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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2

Catalytic Reduction of Carbon Monoxide to Liquid Fuels with Recyclable Hydride Donors

Solar light absorption and catalysis are physically separated processes in natural photosynthesis. Natural cofactors, such as nicotinamide adenine dinucleotides (NADH), transport electrons and hydrogen to regulate and activate enzymes at remote locations. The physical separation of light absorption from catalysis provides some inspiration for artificial photosynthesis. One rather extreme implementation is to use copper wires to transport carriers from photovoltaic cells to dark electrodes, where catalysis occurs. Indeed, with a futuristic electrical grid powered solely by photovoltaics, solar capture could be separated from catalysis by hundreds of miles. An alternative approach, that bares more similarity to natural photosynthesis, employs mobile NADH/NAD + -like species that shuttle between the light absorber and a proximate, yet unilluminated, location where catalysis occurs. Additionally, such a remote approach to solar photocatalysis was recently proposed for the reduction of carbon oxides, CO 2 and CO, to methanol by cascade catalysis. This developing artificial photosynthetic approach offers the promise of catalytic generation of methanol and oxygen gas with sunlight as the sole energy source and CO 2 and water as the only chemical feedstocks. This Viewpoint evaluates the strengths and weaknesses of this approach with an emphasis on CO reduction catalysis with photorecyclable hydride donors while looking forward to what might reasonably be achieved with continued research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Shifting the MLCT of d 6 metal complexes to the red and NIR

Light-active d 6 -coordination compounds hold great promise for light energy conversion, sensors and therapeutic applications. However, the activity in the red-to-NIR spectral region is highly desirable to convert solar light more efficiently, use low-cost red-light sources and activate these chromophores in biological tissue environment. Due to their versatility, tunability and broad intense absorption, d 6 -coordination compounds with metalto-ligand charge transfer (MLCT) transitions are especially interesting. This review article offers a comprehensive collection of strategies to tune MLCT excited states in d 6 metal complexes and gives insights on group 6 to group 9 transition metals and their respective state-of-the-art MLCT engineering towards red-shifted absorption and emission properties with long-lived excited states. Strategies comprise lowering the π* level of the ligands, destabilizing and mixing of the metal-based HOMO, switching within a group of transition metals, matrix effects and insights into dealing with excited state deactivation in the context of the energy gap law.

Metal to ligand charge transfer (MLCT)↗

Spatial patterns of light-harvesting antenna complex arrangements tune the transfer-to-trap efficiency of excitons in purple bacteria.

In photosynthesis, the efficiency with which a photogenerated exciton reaches the reaction center is dictated by chromophore energies and the arrangement of chromophores in the supercomplex. Here, we explore the interplay between the arrangement of light-harvesting antennae and the efficiency of exciton transport in purple bacterial photosynthesis. Using a Miller-Abrahams-based exciton hopping model, we compare different arrangements of light-harvesting proteins on the intracytoplasmic membrane. We find that arrangements with aggregated LH1s have a higher efficiency than arrangements with randomly distributed LH1s in a wide range of physiological light fluences. This effect is robust to the introduction of defects on the intracytoplasmic membrane. Our result explains the absence of species with aggregated LH1 arrangements in low-light niches and the large increase seen in the expression of LH1 dimer complexes in high fluences. We suggest that the effect seen in our study is an adaptive strategy toward solar light fluence across different purple bacterial species.

Onizhuk, Mykyta↗

Discovery of extreme, roughly daily superflares on the recurrent nova V2487 Oph

ABSTRACT V2487 Oph is a recurrent nova with detected eruptions in 1900 and 1998. Startlingly, V2487 Oph shows flares, called ‘Superflares’, with up to 1.10 mag amplitude, fast rises of under one-minute, always with an initial impulsive spike followed by a roughly exponential tail, typically one-hour durations, and with random event times averaging once-per-day. The typical flare energy E is over 1038 erg, while the yearly energy budget is 1041 erg. V2487 Oph Superflares obey three relations; the number distribution of flare energies scales as E−2.34 ± 0.35, the waiting time from one flare to the next is proportional to E of the first event, and flare durations scale as E0.44 ± 0.03. Scenarios involving gravitational energy and nuclear energy fail to satisfy the three relations. The magnetic energy scenario, however, can explain all three relations. This scenario has magnetic field lines above the disc being twisted and amplified by the motions of their footprints, with magnetic reconnection releasing energy that comes out as Superflare light. This exact mechanism is already well known to occur in white light solar flares, in ordinary M-type flare stars, and in the many Superflare stars observed all across the H-R diagram. Superflares on Superflare stars have rise times, light-curve shapes, and durations that are very similar to those on V2487 Oph. So we conclude that the V2487 Oph Superflares are caused by large-scale magnetic reconnection. V2487 Oph is now the most extreme Superflare star, exhibiting the largest known flare energy (1.6 × 1039 erg) and the fastest occurrence rate.

