Photoelectrocatalysis: Principles, nanoemitter applications and routes to bio-inspired systems

An overview on processes that are relevant in light-induced fuel generation, such as water photoelectrolysis or carbon dioxide reduction, is given. Considered processes encompass the photophysics of light absorption, excitation energy transfer to catalytically active sites and interfacial reactions at the catalyst/solution phase boundary. The two major routes envisaged for realization of photoelectrocatalytic systems, e.g. bio-inspired single photon catalysis and multiple photon inorganic or hybrid tandem cells, are outlined. For development of efficient tandem cell structures that are based on non-oxidic semiconductors, stabilization strategies are presented. Physical surface passivation is described using the recently introduced nanoemitter concept which is also applicable in photovoltaic (solid state or electrochemical) solar cells and first results with p-Si and p-InP thin films are presented. Solar-to-hydrogen efficiencies reach 12.1% for homoepitaxial InP thin films covered with Rh nanoislands. In the pursuit to develop biologically inspired systems, enzyme adsorption onto electrochemically nanostructured silicon surfaces is presented and tapping mode atomic force microscopy images of heterodimeric enzymes are shown. An outlook towards future envisaged systems is given. © 2010 The Royal Society of Chemistry.

Comprehensive search for new phases and compounds in binary alloy systems based on platinum-group metals, using a computational first-principles approach

We report a comprehensive study of the binary systems of the platinum-group metals with the transition metals, using high-throughput first-principles calculations. These computations predict stability of new compounds in 28 binary systems where no compounds have been reported in the literature experimentally and a few dozen of as-yet unreported compounds in additional systems. Our calculations also identify stable structures at compound compositions that have been previously reported without detailed structural data and indicate that some experimentally reported compounds may actually be unstable at low temperatures. With these results, we construct enhanced structure maps for the binary alloys of platinum-group metals. These maps are much more complete, systematic, and predictive than those based on empirical results alone.

Development of Multi-modal and Super-resolved Retinal Imaging Systems

Advancements in retinal imaging technologies have drastically improved the quality of eye care in the past couple decades. Scanning laser ophthalmoscopy (SLO) and optical coherence tomography (OCT) are two examples of critical imaging modalities for the diagnosis of retinal pathologies. However current-generation SLO and OCT systems have limitations in diagnostic capability due to the following factors: the use of bulky tabletop systems, monochromatic imaging, and resolution degradation due to ocular aberrations and diffraction.

Bulky tabletop SLO and OCT systems are incapable of imaging patients that are supine, under anesthesia, or otherwise unable to maintain the required posture and fixation. Monochromatic SLO and OCT imaging prevents the identification of various color-specific diagnostic markers visible with color fundus photography like those of neovascular age-related macular degeneration. Resolution degradation due to ocular aberrations and diffraction has prevented the imaging of photoreceptors close to the fovea without the use of adaptive optics (AO), which require bulky and expensive components that limit the potential for widespread clinical use.

In this dissertation, techniques for extending the diagnostic capability of SLO and OCT systems are developed. These techniques include design strategies for miniaturizing and combining SLO and OCT to permit multi-modal, lightweight handheld probes to extend high quality retinal imaging to pediatric eye care. In addition, a method for extending true color retinal imaging to SLO to enable high-contrast, depth-resolved, high-fidelity color fundus imaging is demonstrated using a supercontinuum light source. Finally, the development and combination of SLO with a super-resolution confocal microscopy technique known as optical photon reassignment (OPRA) is demonstrated to enable high-resolution imaging of retinal photoreceptors without the use of adaptive optics.

Nonholonomically Constrained Dynamics and Optimization of Rolling Isolation Systems

Rolling Isolation Systems provide a simple and effective means for protecting components from horizontal floor vibrations. In these systems a platform rolls on four steel balls which, in turn, rest within shallow bowls. The trajectories of the balls is uniquely determined by the horizontal and rotational velocity components of the rolling platform, and thus provides nonholonomic constraints. In general, the bowls are not parabolic, so the potential energy function of this system is not quadratic. This thesis presents the application of Gauss's Principle of Least Constraint to the modeling of rolling isolation platforms. The equations of motion are described in terms of a redundant set of constrained coordinates. Coordinate accelerations are uniquely determined at any point in time via Gauss's Principle by solving a linearly constrained quadratic minimization. In the absence of any modeled damping, the equations of motion conserve energy. This mathematical model is then used to find the bowl profile that minimizes response acceleration subject to displacement constraint.

Systematic characterization of thermodynamic and dynamical phase behavior in systems with short-ranged attraction

In this paper we demonstrate the feasibility and utility of an augmented version of the Gibbs ensemble Monte Carlo method for computing the phase behavior of systems with strong, extremely short-ranged attractions. For generic potential shapes, this approach allows for the investigation of narrower attractive widths than those previously reported. Direct comparison to previous self-consistent Ornstein-Zernike approximation calculations is made. A preliminary investigation of out-of-equilibrium behavior is also performed. Our results suggest that the recent observations of stable cluster phases in systems without long-ranged repulsions are intimately related to gas-crystal and metastable gas-liquid phase separation.

RF MIMO Systems for Wide-Area Indoor Human Motion Monitoring

Human motion monitoring is an important function in numerous applications. In this dissertation, two systems for monitoring motions of multiple human targets in wide-area indoor environments are discussed, both of which use radio frequency (RF) signals to detect, localize, and classify different types of human motion. In the first system, a coherent monostatic multiple-input multiple-output (MIMO) array is used, and a joint spatial-temporal adaptive processing method is developed to resolve micro-Doppler signatures at each location in a wide-area for motion mapping. The downranges are obtained by estimating time-delays from the targets, and the crossranges are obtained by coherently filtering array spatial signals. Motion classification is then applied to each target based on micro-Doppler analysis. In the second system, multiple noncoherent multistatic transmitters (Tx's) and receivers (Rx's) are distributed in a wide-area, and motion mapping is achieved by noncoherently combining bistatic range profiles from multiple Tx-Rx pairs. Also, motion classification is applied to each target by noncoherently combining bistatic micro-Doppler signatures from multiple Tx-Rx pairs. For both systems, simulation and real data results are shown to demonstrate the ability of the proposed methods for monitoring patient repositioning activities for pressure ulcer prevention.