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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Tantalum oxide stabilized molybdenum-doped ruthenium oxide electrocatalysts for PEM water electrolysis

Proton exchange membrane (PEM) water electrolysis offers key advantages, including high current density, high efficiency, and compact system architecture for hydrogen production. However, its widespread implementation is limited by the scarcity and high cost of Ir-based anodic catalysts. Herein, we report an Ir-free electrocatalyst for the acidic oxygen evolution reaction (OER): tantalum oxide (TaO x )–coated molybdenum-doped RuO 2 (TaO x -MoRuO 2 ). The catalyst exhibits a low overpotential of 180 mV at 10 mA cm -2 and excellent durability, with a degradation rate of 0.034 mV h -1 over a 150-hour test at 50 mA cm -2 —surpassing other Ru-based catalysts evaluated under similar conditions. A PEM electrolyzer employing TaO x -MoRuO 2 as the anode maintained stable operation for 100 hours at 500 mA cm -2 . In conclusion, the TaO x coating layer suppresses Ru and Mo dissolution, thus enhancing their stability likely via interfacial electronic reconfiguration of Ru and Mo mediated by bridging oxygen atoms.

Durability↗
DOE OSTI2023

Proton-Conducting Solid Oxide Electrolysis Cells for Large-scale Hydrogen Production at Intermediate Temperatures

Proton-conducting electrolyte based SOECs offer potential for operation at low to intermediate temperatures. Although yttrium-doped barium zirconate (BZY) and ceria-doped barium zirconate (BCY) have conductivity of 0.01 and 0.017 S.cm -1 respectively at 650C in comparison to the conductivity of 0.015 S.cm -1 for 8-YSZ at 850°C, there remains technology gaps and research needs related to understanding of chemical and structural stability in oxidizing and/or reducing atmospheres at intermediate temperatures, material processing and densification techniques, high polarization losses, and electrode poisoning due to intrinsic and extrinsic gas phase contaminants. Synthesis methods have produced proton-conducting materials and cells that met degradation rate targets, showcasing stable hydrogen production. Improved performance was evident in the HSOEC cell, achieving higher hydrogen production at a lower operating temperature compared to standard cells. Collaborations with multiple research facilities ensured scaling up of synthesis processes and milestone achievements for large-scale manufacturing. Assessment of contaminants revealed their adverse effects on electrode performance and structural stability. Contaminants like Cr and Si compounds, in high humidity, degraded electrodes by forming stable silicate and chromates, inhibiting active surface reactions. Getter materials showed promise in capturing contaminants, suggesting potential for mitigation.

08 HYDROGEN↗
DOE OSTI2024

Revealing the role of redox reaction selectivity and mass transfer in current–voltage predictions for ensembles of photocatalysts

Photocatalysts are conceptually simple reaction units where nanoscale semiconductors integrated with catalysts drive a pair of redox reactions on illumination. However, the proximity of reaction sites performing cathodic and anodic reactions poses dire challenges to realize large light-to-fuel conversion efficiencies. In this study, a powerful, yet straightforward, equivalent-circuit detail-balance modeling framework is developed and applied to evaluate the performance of photocatalytic systems featuring multiple light absorbers. Specifically, low bandgap iridium-doped strontium titanate is modeled as a Z-scheme photocatalyst to achieve desirable hydrogen evolution and iron-based redox shuttle oxidation reactions. Our model has unique capabilities to simulate competing redox reactions and address mass-transfer limitations. In a significant departure from state-of-the-art circuit models, our study develops tools to perform load-line analyses by incorporating a net electrochemical load curve that includes both desired and competing redox reactions. Consequently, reaction selectivity is predicted from equivalent circuit models for photocatalytic and photoelectrochemical systems. Our investigation into ensembles comprised of multiple, semi-transparent light absorbers reveals their potential to outperform a single, optically thick light absorber, particularly when operated under mass-transfer-limited conditions. However, this outcome hinges on minimizing mass-transfer rates of select redox species to prevent undesired reactions of hydrogen oxidation and/or redox shuttle reduction. Our findings demonstrate that reaction selectivity can be achieved by tuning asymmetry in redox species mass-transfer even with perfectly symmetric electrocatalytic charge-transfer coefficients. The influences of various kinetic, mass-transfer, and thermodynamic parameters are explored to offer crucial insights for synthesis of the next-generation of photocatalysts and selective coatings, and reactor designs.