Schaefer, Bradley E.↗

Platinum group metal-free (PGM-free) integrated tandem junction photoelectrochemical (PEC) water splitting devices (Final Technical Report)

This project involves using solar light, a photoabsorber, and a catalyst to split water and produce hydrogen. The Department of Energy (DOE) targets for integrated photoelectrochemical (PEC) cells emphasize cost (electrode cost < $200/m 2 ), performance (> 15% solar to hydrogen (STH) efficiency), and stability (> 6 months electrode lifetime), but most approaches skew toward one specific metric. This project exploited interfacial integration of platinum group metal-free (PGM-free) catalysts on the high performance and high value tandem solar cells to attain or exceed the DOE benchmark STH energy conversion efficiency and durability. This was investigated in two thrusts by developing two PEC devices for direct comparison: the first is a high-performance monolithic device based on state-of-the-art GaInP 2 /GaAs tandem solar cells developed at National Renewable Energy Laboratory (NREL), and the second is a high-value device based on earth-abundant wide band gap photoabsorber materials including oxynitride and hybrid organic-inorganic perovskite (HOIP) coupled with commercial narrow band gap silicon (Si). Both these devices were paired with electrocatalysts developed for this purpose at Rutgers University by adapting them to thin films on the photoabsorbers. These catalysts are based on the hydrogen evolution reaction (HER) catalysts (Ni 5 P 4 ), oxygen evolution reaction (OER) catalysts (LiCo 2 O 4 ) previously developed at Rutgers for high-efficiency electrolyzers. For using the high-performance tandem solar cell and Ni 5 P 4 catalysts, we achieved a durability of > 200 h at a STH efficiency of > 10%. For using the high-value wide band gap single junction solar cells on n + Si, we achieved 0.73 mA/cm 2 at 1.23V vs reversible hydrogen electrode (RHE) and -15.9 mA/cm 2 at 0V vs RHE using the oxynitride- and HOIP-based photoelectrodes, respectively. After comparing their photocurrent densities, we down selected the HOIP photoabsorber to couple Si for fabrication of a tandem photocathode. However, due to the COVID-19 pandemic, both the laboratories at Rutgers and NREL were locked down for three months and reopened only partially in 2020. The HOIP/Si tandem photocathode using robust nickel phosphide thin film catalysts cannot be developed within the project period, which is expected to achieve a STH efficiency of > 20%. Also, the low-cost LiCo 2 O 4 OER catalysts need to replace the benchmark IrO 2 for evaluation. Finally, techonomic analysis of full high-performance and high-value integrated PEC devices needs to be carried out for comparison in terms of cost.

08 HYDROGEN↗

Chapter 8. Hybrid Biological–Inorganic Systems for CO 2 Conversion to Fuels

The biological reduction of CO 2 into organic carbon is integral to the formation and maintenance of all life on earth. An urgent need to mitigate the effects of CO 2 on our atmosphere has provided an imperative to exploit biological CO 2 fixation for the conversion of CO2 into valuable and energy rich fuels. Photosynthesis uses only sunlight, water, and CO2 as starting materials to form all biomass.

