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63 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Efficient BiVO 4 /CoFeO x H y photoanodes using controlled annealing and conformal linear-sweep electrocatalyst photodeposition

Although monoclinic bismuth vanadate (BiVO 4 ) is a promising photoanode for solar water splitting, its practical use is hindered by imperfect photocurrent generation/collection, low photovoltage compared to the bandgap, and corrosion side reactions that limit durability. Here, we introduce a controlled-annealing sol–gel process for BiVO 4 thin-film photoanodes along with an optimized linear-sweep-voltammetry photodeposition of CoFeO x H y cocatalysts. The resulting BiVO 4 films annealed at 550 °C exhibited a photocurrent density of 4.1 mA/cm 2 at 1.23 V RHE under 1 sun AM 1.5G solar simulation and a low onset potential of 0.26 V RHE due to high majority carrier conductivity, a crystalline bulk with reduced defects as evidenced by x-ray photoelectron spectroscopy and photoluminescence lifetime analysis, and thus enhanced photocarrier collection. However, significant degradation in performance was found due to interfacial photocorrosion. To protect the surface and speed the oxygen-evolution reaction CoFeO x H y cocatalyst layers were deposited. By varying the number of consecutive sweeps and adjusting the applied bias range, an ultra-thin (~15 nm) CoFeO x H y cocatalyst layer was uniformly grown deposited over 30 cycles on the BiVO 4 surface. The resulting BiVO 4 /CoFeO x H y yielded 4.03 mA/cm 2 at 1.23 V RHE and onset potential of 0.24 V RHE , with stable operation (~15 % loss in photocurrent at 1.23 V RHE relative to ~60 % loss in the uncatalyzed control sample). These conformal CoFeO x H y catalytic layers function simultaneously to selectively collect photoexcited holes from the BiVO 4 , catalyze the water-oxidation reaction, and protect the BiVO 4 from photodegradation.

42 ENGINEERING↗
DOE OSTI2025

Compatibility of Zircaloy-4 in eutectic PbSn and PbBiSn liquid metals

Here, a novel nuclear fuel concept has been proposed, consisting of UO₂ particles suspended in a liquid metal alloy. To evaluate its feasibility, the compatibility of Zircaloy-4 cladding with candidate eutectic PbSn and PbBiSn alloys—as well as with pure Pb, Bi, and Sn—was investigated through 1000-hour exposures at 400 °C and 600 °C. Severe degradation of the Zircaloy-4 specimens was observed in eutectic PbSn at 600 °C, whereas oxidation and oxygen diffusion were evident after exposure at 400 °C. At 600 °C, the formation of Zr₃Fe precipitates at the oxide–alloy interface was identified in specimens exposed to Pb and PbBiSn. Thermodynamic analysis suggested that the observed intermetallic formation resulted from the destabilization of Laves phases due to oxygen ingress at elevated temperatures.

Bismuth↗
NASA NTRS1985

Cycling Performance of the Iron-Chromium Redox Energy Storage System

Extended charge-discharge cycling of this electrochemical storage system at 65 C was performed on 14.5 sq cm single cells and a four cell, 867 sq cm bipolar stack. Both the anolyte and catholyte reactant fluids contained 1 molar concentrations of iron and chromium chlorides in hydrochloric acid and were separated by a low-selectivity, cation-exchange membrane. The effect of cycling on the chromium electrode and the cation-exchange membrane was determined. Bismuth and bismuth-lead catalyzed chromium electrodes and a radiation-grafted polyethylene membrane were evaluated by cycling between 5 and 85 percent state-of-charge at 80 mA/sq cm and by periodic charge-discharge polarization measurements to 140 mA/sq cm. Gradual performance losses were observed during cycling but were recoverable by completely discharging the system. Good scale-up to the 867 sq cm stack was achieved. The only difference appeared to be an unexplained resistive-type loss which resulted in a 75 percent W-hr efficiency (at 80 mA/sq cm versus 81 percent for the 14.5 sq cm cell). A new rebalance cell was developed to maintain reactant ionic balance. The cell successfully reduced ferric ions in the iron reactant stream to ferrous ions while chloride ions were oxidized to chlorine gas.

