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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 469 records · Page 26

Synthesis of platinum nanoparticles on strontium titanate nanocuboids via surface organometallic grafting for the catalytic hydrogenolysis of plastic waste

Pt/SrTiO 3 (Pt/STO), prepared on small scale by atomic layer deposition (ALD), is a capable heterogeneous catalyst for the selective hydrogenolysis of polyolefins to hydrocarbon oils, providing a promising approach for upcycling plastic waste. However, because deposition by ALD is costly and resource-intensive, a new synthesis of Pt/STO is needed to effectively scale catalyst production and pursue the commercialization of upcycling processes. To that effect, this work details a scalable deposition method for Pt/STO made by surface organometallic chemistry (SOMC) techniques using Pt(II) acetylacetonate or and trimethyl(methylcyclopentadienyl)platinum. The STO support was calcined (550 °C), treated with ozone (200 °C), and finally steamed (200 °C) to afford a clean STO surface populated with only hydroxyl groups. Pt precursors were dissolved in toluene and deposited onto STO. After reduction at 300 °C, the STO support was decorated with 1.0–1.5 nm Pt nanoparticles. The size and loading of these nanoparticles were varied by employing a multi-cycle deposition and oxidation and/or reduction process designed to ALD techniques. In conclusion, these Pt/STO catalysts hydrogenolyzed isotactic polypropylene into liquid products (>95% yield) with average molecular weights of 200–300 Da (~25 carbon atoms) and narrow size distributions at 300 °C and 180 psi H 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Biogeochemical reactions and release of iron-bound organic carbon during the redox processes. Final report

Accurate simulation and prediction for reactions of soil organic carbon (OC) under different biogeochemical conditions remain a grand challenge. This project aims to investigate the transformation and degradation of OC under anaerobic and aerobic conditions as well as anaerobic-aerobic transitions, as well as its coupling with reactions for iron (Fe) oxide minerals. We determined that OC can serve as electron shuttle (including pyrogenic OC) and donor for accelerating the reduction of Fe oxide. The presence of OC can inhibit the transformation of poor crystalline Fe oxide (ferrihydrite) to other more crystalline forms. Reduction of Fe oxide can lead to the mobilization of OC, depending on the ratio of OC/Fe. More condensed aromatic OC can be selectively associated with Fe oxide and also resistant to the reduction release, enhancing their stability during the anaerobic reactions. Under aerobic condition, the association with Fe oxide can inhibit the degradation of OC and also its priming effects on the degradation of indigenous soil OC. During an anaerobic-aerobic transition, OC mineralization was inhibited substantially compared to controls incubated only aerobically. Our field measurement in the Arctic region revealed the importance of deep soil temperature in regulating the generation of CO 2 and CH 4 . These results highlighted the importance of redox reactions in controlling the fate and stability of soil OC. For future studies, investigations are required to fill in the knowledge gap regarding the structure and chemical nature of important organic ligands for Fe, accurate quantification of Fe-bound OC in soils, the long-term effects of anaerobic-aerobic transitions on the OC mineralization as well as response of microbial communities to redox transitions.

54 ENVIRONMENTAL SCIENCES↗

Phase Transition Dynamics in a Complex Oxide Heterostructure

Understanding the behavior of defects in the complex oxides is key to controlling myriad ionic and electronic properties in these multifunctional materials. The observation of defect dynamics, however, requires a unique probe-one sensitive to the configuration of defects as well as its time evolution. Here, we present measurements of oxygen vacancy ordering in epitaxial thin films of SrCoO x and the brownmillerite-perovskite phase transition employing x-ray photon correlation spectroscopy. These and associated synchrotron measurements and theory calculations reveal the close interaction between the kinetics and the dynamics of the phase transition, showing how spatial and temporal fluctuations of heterointerface evolve during the transformation process. The energetics of the transition are correlated with the behavior of oxygen vacancies, and the dimensionality of the transformation is shown to depend strongly on whether the phase is undergoing oxidation or reduction. Finally, the experimental and theoretical methods described here are broadly applicable to in situ measurements of dynamic phase behavior and demonstrate how coherence may be employed for novel studies of the complex oxides as enabled by the arrival of fourth-generation hard x-ray coherent light sources.