CO2 Conversion to Fuels↗

Long-Term Degradation of Passivated Emitter and Rear Contact Silicon Solar Cell under Light and Heat

Advanced designs enable high-efficiency solar cells; however, more complex structures create new long-term stability concerns. Herein, the long-term degradation processes affecting advanced silicon solar cells using laboratory-based illumination and heating over hundreds of hours are investigated. The activation energy for the degradation of voltage is estimated and the degradation rates to normal solar cell operating temperature ranges are extrapolated. The cell degradation observed at high temperatures in the lab is kinetically similar to the process affecting field-deployed modules contributing to 0.37% year-1 of annualized degradation. Electroluminescence and photoluminescence mapping show that the degradation is dominated by minority carrier lifetime reduction. Suns-open-circuit voltage and light beam-induced current results indicate that the degradation could result from passivation degradation at the surface or defect formation in the near-subsurface region, leading to increased minority carrier recombination. This work highlights a long-term degradation process under elevated temperature and illumination that may continue to affect cells in an irreversible manner that is separate from recoverable light-induced degradation and light- and elevated temperature-induced degradation.

14 SOLAR ENERGY↗

Implantable photoelectronic charging (I-PEC) for medical implants

Medical implants with functionalities such as sensing, health monitoring, stimulation, diagnosis, and physiological treatment are rapidly growing. With the increasing functional sophistication and addition of modules such as data transmission, on-chip processing, and data storage, energy demand of the implantable system is also growing. Using implantable energy harvester either to recharge or ultimately replace hazardous battery is essential to provide a long-term sustainable solution. Furthermore, energy harvesting techniques using piezoelectric, thermoelectric, radio frequency power transmission, biofuel, and photoelectronic (or sometimes termed as “photovoltaic” in terms of solar light harvesting, i.e., PV) conversion, have been attempted for the implantable, but these methods are currently limited by insufficient power output, large footprint, and low efficiency. Nevertheless, the planar PV with potential of lighter weight, higher energy density, and higher efficiency, provides promising power solution for in-body medical implants. In this short review, we will discuss the potential opportunities and challenges associated with PV's for medical implants, covering materials, to devices, and to system level requirements.

60 APPLIED LIFE SCIENCES↗

Origin of high optical contrast in zinc-zinc oxide electrodeposits for dynamic windows

The control of solar light and heat emission through windows is an important strategy for increasing the energy efficiency of buildings. Reversible Zn electrodeposition has recently emerged as a promising method for constructing electronically tintable robust dynamic windows. In Zn electrodeposits formed from dimethyl sulfoxide (DMSO) electrolytes during device tinting, we observe extraordinary absorption that is in excess of what is predicted by the Beer-Lambert law for a uniform Zn thin film. Here, the charge required to electroplate these films is abnormally low, significantly less than previously reported dynamic windows based on reversible metal electrodeposition, which facilitates the construction of large-area devices that switch uniformly. Finite-difference time-domain (FDTD) simulations are used to investigate the origin of this enhanced absorption, which arises from plasmonic effects among the Zn nanoparticles and ZnO dendrites in the film. The dielectric ZnO dendrites promote absorption via slit-like Zn-dielectric-Zn structures that from hybrid surface plasmon resonance at metal walls. Through these investigations, we provide design principles to construct low-charge and high-contrast metal and metal oxide-based dynamic windows.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Understanding Anomalous Gas-Phase Peak Shifts in Dip-and-Pull Ambient Pressure XPS Experiments

Dip-and-pull ambient pressure X-ray photoelectron spectroscopy (AP-XPS) holds promise to uncover elementary processes of (photo)electrochemistry. We show, however, that the sample for such experiments should preferably be nonporous and the potential on the surface homogeneous. We carried out dip-and-pull AP-XPS experiments on a hematite thin film sample under the photoelectrochemical oxygen evolution reaction (OER) and find unexpected O 1s core level shifts. Upon electrochemical biasing under simulated solar light illumination, the gas-phase water peak shifted more than the electrolyte peak. To uncover the origin of the unexpected larger shift of the gas-phase peak, we performed electrostatic simulations using COMSOL, to map the potential field in the relevant volume between the sample and the first aperture of the XPS spectrometer. A number of geometric models were considered. We find that when the potential on the sample surface is inhomogeneous, e.g., with ionically isolated electrolyte patches, the gas-phase peak of the spectrum can shift more than the peak due to the electrolyte film. This suggests that at the measured sample position, the local potential was not as set by the potentiostat. Despite this, we find reversible consumption and replenishment of hydroxide in the spectra, which, due to OH– being the reactant of the OER in alkaline electrolyte, makes sense chemically. We propose that this is linked to OH– diffusion across the measured sample position, driven by the potential dependent consumption and replenishment of OH– at the nearby well-connected surface regions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoscale Confinement of Photo-Injected Electrons at Hybrid Interfaces

