplets: measurement of binding energies of water clusters.

Helium droplet beam methods have emerged as a versatile technique that can be used to assemble a wide variety of atomic and molecular clusters. We have developed a method to measure the binding energies of clusters assembled in helium droplets by determining the minimum droplet sizes required to assemble and detect selected clusters in the spectrum of the doped droplet beam. The differences in the droplet sizes required between the various multimers are then used to estimate the incremental binding energies. We have applied this method to measure the binding energies of cyclic water clusters from the dimer to the tetramer. We obtain measured values of D(0) that are in agreement with theoretical estimates to within ∼20%. Our results suggest that this threshold-based approach should be generally applicable using either mass spectrometry or optical spectroscopy techniques for detection, provided that the clusters selected for study are at least as strongly bound as those of water, and that a peak in the overall spectrum of the beam corresponding only to the cluster chosen (at least in the vicinity of the threshold) can be located.

Infrared spectroscopy of HCN-salt complexes formed in liquid-helium nanodroplets

Rotationally resolved infrared spectra are reported for the binary complexes of HCN and LiF, LiCl, NaF, and NaCl, formed in helium nanodroplets. Stark spectroscopy is used to determine the dipole moments for these complexes. Ab initio calculations are also reported for these complexes, revealing the existence of several different isomers of these binary systems. In the frequency region examined in this experimental study we only observe one of these, corresponding to the salt binding to the nitrogen end of the HCN molecule. The experimental rotational constants, dipole moments, and vibrational frequency shifts are all compared with the results from ab initio calculations for this isomer.

Investigating the Performance of Novel Energetic Materials Using Optical Diagnostics

The primary goal of this work is to explore optical diagnostic strategies for studying the mechanisms that control the reaction of novel energetic materials. Thus far, predictive models of these mechanisms have been elusive, and advanced diagnostics can help close the gap in the understanding of energetic initiation, ignition, shock-wave formation, propagation, and energy release. The proposed effort focuses on the development of optical diagnostics for imaging the reactions induced via laser ignition, including high-speed schlieren, two-color thermometry, and micro-optical imaging. Measurements are used to draw comparisons between the combustion of microand nano-scale aluminum, the effects of different fuel-oxidizer mixtures, and the influence of different passivation methods.