36 MATERIALS SCIENCE↗

Integrating Tide‐Driven Wetland Soil Redox and Biogeochemical Interactions Into a Land Surface Model

Abstract Redox processes, aqueous and solid‐phase chemistry, and pH dynamics are key drivers of subsurface biogeochemical cycling and methanogenesis in terrestrial and wetland ecosystems but are typically not included in terrestrial carbon cycle models. These omissions may introduce errors when simulating systems where redox interactions and pH fluctuations are important, such as wetlands where saturation of soils can produce anoxic conditions and coastal systems where sulfate inputs from seawater can influence biogeochemistry. Integrating cycling of redox‐sensitive elements could therefore allow models to better represent key elements of carbon cycling and greenhouse gas production. We describe a model framework that couples the Energy Exascale Earth System Model (E3SM) Land Model (ELM) with PFLOTRAN biogeochemistry, allowing geochemical processes and redox interactions to be integrated with land surface model simulations. We implemented a reaction network including aerobic decomposition, fermentation, sulfate reduction, sulfide oxidation, methanogenesis, and methanotrophy as well as pH dynamics along with iron oxide and iron sulfide mineral precipitation and dissolution. We simulated biogeochemical cycling in tidal wetlands subject to either saltwater or freshwater inputs driven by tidal hydrological dynamics. In simulations with saltwater tidal inputs, sulfate reduction led to accumulation of sulfide, higher dissolved inorganic carbon concentrations, lower dissolved organic carbon concentrations, and lower methane emissions than simulations with freshwater tidal inputs. Model simulations compared well with measured porewater concentrations and surface gas emissions from coastal wetlands in the Northeastern United States. These results demonstrate how simulating geochemical reaction networks can improve land surface model simulations of subsurface biogeochemistry and carbon cycling.

54 ENVIRONMENTAL SCIENCES↗

Surface Analysis Insight Note: Observations relating to photoemission peak shapes, oxidation state, and chemistry of titanium oxide films

It is common practice to describe the coordination of metal atoms in a binding configuration with their nearest neighbors in terms of oxidation state, a measure by which the number of electrons redistributed between atoms forming chemical bonds. In XPS terms, change to an oxidation state is commonly inferred by correlating photoemission signal with binding energy. The assumption, when classifying photoemission signals into distinct spectral shapes, is that a distribution of intensities shifted to lower binding energy is evidence of a reduction in oxidation state. In this Insight note, we raise the prospect that changes in photoemission peak shape may occur without obvious changes, determined by XPS in stoichiometry for a material. It is well known that TiO 2 measured by XPS yields reproducible Ti 2p photoemission peaks. However, on exposing TiO 2 to ion beams, Ti 2p photoemission evolves to complex distributions in intensity, which are particularly difficult to analyze by traditional fitting of bell-shaped curves to these data. For these reasons, in this Insight note, a thin film of TiO 2 deposited on a silicon substrate is chosen for analysis by XPS and linear algebraic techniques. Alterations in spectral shapes created from modified TiO 2 , which might be interpreted as the change in oxidation state, are assessed in terms of relative proportions of titanium to oxygen. It is found through detailed analysis of spectra that quantification by XPS, using procedures routinely used in practice, is not in accord with the typical interpretations of photoemission shapes. The data processing methods used and results presented in this work are of particular relevance to elucidating fundamental phenomena governing the surface evolution of materials-enabled energy processes where cyclic/non-steady usage changes the nature of bonding, especially in the presence of contaminants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Triggering C-N Coupling on Metal Oxide Nanocomposite for the Electrochemical Reduction of CO 2 and NO x ⁻ to Formamide