A prerequisite for advancing hybrid solar light harvesting systems is a comprehensive understanding of the spatiotemporal dynamics of photoinduced interfacial charge separation. Here, we demonstrate access to this transient charge redistribution for a model hybrid system of nanoporous zinc oxide (ZnO) and ruthenium bipyridyl chromophores. The site-selective probing of the molecular electron donor and semiconductor acceptor by time-resolved X-ray photoemission provides direct insight into the depth distribution of the photoinjected electrons and their interaction with the local band structure on a nanometer length scale. Our results show that these electrons remain localized within less than 6 nm from the interface, due to enhanced downward band bending by the photoinjected charge carriers. This spatial confinement suggests that light-induced charge generation and transport in nanoscale ZnO photocatalytic devices proceeds predominantly within the defect-rich surface region, which may lead to enhanced surface recombination and explain their lower performance compared to titanium dioxide (TiO 2 )-based systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Surface Terminations of 2D Bi 2 WO 6 on Photocatalytic Hydrogen Evolution from Water Splitting

Two-dimensional (2D)-structured photocatalysts with atomically thin layers not only have the potential to enhance hydrogen generation efficiency but also allow more direct investigations of the effects of surface terminations on photocatalytic activity. In this work, taking 2D Bi 2 WO 6 as a model, we found that the configuration of bilayer Bi 2 O 2 sandwiched by alternating WO 4 layers enabled the thermodynamic driving potential for photocatalytic hydrogen evolution. Without Pt deposition, the H 2 generation efficiency can reach to 56.9 μmol/g/h by 2D Bi 2 WO 6 as compared with no activity of Bi 2 WO 6 nanocrystals under simulated solar light. This configuration is easily functionalized by adsorption of Cl – /Br – to form Bi–Cl/Bi–Br bonds, which leads to the decrease of recombination in photogenerated charge carriers and narrower band gaps. This work highlights an effective way to design photocatalysts with efficient hydrogen evolution by tuning the surface terminations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cobalt Oxide-Coated Single Crystalline Bismuth Vanadate Photoanodes for Efficient Photoelectrochemical Chlorine Generation

Bismuth vanadate (BiVO 4 ) is an outstanding photoanode material for photoelectrochemical water splitting. Here in this work, a series of single crystalline BiVO 4 photoanodes are synthesized by pulsed laser deposition (PLD). Once coated with a thin layer of cobalt oxide (CoO x ) cocatalyst, also by PLD, the photoanodes support efficient photoelectrochemical generation of chlorine (Cl 2 ) from brine under simulated solar light. The activity of the chlorine generation reaction (ClER) is optimized when the thickness of CoO x is about 3 nm, with the faradic efficiency of ClER exceeding 60%. Detailed studies show that the CoO x cocatalyst layer is amorphous, uniform in thickness, and chemically robust. As such, the cocatalyst also effectively protects the underlying BiVO 4 photoanodes against chlorine corrosion. This work provides insights into using artificial photosynthesis for byproducts that carry significant economic value while avoiding the energetically expensive oxygen evolution reactions.

36 MATERIALS SCIENCE↗

Atomic Structure, Dynamics, Changes in Chemical Bonding and Semiconductor-Metal Transition in Sb 2 Se 3 : A Remarkable Material for Quantum Networks and Energy Applications

