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Ardo, Shane

Publications and source records attributed to Ardo, Shane.

30 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Photoacid-Modified Nafion Membrane Morphology Determined by Resonant X-ray Scattering and Spectroscopy

Covalent attachment of photoacid dye molecules to perfluorinated sulfonic acid membranes is a promising route to enable active light-driven ion pumps, but the complex relationship between chemical modification and morphology is not well understood in this class of functional materials. In this study we demonstrate the effect of bound photoacid dyes on phase-segregated membrane morphology. Resonant X-ray scattering near the sulfur K-edge reveals that introduction of photoacid dyes to the end of the ionomer side chains enhances phase segregation among ionomer domains, and the ionomer domain spacing increases with increasing amount of bound dye. Furthermore, relative crystallinity is marginally enhanced within semicrystalline domains composed of the perfluorinated backbone. Finally, X-ray absorption spectroscopy coupled with first-principles density functional theory calculations suggest that above a critical concentration, the multiple hydrophilic groups on the attached photoacid dye may help increase residual water content and promote hydration of adjacent sulfonic acid side chains under dry or ambient conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Report of the Basic Energy Sciences Roundtable on Liquid Solar Fuels

This report is based on a BES Roundtable on Liquid Solar Fuels, which was held August 20-21, 2019. The goal of the roundtable was to identify research opportunities to overcome scientific and technical barriers in the generation of liquid solar fuels via artificial photosynthesis.

14 SOLAR ENERGY↗
DOE OSTI2019

5-Methoxyquinoline Photobasicity Is Mediated by Water Oxidation

A mechanism explaining the photobasicity of 5-methoxyquinoline (5-MeOQ) is proposed on the basis of nonadiabatic molecular dynamics simulations using time-dependent hybrid density functional theory (TDDFT) and fewest switches surface hopping (SH) and analysis of existing ultrafast spectroscopy experiments. According to the TDDFT-SH simulations, the rate-determining step is hole transfer from photoexcited 5-MeOQ to adjacent water molecules within ~5 ps followed by rapid electron-coupled proton transfer and deactivation to the ground state. This fast redox-catalyzed proton transfer mechanism is consistent with simple thermodynamic arguments, correlated wavefunction calculations, and recent isotope substitution time-resolved fluorescence experiments. Although energetically feasible, direct protonation of 5-MeOQ in the S 1 state appears to be too slow to contribute significantly to 5-MeOQ photobasicity in aqueous solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Calculations of theoretical efficiencies for electrochemically-mediated tandem solar water splitting as a function of bandgap energies and redox shuttle potential

Tandem Z-scheme solar water splitting devices composed of two light-absorbers that are connected electrochemically by a soluble redox shuttle constitute a promising technology for cost-effective solar hydrogen production. In this work, efficiency limits of these devices are modeled by combining the detailed-balance model of the light-absorbers with Butler–Volmer electron-transfer kinetics. The impacts of the redox shuttle thermodynamic potential, light-absorber bandgaps, and electrocatalytic parameters on the solar-to-hydrogen conversion (STH) efficiency are modeled. We report that the thermodynamic potential of the redox shuttle with respect to the hydrogen and oxygen evolution potentials has a direct effect on both the STH efficiency and the optimal tandem light-absorber bandgaps needed to achieve the maximum possible STH efficiency. At 1 sun illumination and assuming ideal and optimally selective electrocatalytic parameters, the STH efficiency varies from a minimum of 21%, for a redox shuttle potential of 0 V vs. the reversible hydrogen electrode (RHE), to a maximum of 34%, for a redox shuttle potential of either 0.36 V or 1.06 V vs. RHE. To attain the maximum possible STH efficiency of 34%, the light-absorber bandgaps must be 1.53 eV and 0.75 eV, yet the optimal redox shuttle potential depends on whether the hydrogen-evolving or oxygen-evolving light-absorber has the larger bandgap. Results also underscore the importance of optimizing the absorptance of the top light-absorber, which enables large STH efficiencies to be achieved with a wider range of bandgap combinations. Moreover, given the large overpotentials for the oxygen evolution reaction and reasonably low overpotentials for most redox shuttle reactions, the tandem design is more efficient than a single light-absorber design even when the potential of the redox shuttle exceeds 1.23 V vs. RHE. When the exchange current density of the redox shuttle reactions is as low as 10 -5 mA cm -2 , STH efficiencies as large as 22% are still achievable as long as selective catalysis and optimal redox shuttle potential are assumed, suggesting that even slow redox shuttle reactions may not limit the practicality of these devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Curtailing Perovskite Processing Limitations via Lamination at the Perovskite/Perovskite Interface

Standard layer-by-layer solution processing methods constrain lead-halide perovskite device architectures. The layer below the perovskite must be robust to the strong organic solvents used to form the perovskite while the layer above has a limited thermal budget and must be processed in nonpolar solvents to prevent perovskite degradation. To circumvent these limitations, we developed a procedure where two transparent conductive oxide/transport material/perovskite half stacks are independently fabricated and then laminated together at the perovskite/perovskite interface. Using ultraviolet-visible absorption spectroscopy, external quantum efficiency, X-ray diffraction, and time-resolved photoluminesence spectroscopy, we show that this procedure improves photovoltaic properties of the perovskite layer. Applying this procedure, semitransparent devices employing two high-temperature oxide transport layers were fabricated, which realized an average efficiency of 9.6% (maximum: 10.6%) despite series resistance limitations from the substrate design. Overall, the developed lamination procedure curtails processing constraints, enables new device designs, and affords new opportunities for optimization.