The co-electroreduction of CO 2 and NO x ⁻ (NO 3 ⁻ /NO 2 ⁻ ) to generate formamide (HCONH 2 ) offers an opportunity for downstream chemical and polymer manufacturing decarbonization; however, significant challenges lie in the C-N coupling and the associated low product selectivity. Herein, p-block metal oxides are incorporated in copper oxides to provide more accessible active sites for reactant adsorption and activation, tuning the reaction selectivity toward the formamide production. Through in situ Raman and synchrotron-based infrared spectroscopy measurements, C-N bond formation is demonstrated in real-time with the CuO x /BiO x catalyst, where the C-N bond is detected via a *CHO and *NH 2 intermediates formation, in agreement with the density functional theory calculations. When tested in a flow electrolyzer, a formamide yield rate of 134 ± 11 mmol h -1 g cat -1 is reported, the first report of co-electroreduction of CO 2 and NO x ⁻ to formamide beyond conventional H-cell measurements. These new insights on the C-N coupling mechanisms and scale-up capability provide directions for further development of electrocatalysts for the formamide production.

36 MATERIALS SCIENCE↗

Epitaxial and Strong Support Interactions between Pt and LaFeO 3 Films Stabilize Pt Dispersion

The ability to stabilize very small Pt crystallites in supported-metal catalysts following harsh treatments is an important industrial problem. Herein, we demonstrate that Pt particles can be maintained in the 1- to 2-nm range following multiple oxidation and reduction cycles at 1073 K when the particles are supported on 0.5-nm LaFeO 3 films that have been deposited onto MgAl 2 O 4 using atomic layer deposition (ALD). Characterization by Scanning Transmission Electron Microscopy (STEM) suggest that, when the catalyst is oxidized at 1073 K, the Pt crystallites are oriented with respect to the underlying LaFeO 3 . X-Ray Absorption Spectroscopy (XAS) also shows evidence for changes in the Pt environment. CO-oxidation rates for the reduced catalyst remain unchanged after five redox cycles at 1073 K. Epitaxial growth of Pt clusters and the consequent strong metal-support interaction between Pt and LaFeO 3 are indicated to be prime reasons for the enhanced catalytic performances.

36 MATERIALS SCIENCE↗

Mechanism of Tyrosine-Driven Deprotonation in Photosystem II Revealed by Multiscale Simulations

Photosystem II (PSII) drives light-induced water oxidation via stepwise redox transitions of its oxygen-evolving complex (OEC), a Mn 4 Ca cluster advancing through five intermediate S-states (S 0 –S 4 ). The S 2 → S 3 transition involves a redox event in which a Mn ion donates an electron to the redox-active tyrosine YZ, coupled to deprotonation of an OEC-bound water ligand─yet the underlying coupling mechanism remains unresolved. Time-resolved serial femtosecond crystallography (TR-SFX) has revealed transient electron density shifts near the redox-active tyrosine Y Z , interpreted as sequential oxidation and reduction, with reduction initiating ∼1 μs after excitation and substantially progressed by 30 μs. However, this interpretation conflicts with kinetics from photothermal beam deflection (PBD), time-resolved X-ray absorption spectroscopy (TR-XAS), and electron paramagnetic resonance (EPR), which place electron transfer at 190–400 μs and proton transfer around 30 μs. Here, we reconcile these discrepancies using quantum mechanics/molecular mechanics (QM/MM) and molecular dynamics (MD) simulations. We show that oxidation of P680 and Y Z breaks the symmetry of the nearby hydrogen bonds involving water molecule W4, displacing Y Z and replicating the TR-SFX features of Y Z and Q165 observed at 1 μs. This local perturbation propagates through a hydrogen-bond network, transmitting the electrostatic signal from Y Z to the E65-E312 dyad and triggering redox-coupled deprotonation via the Cl1 channel. By 30 μs, the hydrogen-bond symmetry is restored through deprotonation of W2 (or alternatively W1), reproducing the disappearance of TR-SFX density differences around Y Z and Q165 without requiring Y Z reduction. Our proposed mechanism also gives molecular insights into the O6* density, assigning it to water reorganization rather than a discrete Ca-bound hydroxide species. Here, our results reveal a detailed atomistic mechanism linking Y Z oxidation to long-range proton release and suggest a functional role for the nearby Cl – ion in proton transfer. More broadly, this study underscores the importance of hydrogen-bond dynamics in mediating redox-driven proton transport and demonstrates how integrative simulations can resolve mechanistic ambiguities.

