Robert H. Coridan

Methods for comparing the performance of energy-conversion systems for use in solar fuels and solar electricity generation

The energy-conversion efficiency is a key metric that facilitates comparison of the performance of various approaches to solar energy conversion. However, a suite of disparate methodologies has been proposed and used historically to evaluate the efficiency of systems that produce fuels, either directly or indirectly, with sunlight and/or electrical power as the system inputs. A general expression for the system efficiency is given as the ratio of the total output power (electrical plus chemical) divided by the total input power (electrical plus solar). The solar-to-hydrogen (STH) efficiency follows from this globally applicable system efficiency but only is applicable in the special case for systems in which the only input power is sunlight and the only output power is in the form of hydrogen fuel derived from solar-driven water splitting. Herein, system-level efficiencies, beyond the STH efficiency, as well as component-level figures of merit are defined and discussed to describe the relative energy-conversion performance of key photoactive components of complete systems. These figures of merit facilitate the comparison of electrode materials and interfaces without conflating their fundamental properties with the engineering of the cell setup. The resulting information about the components can then be used in conjunction with a graphical circuit analysis formalism to obtain “optimal” system efficiencies that can be compared between various approaches. The approach provides a consistent method for comparison of the performance at the system and component levels of various technologies that produce fuels and/or electricity from sunlight.

Photoelectrochemistry of core–shell tandem junction n–p^+-Si/n-WO_3 microwire array photoelectrodes

Tandem junction (n–p^+-Si/ITO/WO_3/liquid) core–shell microwire devices for solar-driven water splitting have been designed, fabricated and investigated photoelectrochemically. The tandem devices exhibited open-circuit potentials of E_(∝) = −1.21 V versus E^0′(O_2/H_2O), demonstrating additive voltages across the individual junctions (n–p^+-Si E_(∝) = −0.5 V versus solution; WO_3/liquid E_(∝) = −0.73 V versus E^0′(O_2/H_2O)). Optical concentration (12×, AM1.5D) shifted the open-circuit potential to E_(∝) = −1.27 V versus E^0′(O_2/H_2O) and resulted in unassisted H_2 production during two-electrode measurements (anode: tandem device, cathode: Pt disc). The solar energy-conversion efficiencies were very low, 0.0068% and 0.0019% when the cathode compartment was saturated with Ar or H_2, respectively, due to the non-optimal photovoltage and band-gap of the WO_3 that was used in the demonstration system to obtain stability of all of the system components under common operating conditions while also insuring product separation for safety purposes.

Photoelectrochemical behavior of hierarchically structured Si/WO3 core-shell tandem photoanodes.

WO3 thin films have been deposited in a hierarchically structured core-shell morphology, with the cores consisting of an array of Si microwires and the shells consisting of a controlled morphology WO3 layer. Porosity was introduced into the WO3 outer shell by using a self-assembled microsphere colloidal crystal as a mask during the deposition of the WO3 shell. Compared to conformal, unstructured WO3 shells on Si microwires, the hierarchically structured core-shell photoanodes exhibited enhanced near-visible spectral response behavior, due to increased light absorption and reduced distances over which photogenerated carriers were collected. The use of structured substrates also improved the growth rate of microsphere-based colloidal crystals and suggests strategies for the use of colloidal materials in large-scale applications.

Modeling, Simulation, and Implementation of Solar-Driven Water-Splitting Devices.

An integrated cell for the solar-driven splitting of water consists of multiple functional components and couples various photoelectrochemical (PEC) processes at different length and time scales. The overall solar-to-hydrogen (STH) conversion efficiency of such a system depends on the performance and materials properties of the individual components as well as on the component integration, overall device architecture, and system operating conditions. This Review focuses on the modeling- and simulation-guided development and implementation of solar-driven water-splitting prototypes from a holistic viewpoint that explores the various interplays between the components. The underlying physics and interactions at the cell level is are reviewed and discussed, followed by an overview of the use of the cell model to provide target properties of materials and guide the design of a range of traditional and unique device architectures.

Photoelectrochemical oxidation of anions by WO3 in aqueous and nonaqueous electrolytes

The behavior of WO3 photoanodes has been investigated in contact with a combination of four anions (Cl−, CH3SO3−, HSO4−, and ClO4−) and three solvents (water, acetonitrile, and propylene carbonate), to elucidate the role of the semiconductor surface, the electrolyte, and redox kinetics on the current density vs. potential properties of n-type WO3. In 1.0 M aqueous strong acids, although the flat-band potential (Efb) of WO3 was dominated by electrochemical intercalation of protons into WO3, the nature of the electrolyte influenced the onset potential (Eon) of the anodic photocurrent. In aprotic solvents, the electrolyte anion shifted both Efb and Eon, but did not significantly alter the overall profile of the voltammetric data. For 0.50 M tetra(n-butyl)ammonium perchlorate in propylene carbonate, the internal quantum yield exceeded unity at excitation wavelengths of 300–390 nm, indicative of current doubling. A regenerative photoelectrochemical cell based on the reversible redox couple B10Br10˙−/2− in acetonitrile, with a solution potential of ∼1.7 V vs. the normal hydrogen electrode, exhibited an open-circuit photovoltage of 1.32 V under 100 mW cm−2 of simulated Air Mass 1.5 global illumination.

Direct photolithographic patterning of cuprous oxide thin films via photoelectrodeposition

External fields can be used to regulate the morphological and chemical properties of electrochemically synthesized materials. One example is phototropism, where the coaction of light absorption and carrier generation can induce controllable variations in the material as it grows under illumination. Here we describe the photoelectrodeposition of photocathodic cuprous oxide (Cu2O). Illuminating the growing film with photon energies in excess of the band gap of Cu2O results in nanoscale morphological changes in the structure of thin films and intrinsically dopes the material during growth. The result is a ‘black’ Cu2O film that is chemically distinct but crystallographically identical to an ordinary film grown in the dark. The flat band potential of the film is controlled by the growth illumination intensity and the photodoping is reversible under thermal oxidation. We explore the nature of the intrinsic dopant, the emergence of nanocrystalline Cu metal inclusions in the Cu2O matrix, and the potential of for this effect to be used in the fabrication of new semiconductor heterostructures. This chemical distinction between the native and black Cu2O can be exploited to pattern films with a photomask as an example of direct photolithography.