14 SOLAR ENERGY↗
DOE OSTI2018

Pathways to electrochemical solar-hydrogen technologies

Solar-powered electrochemical production of hydrogen through water electrolysis is an active and important research endeavor. However, technologies and roadmaps for implementation of this process do not exist. In this perspective paper, we describe potential pathways for solar-hydrogen technologies into the marketplace in the form of photoelectrochemical or photovoltaic-driven electrolysis devices and systems. We detail technical approaches for device and system architectures, economic drivers, societal perceptions, political impacts, technological challenges, and research opportunities. Implementation scenarios are broken down into short-term and long-term markets, and a specific technology roadmap is defined. In the short term, the only plausible economical option will be photovoltaic-driven electrolysis systems for niche applications. In the long term, electrochemical solar-hydrogen technologies could be deployed more broadly in energy markets but will require advances in the technology, significant cost reductions, and/or policy changes. Ultimately, a transition to a society that significantly relies on solar-hydrogen technologies will benefit from continued creativity and influence from the scientific community.

14 SOLAR ENERGY↗
DOE OSTI2017

Evaluating particle-suspension reactor designs for Z-scheme solar water splitting via transport and kinetic modeling

Sunlight-driven water splitting to produce hydrogen and oxygen provides a pathway to store available solar energy in the form of stable, energy-dense chemical bonds. Here we investigate a tandem particle-suspension reactor design for solar water splitting comprising micron-scale photocatalyst particles suspended in an aqueous solution with soluble redox shuttles. A porous separator facilitates redox species transport between the hydrogen and oxygen evolution reaction compartments while averting gas crossover. A two-dimensional, transient model of the reactor is presented to illustrate the coupling between light absorption, interfacial electron-transfer kinetics and species transport, and their combined impacts on overall solar-to-hydrogen conversion efficiency. The volumetric reactivity of the suspended semiconductor particles is dictated by combining the (photo)current-voltage behavior of a photodiode with Butler-Volmer electron-transfer kinetics. For the first time, a quantitative approach to determine the impacts of surface-dependent redox shuttle kinetic parameters on reaction selectivity in a Z-scheme system is established. Model results provide insights on the effects of optical, transport and kinetic properties of the semiconductor particles and the redox shuttles on the overall reactor performance. Solar-to-hydrogen reactor efficiencies predicted with BiVO 4 particles for oxygen evolution are at least two times larger than efficiencies achieved with wider band-gap TiO 2 particles due to enhanced visible light absorption; hydrogen evolution with SrTiO 3 :Rh particles was considered for both cases. Superior performance is predicted with proton-coupled electron transfer redox shuttles (para-benzoquinone/hydroquinone and iodide/iodate) that absorb little-to-no visible light, while also facilitating operation at near-neutral pH conditions, as compared to the non-proton-coupled triiodide/iodide and iron(iii)/iron(ii) redox shuttles. For 1 cm tall reaction compartments, diffusive species transport is fast enough to sustain reactor operation at a 1% solar-to-hydrogen conversion efficiency for both para-benzoquinone/hydroquinone and iodate/iodide redox shuttles with less than 2.2 mg L -1 of each of BiVO 4 and SrTiO 3 :Rh particles in the solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Modellierung, Simulation und Implementierung von Zellen für die solargetriebene Wasserspaltung

Abstract Eine integrierte Zelle für die solargetriebene Wasserspaltung besteht aus mehreren funktionellen Komponenten und kombiniert verschiedene photoelektrochemische (PEC‐)Prozesse auf unterschiedlichen Längen‐ und Zeitskalen. Der Gesamtwirkungsgrad eines derartigen Systems für die Umwandlung von Solarenergie in Wasserstoff (solar‐to‐hydrogen; STH) wird von der Leistung und den Materialeigenschaften seiner Einzelkomponenten sowie ihrer Integration, von seiner Gesamtarchitektur und den Betriebsbedingungen bestimmt. Dieser Aufsatz beschäftigt sich mit der Implementierung von solargetriebenen Prototypen für die Wasserspaltung auf der Basis von Modellierungen und Simulationen, welche die Wechselwirkungen zwischen den Einzelbauteilen in ihrer Gesamtheit berücksichtigen. Physik und Wechselwirkungen innerhalb der Zelle werden diskutiert, und die Anwendung des Zellmodells für die Bestimmung der benötigten Materialeigenschaften sowie beim Design von herkömmlichen und ungewöhnlichen Architekturen wird erörtert.

Xiang, Chengxiang↗
DOE OSTI2016

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.

14 SOLAR ENERGY↗