25 ENERGY STORAGE↗
DOE OSTI2024

Temperature Distribution Within an Ignition Kernel Initiated by a Laser-Induced Plasma

The sizes of, and temperature distributions within, ignition kernels initiated by a Q-switched neodymium-doped yttrium aluminum garnet laser-induced plasma in an unconfined lean premixed hydrogen-air upward jet flow are investigated. The experiments involved a range of jet velocities and a range of deposited laser energies at a fixed height above the exit along the axis of a burner. The growth of, and the temperature distributions within, the ignition kernels, as affected by the size and the energy distribution of the laser-induced plasma, are monitored with an infrared camera. The initial ignition kernels’ areas are larger with higher laser pulse energies and remain unchanged up to [Formula: see text] and then increase by factors of up to 3 at [Formula: see text]. The change in the kernel area caused by the jet velocities is less than 1.5%. An increase of the bulk velocity by 190% decreases the ignition kernel temperature by 6%. This reduction in the ignition kernel temperatures is because of an increase in energy losses by a factor of 2 and decreases in heat releases by 2% at [Formula: see text] and by 11% at [Formula: see text]. The present contributions are: measurements of and insights into temperature distributions and kernel development rates during the laser-induced plasma ignition process at different deposited energies and flow velocities.

Engineering↗
NASA NTRS2016

Planar Field Emitters and High Efficiency Photocathodes Based on Ultrananocrystalline Diamond

A method of forming a field emitter comprises disposing a first layer on a substrate. The first layer is seeded with nanodiamond particles. The substrate with the first layer disposed thereon is maintained at a first temperature and a first pressure in a mixture of gases which includes nitrogen. The first layer is exposed to a microwave plasma to form a nitrogen doped ultrananocrystalline diamond film on the first layer, which has a percentage of nitrogen in the range of about 0.05 atom % to about 0.5 atom %. The field emitter has about 10.sup.12 to about 10.sup.14 emitting sites per cm.sup.2. A photocathode can also be formed similarly by forming a nitrogen doped ultrananocrystalline diamond film on a substrate similar to the field emitter, and then hydrogen terminating the film. The photocathode is responsive to near ultraviolet light as well as to visible light.

Sumant, Anirudha V.↗
NASA NTRS2004

Hydrogen Passivation of Interstitial Zn Defects in Heteroepitaxial InP Cell Structures and Influence on Device Characteristics

Hydrogen passivation of heteroepitaxial InP solar cells is of recent interest for deactivation of dislocations and other defects caused by the cell/substrate lattice mismatch that currently limit the photovoltaic performance of these devices. In this paper we present strong evidence that, in addition to direct hydrogen-dislocation interactions, hydrogen forms complexes with the high concentration of interstitial Zn defects present within the p(+) Zn-doped emitter of MOCVD-grown heteroepitaxial InP devices, resulting in a dramatic increase of the forward bias turn-on voltage by as much as 280 mV, from ~680 mV to ~960 mV. This shift is reproducible and thermally reversible and no such effect is observed for either n(+)p structures or homoepitaxial p(+)n structures grown under identical conditions. A combination of photoluminescence (PL), electrochemical C-V dopant profiling, SIMS and I-V measurements were performed on a set of samples having undergone a matrix of hydrogenation and post-hydrogenation annealing conditions to investigate the source of this voltage enhancement and confirm the expected role of interstitial Zn and hydrogen. A precise correlation between all measurements is demonstrated which indicates that Zn interstitials within the p(+) emitter and their interaction with hydrogen are indeed responsible for this device behavior.