Antimony sesquiselenide has become an outstanding functional material for photovoltaics, energy storage and transformation, memory and photonic applications. Sb 2 Se 3 is one of the most successful emerging solar light absorbers and has also been identified as a highly promising ultralow-loss phase-change material (PCM) for next-generation coherent nanophotonic processors, photonic tensor cores, quantum and neuromorphic networks. Unlike benchmark telluride PCMs, Sb 2 Se 3 features a quasi-one-dimensional (1D) crystalline structure consisting of (Sb 4 Se 6 ) ∞ ribbons, lacks the typical PCM chemical bonding, and undergoes an extended semiconductor-metal transition above the melting point. Consequently, the origin of high optical contrast between crystalline (SET) and amorphous (RESET) logic states remains elusive and presents a significant challenge. Using high-energy X-ray diffraction and Raman spectroscopy over a wide temperature range, supported by first-principles simulations and complemented by thermal, optical and electrical measurements, as well as by 121 Sb-Mossbauer spectroscopy, the quasi-1D network of orthorhombic antimony sesquiselenide was found to undergo significant evolution in amorphous and supercooled Sb 2 Se 3 , leading to lower coordination, shorter interatomic distances and a higher p-electron density on antimony, indicating changes in chemical bonding. The observed novel Sb 2 Se 3 nanocrystalline polymorph, characterized by trigonal antimony coordination and more isolated Sb-Se ribbons, could help reduce multiple trapping defect states in the bandgap, which are typical of orthorhombic Sb 2 Se 3 , thereby enhancing the power-conversion efficiency of photovoltaic devices. Semimetallic and metallic liquid Sb 2 Se 3 exhibit a gradual transformation into a denser 2D and/or 3D network with higher antimony coordination. Localized electron states in the pseudogap are becoming extended, leading to an increase in electronic conductivity σ following the relationship σ ∝ N(E F ) 2 . Liquid Sb 2 Se 3 also appears to be strongly fragile, with a nonmonotonic change in viscosity and higher atomic mobility in the metallic liquid. Furthermore, these results explain extraordinary functionalities of Sb 2 Se 3 for photonic and energy applications.

antimony↗

The electric fields and “lightning jets” of the Sun and solar wind

A model of electric energization of the solar wind and corona is developed, including electro-magnetic particle effects precluded by traditional magneto-hydro (MHD) assumptions. Using standard 1D radial solar models for particle density and temperature, the core gravito-electric field is calculated; and the range of possible photospheric photo-electric fields is estimated. The extant DC field apparently arises from about 460 C of charge displacement, mainly caused by the immense solar energy flux pushing electrons outward. Energetically, this electric field can accelerate surface protons out of the 2 keV gravity well and up to the 4 keV energies observed in the fast solar wind. The electrical energy is released in pervasive, persistent “proton lightning jets,” which are proton beams, charge-neutralized by co-propagating electrons. The jets are formed by pinched “avalanche breakdown” of the weakly ionized photosphere, probably initiated on the down-welling edges of solar surface granulations. These energetic jets will glow as discrete filamentary surface spicules and will be observed in reflected solar light as the diffuse K-corona. Significantly, the total charge displacement and observed fast wind speed are quantitatively predicted by a novel “virial limit”: the (positive) electrical potential energy at r = 0 is limited in magnitude to the 10 keV gravitational well at r = 0.

Physics↗

Progress and Application of Halide Perovskite Materials for Solar Cells and Light Emitting Devices

Halide perovskite materials have attracted worldwide attention in the photovoltaic area due to the rapid improvement in efficiency, from less than 4% in 2009 to 26.1% in 2023 with only a nanometer lever photo-active layer. Meanwhile, this nova star found applications in many other areas, such as light emitting, sensor, etc. This review started with the fundamentals of physics and chemistry behind the excellent performance of halide perovskite materials for photovoltaic/light emitting and the methods for preparing them. Then, it described the basic principles for solar cells and light emitting devices. It summarized the strategies including nanotechnology to improve the performance and the application of halide perovskite materials in these two areas: from structure–property relation to how each component in the devices affects the overall performance. Moreover, this review listed the challenges for the future applications of halide perovskite materials.

36 MATERIALS SCIENCE↗

Quieting a noisy antenna reproduces photosynthetic light-harvesting spectra

Photosynthesis achieves near unity light-harvesting quantum efficiency yet it remains unknown whether there exists a fundamental organizing principle giving rise to robust light harvesting in the presence of dynamic light conditions and noisy physiological environments. Here, we present a noise-canceling network model that relates noisy physiological conditions, power conversion efficiency, and the resulting absorption spectra of photosynthetic organisms. Using light conditions in full solar exposure, light filtered by oxygenic phototrophs, and light filtered under seawater, we derived optimal absorption characteristics for efficient solar power conversion. We show how light-harvesting antennae can be tuned to maximize power conversion efficiency by minimizing excitation noise, thus providing a unified theoretical basis for the observed wavelength dependence of absorption in green plants, purple bacteria, and green sulfur bacteria.

Science & Technology - Other Topics↗