Deprotonation↗

Oxidation of Copper Alloy Candidates for Rocket Engine Applications

The gateway to affordable and reliable space transportation in the near future remains long-lived rocket-based propulsion systems; and because of their high conductivities, copper alloys remain the best materials for lining rocket engines and dissipating their enormous thermal loads. However, Cu and its alloys are prone to oxidative degradation -- especially via the ratcheting phenomenon of blanching, which occurs in situations where the local ambient can oscillate between oxidation and reduction, as it does in a H2/02- fuelled rocket engine. Accordingly, resistance to blanching degradation is one of the key requirements for the next generation of reusable launch vehicle (RLV) liner materials. Candidate copper alloys have been studied with a view to comparing their oxidation behavior, and hence resistance to blanching, in ambients corresponding to conditions expected in rocket engine service. These candidate materials include GRCop-84 and GRCop-42 (Cu - Cr-8 - Nb-4 and Cu - Cr-4 - Nb-2 respectively); NARloy-Z (Cu-3%Ag-0.5%Y), and GlidCop (Cu-O.l5%Al2O3 ODS alloy); they represent different approaches to improving the mechanical properties of Cu without incurring a large drop in thermal conductivity. Pure Cu (OFHC-Cu) was included in the study to provide a baseline for comparison. The samples were exposed for 10 hours in the TGA to oxygen partial pressures ranging from 322 ppm to 1.0 atmosphere and at temperatures of up to 700 C, and examined by SEM-EDS and other techniques of metallography. This paper will summarize the results obtained.

Ogbuji, Linus U. Thomas↗

Molecular Mechanisms of Circadian Regulation During Spaceflight

Disruption of the regular environmental circadian cues in addition to stringent and demanding operational schedules are two main factors that undoubtedly impact sleep patterns and vigilant performance in the astronaut crews during spaceflight. Most research is focused on the behavioral aspects of the risk of circadian desynchronization, characterized by fatigue and health and performance decrement. A common countermeasure for circadian re-entrainment utilizes blue-green light to entrain the circadian clock and mitigate this risk. However, an effective countermeasure targeting the photoreceptor system requires that the basic circadian molecular machinery remains intact during spaceflight. The molecular clock consists of sets of proteins that perform different functions within the clock machinery: circadian oscillators (genes whose expression levels cycle during the day, keep the pass of cellular time and regulate downstream effector genes), the effector or output genes (those which impact the physiology of the tissue or organism), and the input genes (responsible for sensing the environmental cues that allow circadian entrainment). The main environmental cue is light. As opposed to the known photoreceptors (rods and cones), the non-visual light stimulus is received by a subset of the population of retinal ganglion cells called intrinsically photosensitive retinal ganglion cells (ipRGC) that express melanopsin (opsin 4 -Opn4-) as the photoreceptor. We hypothesize that spaceflight may affect ipRGC and melanopsin expression, which may be a contributing cause of circadian disruption during spaceflight. To answer this question, eyes from albino Balb/cJ mice aboard STS-133 were collected for histological analysis and gene expression profiling of the retina at 1 and 7 days after landing. Both vivarium and AEM (animal enclosure module) mice were used as ground controls. Opn4 expression was analyzed by real time RT/qPCR and retinal sections were stained for Opn4 immunofluorescence. Opn4 was decreased (abrogated in one case) in retinas that concurrently showed higher evidence of oxidative stress. We propose that oxidative stress can lead to a decrease in melanopsin expression, likely via ipRGC loss or impairment, and thus, it can be a contributing factor to circadian disruption during spaceflight. Countermeasures contemplating the use of light should therefore be complemented with melanopsin expression maintenance and/or reduction in oxidative stress.