Ringel, S. A.↗
DOE OSTI2023

Isotope effect in formaldehyde steam reforming on Pt/m-ZrO 2 : Insight into chemical promotion by alkalis

Infrared spectroscopy, temperature programmed reaction mass spectrometry (TP-reaction/MS), and catalyst testing were used to investigate alkali promotion of dehydrogenation selectivity during formaldehyde steam reforming (FSR) on Pt/m-ZrO 2 . In a preferred pathway, formaldehyde reacts with water forming hydrogen and formate, followed by forward formate decomposition to CO 2 and H 2 . Alkali-doping of 2 wt% Pt/m-ZrO 2 increases catalyst basicity, which weakens the formate C-H bond promoting formate dehydrogenation / decarboxylation. Promotion by alkali in FSR was observed through a formate nu(CH) band shift to lower wavenumbers in infrared spectroscopy, and through a decrease in the normal isotope effect in switching from H-to D-labeled formalde-hyde in TP-reaction/MS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Physi-sorption of H 2 on pure and boron-doped graphene monolayers: A dispersion-corrected DFT study

Carbon based materials are of interest as potential candidates for H 2 storage. Earlier work has been inconclusive on the effect of boron doping on the energy of H 2 binding. However, earlier work has been inconclusive on the definitive effect of boron doping on the energy of H 2 binding, i.e. isosteric heats of adsorption (Qst). In this work, we completed a systematic DFT study to evaluate this effect, and found that doping graphene with boron provides only minor enhancement in H 2 binding. More importantly, the presence of the electron deficient boron into a graphene ring introduces a defect, such as terminal hydrogen or distortion from planarity, which creates hydrogen adsorption sites with slightly increased Qst. The increase is from ~ 5 kJ/mol H 2 for the pure carbon matrix to ~6 - 7 kJ/mol for the boron doped system. The more strongly bond H 2 is located near the defect and shows little direct interaction with the boron. Most significant enhancement is found in systems where H 2 is confined between layers at a distance of about 7Å. In this case, the H 2 binding nearly doubles, to ~10 kJ/mol for both pure, undistorted graphene, and the 2% boron doped system, containing tetrahedral C atom distortion. Interestingly, at higher doping levels of boron, we found that the Qst decreases compared to the all carbon materials. These finding suggest that interplanar nanoconfinement may be more effective way to enhance H 2 binding than boron doping.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2011

Fabrication method for a room temperature hydrogen sensor

A sensor for selectively determining the presence and measuring the amount of hydrogen in the vicinity of the sensor. The sensor comprises a MEMS device coated with a nanostructured thin film of indium oxide doped tin oxide with an over layer of nanostructured barium cerate with platinum catalyst nanoparticles. Initial exposure to a UV light source, at room temperature, causes burning of organic residues present on the sensor surface and provides a clean surface for sensing hydrogen at room temperature. A giant room temperature hydrogen sensitivity is observed after making the UV source off. The hydrogen sensor of the invention can be usefully employed for the detection of hydrogen in an environment susceptible to the incursion or generation of hydrogen and may be conveniently used at room temperature.

Seal, Sudipta↗
DOE OSTI2023

Visualizing Overall Water Splitting on Single Microcrystals of Phosphorus-Doped BiVO 4 by Photo-SECM

Particulate bismuth vanadate (BiVO4) has attracted considerable interest as a promising photo(electro)catalyst for visible-light-driven water oxidation, however, overall water splitting (OWS) has been difficult to attain because its conduction band is too positive for efficient hydrogen evolution. Using photo-scanning electrochemical microscopy (photo-SECM) with a chemically modified nanotip, we visualized for the first time the OWS at a single truncated bipyramidal microcrystal of phosphorus-doped BiVO 4 . The tip simultaneously served as a light guide to illuminate the photocatalyst and as an electrochemical nanoprobe to observe and quantitatively measure local oxygen and hydrogen fluxes. The obtained current patterns for both O 2 and H 2 agree well with the accumulation of photogenerated holes and electrons on {010} basal and {110} lateral facets, respectively. Furthermore, the developed experimental approach is an important step towards nanoelectrochemical mapping of the activity of photocatalyst particles at the sub-facet level.