Gahn, R. F.↗
NASA NTRS1985

Cycling performance of the iron-chromium redox energy storage system

Extended charge-discharge cycling of this electrochemical storage system at 65 C was performed on 14.5 sq cm single cells and a four cell, 867 sq cm bipolar stack. Both the anolyte and catholyte reactant fluids contained 1 molar concentrations of iron and chromium chlorides in hydrochloric acid and were separated by a low-selectivity, cation-exchange membrane. The effect of cycling on the chromium electrode and the cation-exchange membrane was determined. Bismuth and bismuth-lead catalyzed chromium electrodes and a radiation-grafted polyethylene membrane were evaluated by cycling between 5 and 85 percent state-of-charge at 80 mA/sq cm and by periodic charge-discharge polarization measurements to 140 mA/sq cm. Gradual performance losses were observed during cycling but were recoverable by completely discharging the system. Good scale-up to the 867 sq cm stack was achieved. The only difference appeared to be an unexplained resistive-type loss which resulted in a 75 percent W-hr efficiency (at 80 mA/sq cm versus 81 percent for the 14.5 sq cm cell). A new rebalance cell was developed to maintain reactant ionic balance. The cell successfully reduced ferric ions in the iron reactant stream to ferrous ions while chloride ions were oxidized to chlorine gas.

Gahn, R. F.↗
NASA NTRS1993

Reaction of YBa2Cu3O(7-beta) with Gold, Silver, Bismuth and Lead: Substitution Chemistry and Composite Fabrication

The reaction of YBa2Cu3O(7-beta) with Au, Ag, Bi, and Ph ions or metal is described. Three types of materials were produced: a well-defined series of homogeneous superconductors was obtained for Au ion substitution with little effect on T(sub c); attempted Ag and Bi ion substitution resulted in multi-phase samples with slightly enhanced T(sub c); finally, attempts to produce superconducting metal/superconducting ceramic composites with Pb and Bi powders resulted in multi-phase samples with drastically diminished superconducting properties. For Au- substituted superconductors, YBa2(Cu(l-x)Au(x))3O(7-beta), a substitution series (x = 0 - 0.1) has been synthesized. For x = 0.1 there was no change in the a and b lattice parameters (a = 3.826 A and b = 3.889 A) but a 0.06 A c axis expansion to 11.75 A was observed. The valence of Cu and Au in YBa2Au(0.3)Cu(2.7)O(7-beta) was investigated using X-ray Absorption Near-Edge Structure (XANES). X-ray studies indicate that Au goes into the Cu(l) site and Cu K edge XANES shows that this has little effect on the oxidation state of the remaining copper. A small effect on T(sub c) is observed (T(sub c) = 89 K for x = 0.10). Ag and Bi addition results in a rise in T(sub c) and a decrease in (delta)T(sub c) at low levels (x = 0.10 Ag, T(sub c) = 94 K and (delta)T(sub c) = 0.5 K; x = 0.02 Bi, T(sub c) = 94 K and (delta)T(sub c) = 1K) relative to typical values for YBa2Cu3O(7-beta) (T(sub c) = 91 K, (delta)T(sub c) = 2 K). Attempts at fabrication of Pb- and Pb(1-x)Bi(x)-superconductor composites are described. Cold pressing followed by low temperature (200 C) sintering resulted in a composite which excluded flux below 90 K but did not show zero electrical resistance until the metal (alloy) superconducting transition. X-ray diffraction showed the presence of pervoskite and metal. Processing at moderate (450 C) or high (950 C) temperatures resulted in oxygen-depleted pervoskite and/or metal oxides. These materials displayed greatly degraded superconducting properties. Processing at 800 C resulted in high T(sub c) only for composites containing greater than 90% weight fraction ceramic. Reaction of metal with YBa2Cu3O(7-beta) formed superconducting lead/bismuth-based oxides and other binary oxides.

