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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Thermal Stability of Metal Nanocrystals: An Investigation of the Surface and Bulk Reconstructions of Pd Concave Icosahedra [On the Thermal Stability of Metal Nanocrystals: An Investigation of the Surface and Bulk Reconstructions of Pd Concave Icosahedra]

Despite the remarkable success in controlling the synthesis of metal nanocrystals, it still remains a grand challenge to stabilize and preserve the shapes or internal structures of metastable kinetic products. In this work, we address this issue by systematically investigating the surface and bulk reconstructions experienced by a Pd concave icosahedron when subjected to heating up to 600 °C in vacuum. We used in situ high-resolution transmission electron microscopy to identify the equilibration pathways of this far-from-equilibrium structure. We were able to capture key structural transformations occurring during the thermal annealing process, which were mechanistically rationalized by implementing self-consistent plane-wave density functional theory (DFT) calculations. Specifically, the concave icosahedron was found to evolve into a regular icosahedron via surface reconstruction in the range of 200–400 °C, and then transform into a pseudospherical crystalline structure through bulk reconstruction when further heated to 600 °C. As a result, the mechanistic understanding may lead to the development of strategies for enhancing the thermal stability of metal nanocrystals.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Caloric Restriction Impairs Regulatory T cells Within the Tumor Microenvironment After Radiation and Primes Effector T cells

Outcomes for triple negative breast cancer (TNBC) are poor and may be improved by increasing CD8{sup +} tumor infiltrating lymphocytes (TIL) to augment antitumor immunity. Radiation (RT) can promote immunogenic cell death with increased antitumor T cell activity but also stimulates suppressive regulatory T cells (Tregs). Because metabolic alterations affect immune homeostasis and prior studies show caloric restriction (CR) combined with RT improves preclinical TNBC outcomes, we hypothesized that CR augments RT, in part, by altering intratumoral immunity. Using an in vivo model of TNBC, we treated mice with ad libitum (AL) diet, radiation, a CR diet, or CR + RT, and demonstrated an immune suppressive environment with a significant increase in CD4{sup +} CD25{sup +}Foxp3{sup +} Tregs after RT but not in CR-fed mice. CD8:Treg ratio in CR + RT TIL increased 4-fold compared with AL + RT mice. In vivo CD8 depletion was performed to assess the role of effector T cells in mitigating the effects of CR, and it was found that in mice undergoing CR, depletion of CD8 T cells resulted in increased tumor progression and decreased median survival compared with isotype control–treated mice. In addition, PD-1 expression on CD3{sup +}CD8{sup +} T cells within the tumor microenvironment was significantly increased in CR + RT versus AL + RT treated mice as per immunofluorescence. Serum from breast cancer patients undergoing RT alone or CR and RT was collected pre- and postintervention, and a cytokine array demonstrated that patients treated with CR + RT had notable decreases in immunosuppressive cytokines such as IL-2Rγ, IL-10Rβ, and TGF-β2 and 3 compared with patients receiving RT alone. In conclusion, combining CR with RT decreases intratumoral Tregs, increases CD8:Treg, and increases PD-1 expression via a process dependent on CD8 T cells in a TNBC model. Breast cancer patients undergoing CR concurrently with RT also had significant reduction in immunosuppressive cytokine levels compared with those receiving RT alone.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2017

Stabilizing CuPd Nanoparticles via CuPd Coupling to WO 2.72 Nanorods in Electrochemical Oxidation of Formic Acid

Stabilizing a 3d-transition metal component M from an MPd alloy structure in an acidic environment is key to the enhancement of MPd catalysis for various reactions. Here we show a strategy to stabilize Cu in 5 nm CuPd nanoparticles (NPs) by coupling the CuPd NPs with perovskite-type WO 2.72 nanorods (NRs). The CuPd NPs are prepared by controlled diffusion of Cu into Pd NPs and the coupled CuPd/WO 2.72 are synthesized by growing WO 2.72 NRs in the presence of CuPd NPs. The CuPd/WO 2.72 can stabilize Cu in 0.1 M HClO4 solution and, as a result, they show Cu, Pd composition dependent activity for the electrochemical oxidation of formic acid in 0.1 M HClO 4 + 0.1 M HCOOH. Among three different CuPd/WO 2.72 studied, the Cu 48 Pd 52 /WO 2.72 is the most efficient catalyst with its mass activity reaching 2086 mA/mgPd in a broad potential range of 0.40 to 0.80 V (vs. RHE) and staying at this value after the 12 h chronoamperometry test at 0.40 V. The synthesis can be extended to obtain other MPd/WO 2.72 (M = Fe, Co, Ni), making it possible to study MPd-WO 2.72 interactions and MPd stabilization on enhancing MPd catalysis for various chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

An optimization-based strategy for peridynamic-FEM coupling and for the prescription of nonlocal boundary conditions