bismuth vanadate↗
DOE OSTI2025

Radiolytic Production of Radical Species in Gibbsite Doped with Iron and Chromium Ions

Gibbsite (aluminum hydroxide, Al(OH) 3 ) nanoparticles, synthesized from aluminum chloride or aluminum nitrate, were doped with metal ions, Cr(III) or Fe(III), and then irradiated with γ rays to determine the effect of the dopants on radiolytic hydrogen (H 2 ) production and radical generation. The addition of Cr(III) and Fe(III) ions at concentrations of 0.5% or 5% decreased the concentration of stable oxygen-centered radicals, with the strongest suppression in Cr(III) doped samples. A decrease in H 2 yields was observed with increasing Cr(III) or Fe(III) concentrations, with the greatest effect observed for the Fe(III)-doped samples. Reduction of the Cr(III) to Cr(II) and Fe(III) to Fe(II) was also observed, probably due to scavenging of radiolytically produced electrons. However, further processes differ for Fe(III)- and Cr(III)-doped systems. Both ions are reduced by the free electrons, leading to a decrease in H 2 production, but they react differently with the oxygen radicals. Cr(III) can be oxidized by oxygen radicals, whereas Fe(III) cannot. Fe(II) can interact with peroxides, possible products of intermediate oxygen oxidation, converting back to Fe(III) and leaving oxygen radicals behind. These oxidation reactions lead to a difference in the observed relative effects on H 2 yields and oxygen radical production between Cr(III)- and Fe(III)-doped gibbsite. In conclusion, the connection between electron scavenging and H 2 production indicates that radiolytically produced electrons are precursors to H 2 .

Anions↗
DOE OSTI2022

Reverse water-gas shift: Na doping of m-ZrO 2 supported Pt for selectivity control

Reverse water-gas shift (RWGS) is a vital step in producing syngas for the chemical conversion of CO 2 to liquid transportation fuels and chemicals. Na-doping of m-ZrO 2 supported Pt catalysts allowed selectivity control by systematically increasing the ratio of relative rates of r CO /r CH4 . This was achieved by facilitating the formation of formate intermediate species, which precedes CO formation, and by suppressing the metallic Pt 0 active sites responsible for CH 4 formation. Here, a 2.5%Na-2%Pt/m-ZrO 2 catalyst was first tested for the forward water-gas shift (FWGS) reaction and found to have 50% higher CO conversion at 285°C compared to the undoped catalyst. Results of DRIFTS spectroscopy of adsorbed CO confirmed a formate ν(CH) band shift to lower wavenumbers (2870–2802 cm —1 ) with the addition of Na and more rapid forward formate decomposition in steam to H 2 and carbonate species, the precursor to CO 2 . This is consistent with C-H bond breaking being the rate limiting step of a FWGS mechanism occurring at the metal-support junction. Consistent with this, DRIFTS of RWGS in 4%CO 2 + 60%H 2 showed more facile formation of formate for the Na-doped catalyst and, once again, the ν(CH) band was shifted to lower wavenumbers (2874–2803 cm —1 ) with Na-doping. In addition, Na doping resulted in a systematic decrease in the Pt-carbonyl band in DRIFTS of adsorbed CO as well as DRIFTS of in-situ RWGS reaction tests, suggesting that Na blocked a fraction of on-top Pt sites, breaking up ensembles of Pt 0 responsible for methanation. The selectivity of the 2.5%Na-doped catalyst, unlike its undoped counterpart, was remarkably resistant to methanation (e.g., selectivity < 0.2% CH 4 with pressures of up to 20 bar).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Local p‐ and n‐Type Doping of an Oxide Semiconductor via Electric‐Field‐Driven Defect Migration