Hepp, Aloysius F.↗
NASA NTRS2007

Concurrent CO2 Control and O2 Generation for Advanced Life Support

The electrochemical reduction of carbon dioxide (CO2) using ceramic oxygen generators (COGs) is well known and widely studied, however, conventional devices using yttria-stabilized zirconia (YSZ) electrolytes operate at temperatures greater than 700 C. Operating at such high temperatures increases system mass compared to lower temperature systems because of increased energy overhead to get the COG up to operating temperature and the need for heavier insulation and/or heat exchangers to reduce the COG oxygen (O2) output temperature for comfortable inhalation. Recently, the University of Florida developed novel ceramic oxygen generators employing a bilayer electrolyte of gadolinia-doped ceria and erbia-stabilized bismuth for NASA's future exploration of Mars. To reduce landed mass and operation expenditures during the mission, in-situ resource utilization was proposed using these COGs to obtain both lifesupporting oxygen and oxidant/propellant fuel, by converting CO2 from the Mars atmosphere. The results showed that oxygen could be reliably produced from CO2 at temperatures as low as 400 C. These results indicate that this technology could be adapted to CO2 removal from a spacesuit and other applications in which CO2 removal was an issue. The strategy proposed for CO2 removal for advanced life support systems employs a catalytic layer combined with a COG so that it is reduced all the way to solid carbon and oxygen. Hence, a three-phased approach was used for the development of a viable low weight COG for CO2 removal. First, to reduce the COG operating temperature a high oxide ion conductivity electrolyte was developed. Second, to promote full CO2 reduction while avoiding the problem of carbon deposition on the COG cathode, novel cathodes and a removable catalytic carbon deposition layer were designed. Third, to improve efficiency, a pre-stage for CO2 absorption was used to concentrate CO2 from the exhalate before sending it to the COG. These subsystems were then integrated into a single CO2 removal system. This paper describes our progress to date on these tasks.

Paul, Heather L.↗
NASA NTRS1993

Casting of superconducting composite materials (M-4)

An aluminum-lead-bismuth alloy is a flexible alloy and is promising for easily workable embedded-type, filament-dispersed superconducting wire material. It is difficult to produce homogeneous ingots of this material because it is easily separated into elements when melted on Earth due to the large specific gravity differences. In this experiment, a homogeneous alloy will first be produced in molten state in microgravity. It will then be returned to Earth and processed into a wire or tape form. It will then be dispersed as the second phase in micro texture form into the primary phase of aluminum. Superconducting wire material with high-critical-magnetic-field characteristics will be produced. The texture of the material will be observed, and its performance will be evaluated. In addition to the above alloy, a four-element alloy will be produced from silver, a rare Earth element, barium, and copper. The alloys will be oxidized and drawn into wire after being returned to Earth. The materials are expected to be forerunners in obtaining superconducting wire materials from oxide superconductors.

Togano, Kazumasa↗
DOE OSTI2026

Nanoarchitectonic Semiconductor–Bio Hybrid Systems with Enhanced Charge Transfer for Hydrogen Peroxide Production

Nanoarchitectonics offers a systematic approach to creating an artificial framework by integrating different multiscale components such as semiconductor lattices and biological substances. However, most nanoarchitectonic abiotic-biotic hybrid systems have intrinsic limitations in imparting nonequilibrium biological features into semiconductor lattices at the nanoscale. Here, in this study, we report a new nanoarchitectonic system integrating bismuth oxychloride (BiOCl) nanosheets with purple membrane (PM) patches. PM is an archaeal subcellular fraction capable of unidirectionally transferring photogenerated charge carriers to its surroundings at the nanoscale independent of archaeal metabolism and retaining this dynamic functionality after isolation from living archaea. Microscopy, spectroscopy, electrochemical, and synchrotron X-ray scattering analyses verify that the nanoarchitectonic hybridization between BiOCl and PM generates a vertical heterostructure, thereby enhancing photogenerated charge-carrier dynamics and enabling the associated photocatalytic capacity. The resulting PM-BiOCl hybrid nanosheets efficiently convert dioxygen into hydrogen peroxide through a two-electron and two-proton transfer process under ambient conditions while simultaneously converting ethylene glycol into value-added chemicals. This study presents a nanoarchitectonic approach that leverages the photogenerated charge-carrier dynamics of the archaeal subcellular fractions to modulate the optoelectronic and catalytic capacity limitations of semiconductors.

catalysis↗