We develop and analyze an optimization-based method for the coupling of a static peridynamic (PD) model and a static classical elasticity model. The approach formulates the coupling as a control problem in which the states are the solutions of the PD and classical equations, the objective is to minimize their mismatch on an overlap of the PD and classical domains, and the controls are virtual volume constraints and boundary conditions applied at the local-nonlocal interface. Our numerical tests performed on three-dimensional geometries illustrate the consistency and accuracy of our method, its numerical convergence, and its applicability to realistic engineering geometries. We demonstrate the coupling strategy as a means to reduce computational expense by confining the nonlocal model to a subdomain of interest, and as a means to transmit local (e.g., traction) boundary conditions applied at a surface to a nonlocal model in the bulk of the domain.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Chemisorbed oxygen or surface oxides steer the selectivity in Pd electrocatalytic propene oxidation observed by operando Pd L-edge X-ray absorption spectroscopy

Controlled electrochemical oxidation of hydrocarbons to desired products is an attractive approach in catalysis. Here we study the electrochemical propene oxidation under operando conditions using Pd L-edge X-ray absorption spectroscopy (XAS) as a sensitive probe to elucidate surface processes occurring during catalysis. Together with ab initio multiple-scattering calculations, our XAS results enable assignment of characteristic changes of the Pd L-edge intensity and energy position in terms of a mechanistic understanding of the selective oxidation of propene. The results, supported by electrochemical density functional theory DFT simulations, show that in the potential range of 0.8–1.0 V vs. the reversible hydrogen electrode (RHE), selective oxidation of propene to acrolein and acrylic acid occurs on the metallic Pd surface. Here, these reactions are proposed to proceed via the Langmuir–Hinshelwood mechanism. In contrast, for the potential range of 1.1–1.3 V vs. RHE, selective oxidation of propene to propylene glycol takes place on a Pd oxide surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

CSI related dynamics and control issues in space robotics

The research addressed includes: (1) CSI issues in space robotics; (2) control of elastic payloads, which includes 1-DOF example, and 3-DOF harmonic drive arm with elastic beam; and (3) control of large space arms with elastic links, which includes testbed description, modeling, and experimental implementation of colocated PD and end-point tip position controllers.

Schmitz, Eric↗
DOE OSTI2020

Deep Understanding of Strong Metal Interface Confinement: A Journey of Pd/FeO x Catalysts

Tuning the atomic interface configuration of noble metals (NMs) and transition-metal oxides is an effective straightforward yet challenging strategy to modulate the activity and stability of heterogeneous catalysts. Herein, Pd supported on mesoporous Fe 2 O 3 with a high specific surface area was rationally designed and chosen to construct the Pd/iron oxide interface. As a versatile model, the physicochemical environments of Pd nanoparticles (NPs) could be precisely controlled by taming the reduction temperature. The experimental and density functional theory calculation results unveiled that the catalyst in the support–metal interface confinement (SMIC) state showed significantly enhanced catalytic activity and sintering resistance for CO oxidation. The constructed Fe sites at the interfaces between FeO x overlayers and Pd NPs not only provided additional coordinative unsaturated ferrous sites for the adsorption and activation of O 2 , thereby facilitating the activation efficiency of O 2 , but also impressively changed the reaction pathway of CO oxidation. As a result, the catalyst followed the Pd/Fe dual-site mechanism instead of the classical Mars–van Krevelen mechanism. For the catalyst in the strong metal–support interaction (SMSI) state, its catalytic activity was seriously suppressed because of the excessive encapsulation of the active Pd sites by FeO x overlayers. Thus, the present study therefore provides detailed insights into the SMIC and SMSI in ferric oxide-supported Pd catalysts, which could guide the preparation of highly efficient supported catalysts for practical applications.

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

Response characteristics of stable mixed-potential NH 3 sensors in diesel engine exhaust

Here, a mixed-potential, electrochemical sensor platform is extended to NH 3 sensing by the introduction of a new gold alloy working electrode. A planar, pre-commercial NH 3 sensor utilized LANL’s controlled interface approach, and a Pd-Au alloy working electrode was tested in exhaust of a GM 1.9 L diesel engine downstream of a diesel oxidation catalyst through a slipstream arrangement. A fraction of the exhaust was pulled across the sensor with a pump at 20 L/min. In order to simulate NH 3 slip inside of a full SCR emissions control system, NH 3 was injected immediately upstream of the sensor using a calibrated mass flow controller. The sensor response quantitatively tracked the NH 3 as measured via Fourier transform infrared (FTIR) analyzer. A calibration curve was obtained in the exhaust from an ammonia staircase response with the engine running at steady-state engine conditions resulting in low background concentrations of NO x and HC (<20 ppm) during calibration. Exhaust gas recirculation (EGR) switching and sweeps were used to evaluate the NH 3 sensor response under different amounts of total background NO x . The calibration curve was used to directly compare the [NH 3 ] calculated from sensor response to the gas phase composition measured via FTIR. In general, there was excellent quantitative agreement between the sensor response and the actual NH 3 in the exhaust gas, and fast response time such that transients (<5 ppm) could be easily discerned from baseline. A LANL pre-commercial NO x sensor was tested simultaneously with the NH 3 sensor and the extent of cross-sensitivity between the two sensors will be discussed.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Discerning structure sensitivity of Ni-core Pd-shell nanoparticles for enhanced nitrite reduction