Zanello, Susana↗

Electrodeposition of Aluminum in the 1-Ethyl-3-Methylimidazolium Tetrachloroaluminate Ionic Liquid

The electrodeposition of Al was investigated in an ionic liquid (IL), with 1-ethyl-3-methylimidazolium tetrachloroaluminate ([EMIm]AlCl4) as the electrolyte with AlCl3 precursor. The [EMIm]AlCl4 electrolyte exhibited a wide and stable electrochemical window from 3.2 to 2.3 V on a glassy carbon electrode when temperature was increased from 30 °C to 110 °C. The addition of AlCl3 into [EMIm]AlCl4 generated significant well-developed nucleation growth loops, and new coupled reduction and oxidation peaks in cyclic voltammograms corresponding to the Al deposition and dissolution, respectively. A calculation model was proposed predicting compositions of anions in AlCl3/[EMIm]AlCl4 system, and [Al2Cl7]− was found to be the active species for Al deposition. In AlCl3/[EMIm]AlCl4 (1:5), the reduction rate constants were 1.18 × 10−5 cm s−1 and 3.37 × 10−4 cm s−1 at 30 °C and 110 °C, respectively. Scanning electron microscope (SEM), energy dispersive spectroscope (EDS), and X-ray diffraction (XRD) microscope results showed that the metallic Al film had been successfully deposited on glassy carbon electrodes through constant-potential cathodic reductions. The [EMIm]AlCl4 was a promising electrolyte directly used for Al deposition.

Shi, Meng↗

High temperature oxidation of beta-NiAl

The oxidation of single crystal beta-NiAl has been studied primarily using electron microscopy. Oriented metastable Al2O3 phases form during transient oxidation at 800 C. Specific orientation relationships exist on all metal orientations studied and are a result of the small mismatch along aligned close-packed directions in the cation sublattices of the metal and oxide. Transformation of the metastable Al2O3 phases at 1100 C results in an oxide morphology described as the 'lacey' structure of alpha-Al2O3 scales. This structure results from impingement of oriented patches of alpha-Al2O3 as the transformation initiates and moves radially parallel to the surface. Scale growth occurs by diffusion along high angle grain boundaries. A drastic reduction in oxidation rate accompanies the change in oxide morphology.

Koychak, J. K.↗

Impact of sodium vanadium oxide (NaV 3 O 8 , NVO) material synthesis conditions on charge storage mechanism in Zn-ion aqueous batteries

The electrochemical charge storage of sodium vanadate (NaV 3 O 8 or NVO) cathodes in aqueous Zn-ion batteries has been hypothesized to be influenced by the inclusion of structural water for facilitating ion transfer in the material. Materials properties considered important (morphology, crystallite and particle size, surface area) are systematically studied herein through investigation of two NVO materials, NaV 3 O 8 ·0.34H 2 O [NVO(300)] and NaV 3 O 8 ·0.05H 2 O [NVO(500)], with different water content, acicular morphologies with different size and surface area achieved via post-synthesis heat treatment. The electrochemistry of the two materials was evaluated in aqueous Zn-ion cells with 2 M ZnSO 4 electrolyte using cyclic voltammetry, galvanostatic cycling, and rate capability testing. Furthermore, the thinner NVO(300) nanobelts (0.13 μm) demonstrate greater specific capacities and higher effective diffusion coefficients relative to the thicker NVO(500) nanorods. Notably however, while cells containing NVO(500) deliver lower specific capacity, they demonstrate enhanced capacity retention with cycling. The structural changes accompanying oxidation and reduction are elucidated via ex situ X-ray diffraction, transmission electron microscopy, and operando V K-edge X-ray absorption spectroscopy (XAS), where NVO material properties are shown to influence the ion insertion. Operando XAS verified that electron transfer corresponds directly to change in vanadium oxidation state, affirming vanadium redox as the governing electrochemical process.

25 ENERGY STORAGE↗

Low NO(x) heavy fuel combustor program

The 'low nitrogen oxides heavy fuel combustor' program is described. Main program objectives are to generate and demonstrate the technology required to develop durable gas turbine combustors for utility and industrial applications, which are capable of sustained, environmentally acceptable operation with minimally processed petroleum residual fuels. The program will focus on 'dry' reductions of oxides of nitrogen, improved combustor durability, and satisfactory combustion of minimally processed petroleum residual fuels. Other technology advancements sought include: fuel flexibility for operation with petroleum distillates, blends of petroleum distillates and residual fuels, and synfuels (fuel oils derived from coal or shale); acceptable exhaust emissions of carbon monoxide, unburned hydrocarbons, sulfur oxides and smoke; and retrofit capability to existing engines.