Layered oxides exhibit high ionic mobility and chemical flexibility, attracting interest as cathode materials for lithium-ion batteries and the pairing of hydrogen production and carbon capture. Recently, layered oxides emerged as highly tunable semiconductors. For example, by introducing anti-Frenkel defects, the electronic hopping conductance in hexagonal manganites is increased locally by orders of magnitude. Here, local acceptor and donor doping in Er(Mn,Ti)O3 is demonstrated, facilitated by the controlled splitting of anti-Frenkel defects under applied d.c. voltage. By combining density functional theory calculations, scanning probe microscopy, atom probe tomography, and scanning transmission electron microscopy, it is shown that the oxygen defects can readily be moved through the layered crystal structure, leading to nano-sized interstitial-rich (p-type) and vacancy-rich (n-type) regions. The resulting pattern is comparable to dipolar npn-junctions and stable on the timescale of days. These findings reveal the possibility of temporarily functionalizing oxide semiconductors at the nanoscale, giving additional opportunities for the field of oxide electronics and the development of transient electronics in general.

He, Jiali↗
DOE OSTI2020

Oxygen Affinity: The Missing Link Enabling Prediction of Proton Conductivities in Doped Barium Zirconates

Proton-conducting oxides, specifically doped barium zirconates, have garnered much attention as electrolytes for solid-state electrochemical devices operable at intermediate temperatures (400–600 °C). In chemical terms, hydration energy, E hyd , and proton–dopant association energy, E as , are two key parameters that determine whether an oxide exhibits fast proton conduction, but to date ab initio studies have for the most part studied each parameter separately, with no clear correlation with proton conductivity identified in either case. Here, we demonstrate that the oxygen affinity, E O.dopant , defined as the energy released when an oxide ion enters an oxygen vacancy close to a dopant atom, is the missing link between these two parameters and correlates well with experimental proton conductivities in doped barium zirconates. Ab initio calculations of point defects and their complexes in Sc-, In-, Lu-, Er-, Y-, Gd-, and Eu-doped barium zirconates are used to determine E hyd , E as , E O.dopant , and the hydrogen affinity, E H.host , of each system. These four energy terms are related by E hyd = E O.dopant + 2E H.host + 2E as . Complementary impedance spectroscopy measurements reveal that the stronger the calculated oxygen affinity of a system, the higher the proton conductivity at 350 °C. Although the proton trapping site is also an important factor, the results show that oxygen affinity is an excellent predictor of proton conductivity in these materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

Critical behavior in the hydrogen insulator-metal transition

The vibrational Raman spectrum of solid hydrogen has been measured from 77 to 295 K in the vicinity of the recently observed insulator-metal transition and low-temperature phase transition at 150 gigapascals. The measurements provide evidence for a critical point in the pressure-temperature phase boundary of the low-temperature transition. The result suggests that below the critical temperature the insulator-metal transition changes from continuous to discontinuous, consistent with the general criteria originally proposed by Mott (1949) for metallization by band-gap closure. The effect of temperature on hydrogen metallization closely resembles that of the lower-pressure insulator-metal transitions in doped V2O3 alloys.

Hemley, R. J.↗
DOE OSTI2022

Corrosion of U233-Doped Uranium Oxide using Microfluidics Methods

The aim of work this year has been to investigate the role of alpha (α)-radiation and hydrogen (H 2 ) on the corrosion of uranium oxide (UO 2 ) using a microfluidic device. The microfluidic device, termed the Particle-Attached Microfluidic Electrochemical Cell, (PAMEC), enables monitoring of the UO 2 electrochemical corrosion potential (E corr ) under different environments, including de-aerated conditions and in the presence of dissolved H 2 . The Si 3 N 4 window allows us to study morphological and chemical changes under an electron microscope. We have previously demonstrated that the PAMEC matches the results from bulk electrochemical tests with UO 2 [1]. We used the high specific activity uranium (U) isotope, 233 U, (t 1/2 = 160,000 years) incorporated into UO 2 , to generate a localized a-field. The objective of the experiments were to mimic the radiation environment that would be experience at the surface of aged spent nuclear fuel (SNF) during long-term geologic disposal under anoxic conditions. Wittman et al. [2] predicted that in the presence of a pure a-radiation field and under H 2 conditions, the concentration of the radiolytic oxidant H 2 O 2 would be suppressed or even eliminated. In a UO 2 corrosion experiment this would be exhibited through a lowering of the measured UO 2 corrosion potential compared to identical conditions in the absence of dissolved H 2 . We found that the predictions of Wittman and co-workers were supported and that the corrosion potential of the 233 U-doped UO 2 in solution lowered with presence of H 2 gas and increased in the absence of H 2 , when under anoxic conditions. The PAMEC experiments indicate that H 2 O 2 has been eliminated in a solution sparged with H 2 while exposed to an a-radiation field. The corrosion potential of the a-doped 233 U(10%)- 238 UO 2 in a solution sparged with Ar/H 2 matched the corrosion potential of 238 UO 2 in solution sparged with air. This clearly demonstrated that the H 2 O 2 had been eliminated and that the only oxidant present was O 2 in this system in complete agreement with the modeling results of Wittman et al. These results point to the need to improve the Fuel Matrix Degradation (FMD) Process Model training data set that is being used in the FMD surrogate model that is being developed for the repository program. The incorporation of realistic radiation chemistry will improve the scientific basis for the FMD Model.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Photothermal alternative to device fabrication using atomic precision advanced manufacturing techniques

The attachment of dopant precursor molecules to depassivated areas of hydrogen-terminated silicon templated with a scanning tunneling microscope (STM) has been used to create electronic devices with subnanometer precision, typically for quantum physics experiments. This process, which we call atomic precision advanced manufacturing (APAM), dopes silicon beyond the solid-solubility limit and produces electrical and optical characteristics that may also be useful for microelectronic and plasmonic applications. However, scanned probe lithography lacks the throughput required to develop more sophisticated applications. In this work, we demonstrate and characterize an APAM device workflow where scanned probe lithography of the atomic layer resist has been replaced by photolithography. An ultraviolet laser is shown to locally and controllably heat silicon above the temperature required for hydrogen depassivation on a nanosecond timescale, a process resistant to under- and overexposure. STM images indicate a narrow range of energy density where the surface is both depassivated and undamaged. Modeling that accounts for photothermal heating and the subsequent hydrogen desorption kinetics suggests that the silicon surface temperatures reached in our patterning process exceed those required for hydrogen removal in temperature-programmed desorption experiments. A phosphorus-doped van der Pauw structure made by sequentially photodepassivating a predefined area and then exposing it to phosphine is found to have a similar mobility and higher carrier density compared with devices patterned by STM. Lastly, it is also demonstrated that photodepassivation and precursor exposure steps may be performed concomitantly, a potential route to enabling APAM outside of ultrahigh vacuum.

nanoscale devices↗
DOE OSTI2021

On the design and performance of InGaN/Si double-junction photocathodes

Via a combined theoretical and experimental study, we have investigated the synthesis and performance characteristics of InGaN/Si double-junction photoelectrochemical (PEC) water splitting devices, which promise a theoretical solar-to-hydrogen conversion efficiency ~30% under AM 1.5G one-sun illumination. The double-junction photocathodes consist of a p + -InGaN top light absorber and a Si bottom p-n junction, which are connected through a nanowire tunnel junction. The effect of indium composition of the top light absorber as well as the impact of p-type Mg dopant incorporation on the PEC performance was studied. Experimentally, the sample with 32% indium composition showed a maximum photocurrent density of ~9 mA/cm 2 at 0.4 mV vs reverse hydrogen electrode (RHE) with applied bias photon-to-current efficiency (ABPE) of ~9.5%. An optimum p-type doping level ~1 × 10 17 cm -3 was also identified, which results in the best device performance as a result of optimum surface band bending as well as vertical charge carrier (hole) transport. These results also show a good agreement with our theoretical analysis. This work provides significant insights in advancing the design and development of high efficiency PEC devices for artificial photosynthesis using industry ready materials, e.g., Si and GaN, to achieve large-scale, low-cost onsite hydrogen fuel production.

42 ENGINEERING↗