Lister, E.↗

Highly Active and Stable Single Atom Rh 1 /CeO 2 Catalyst for CO Oxidation during Redox Cycling

We report a single atom Rh 1 /CeO 2 catalyst prepared by the high temperature (800 °C) atom trapping (AT) method which is stable under both oxidative and reductive conditions. Infrared spectroscopic and electron microscopy characterization revealed the presence of exclusively ionic Rh species. These ionic Rh species are stable even under reducing conditions (CO at 300 °C) due to the strong interaction between Rh and CeO 2 achieved by the AT method, leading to high and reproducible CO oxidation activity regardless of whether the catalyst is reduced or oxidized. In contrast, ionic Rh species in catalysts synthesized by a conventional impregnation approach (e. g., calcined at 350 °C) can be readily reduced to form Rh nanoclusters/nanoparticles, which are easily oxidized under oxidative conditions, leading to loss of catalytic performance. The single atom Rh 1 /CeO 2 catalysts synthesized by the AT method do not exhibit changes during redox cycling hence are promising catalysts for emission control where redox cycling is encountered, and severe oxidation (fuel cut) leads to loss of performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A High-Entropy Oxide as High-Activity Electrocatalyst for Water Oxidation

High-entropy materials are an emerging pathway in the development of high-activity (electro)catalysts because of the inherent tunability and coexistence of multiple potential active sites, which may lead to earth-abundant catalyst materials for energy-efficient electrochemical energy storage. In this report, we identify how the multication composition in high-entropy perovskite oxides (HEO) contributes to high catalytic activity for the oxygen evolution reaction (OER), i.e., the key kinetically limiting half-reaction in several electrochemical energy conversion technologies, including green hydrogen generation. We compare the activity of the (001) facet of LaCr 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 O 3-δ with the parent compounds (single B-site in the ABO 3 perovskite). While the single B-site perovskites roughly follow the expected volcano-type activity trends, the HEO clearly outperforms all of its parent compounds with 17 to 680 times higher currents at a fixed overpotential. As all samples were grown as an epitaxial layer, our results indicate an intrinsic composition–function relationship, avoiding the effects of complex geometries or unknown surface composition. In-depth X-ray photoemission studies reveal a synergistic effect of simultaneous oxidation and reduction of different transition metal cations during the adsorption of reaction intermediates. The surprisingly high OER activity demonstrates that HEOs are a highly attractive, earth-abundant material class for high-activity OER electrocatalysts, possibly allowing the activity to be fine-tuned beyond the scaling limits of mono- or bimetallic oxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrolyte Oxidation Pathways in Lithium-Ion Batteries

The mitigation of decomposition reactions of lithium-ion battery electrolyte solutions is of critical importance in controlling device lifetime and performance. However, due to the complexity of the system, exacerbated by the diverse set of electrolyte compositions, electrode materials, and operating parameters, a clear understanding of the key chemical mechanisms remains elusive. In this work, operando pressure measurements, solution NMR, and electrochemical methods were combined to study electrolyte oxidation and reduction at multiple cell voltages. Two-compartment LiCoO 2 /Li cells were cycled with a lithium-ion conducting glass–ceramic separator so that the species formed at each electrode could be identified separately and further reactions of these species at the opposite electrode prevented. One principal finding is that chemical oxidation (with an onset voltage of ~4.7 V vs Li/Li + for LiCoO 2 ), rather than electrochemical reaction, is the dominant decomposition process at the positive electrode surface in this system. This is ascribed to the well-known release of reactive oxygen at higher states-of-charge, indicating that reactions of the electrolyte at the positive electrode are intrinsically linked to surface reactivity of the active material. Soluble electrolyte decomposition products formed at both electrodes are characterized, and a detailed reaction scheme is constructed to rationalize the formation of the observed species. The insights on electrolyte decomposition through reactions with reactive oxygen species identified through this work have a direct impact on understanding and mitigating degradation in high-voltage/higher-energy-density LiCoO 2 -based cells, and more generally for cells containing nickel-containing cathode materials (e.g., LiNi x Mn y Co z O 2 ; NMCs), as they lose oxygen at lower operating voltages.

25 ENERGY STORAGE↗