Denitrification using Pd-based catalysts converts N-oxyanions into harmless products. However, the metal cost and scarcity are barriers to application. In this work, we synthesize water-suspended, structure-controlled Ni-core/Pd-shell nanoparticles (Ni@Pd NPs) that show Pd-catalyzed nitrite (NO 2 − ) reduction catalysis promoted by Ni. The NPs immobilized on Al 2 O 3 (0.47 wt % Pd and 0.74 wt % Ni) have higher NH 4 + selectivity and higher catalytic activity than wet-impregnated Pd/Al 2 O 3 (1.0 wt % Pd), i.e., 315.4 vs. 132.1 Lg surface Pd −1 min −1 . X-ray photoelectron spectroscopy (XPS) and CO-diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS) analyses show that Ni increases Pd electron density, which is proposed to lower the bond dissociation energy barrier for nitric oxide surface intermediate. Low-coordinated Pd atoms correlate to high activity and low NH 4 + selectivity. Using CatCost software, we estimate Ni@Pd/Al 2 O 3 to have a ∼40% lower manufacturing cost compared to wet-impregnated Pd/Al 2 O 3 . This rationally designed catalyst illustrates how nickel promotes Pd catalysis and how Pd usage can be lowered for denitrification and other hydrogenation reactions.

CO-DRIFTS↗
DOE OSTI2022

Improvement of Oxygen Reduction Performance in Alkaline Media by Tuning Phase Structure of Pd–Bi Nanocatalysts

Tuning the crystal phase of bimetallic nanocrystals offers an alternative avenue to improving their electrocatalytic performance. Herein, we present a facile and one-pot synthesis approach that is used to enhance the catalytic activity and stability toward oxygen reduction reaction (ORR) in alkaline media via control of the crystal structure of Pd-Bi nanocrystals. By merely altering the types of Pd precursors under the same conditions, the monoclinic structured Pd 5 Bi 2 and conventional face-centered cubic (fcc) structured Pd 3 Bi nanocrystals with comparable size and morphology can be precisely synthesized, respectively. Interestingly, the carbon-supported monoclinic Pd 5 Bi 2 nanocrystals exhibit superior ORR activity in alkaline media, delivering a mass activity (MA) as high as 2.05 A/mg Pd . After 10,000 cycles of ORR durability test, the monoclinic structured Pd 5 Bi 2 /C nanocatalysts still remain a MA of 1.52 A/mg Pd , which is 3.6 times, 16.9 times, and 21.7 times as high as those of the fcc Pd 3 Bi/C counterpart, commercial Pd/C, and Pt/C electrocatalysts, respectively. Moreover, structural characterizations of the monoclinic Pd 5 Bi 2 /C nanocrystals after the durability test demonstrate the excellent retention of the original size, morphology, composition, and crystal phase, greatly alleviating the leaching of the Bi component. Overall, this work provides new insight for the synthesis of multimetallic catalysts with a metastable phase and demonstrates phase-dependent catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2004

Product Distribution Theory and Semi-Coordinate Transformations

Product Distribution (PD) theory is a new framework for doing distributed adaptive control of a multiagent system (MAS). We introduce the technique of "coordinate transformations" in PD theory gradient descent. These transformations selectively couple a few agents with each other into "meta-agents". Intuitively, this can be viewed as a generalization of forming binding contracts between those agents. Doing this sacrifices a bit of the distributed nature of the MAS, in that there must now be communication from multiple agents in determining what joint-move is finally implemented However, as we demonstrate in computer experiments, these transformations improve the performance of the MAS.

Airiau, Stephane↗
DOE OSTI2017

Optimizing the ORR activity of Pd based nanocatalysts by tuning their strain and particle size

Controlling of the particle size and surface strain is the key to tuning the surface chemistry and optimizing the catalytic performance of electrocatalysts. In this study, we show that by introducing both Fe and Co into Pd lattices, the surface strain of Pd nanocatalysts can be tuned to optimize their oxygen reduction activity in both fuel cells and Zn–air batteries. The Pd 2 FeCo/C alloy particles are uniquely coated with an ultrathin Fe 2 O 3 shell which is in situ formed during a thermal annealing treatment. The thin shell acts as an effective barrier that prevents the coalescence and ripening of Pd 2 FeCo/C nanoparticles. Compared with Pd/C, Pd 2 FeCo/C exhibits higher catalytic activity and long-term stability for the ORR, signifying changes in catalytic behavior due to particle sizes and strain effects. Moreover, by spontaneous decoration of Pt on the surface of Pd 2 FeCo/C, the Pd 2 FeCo@Pt/C core@shell structure was formed and the Pt mass activity was about 37.6 and 112.5 times higher than that on Pt/C in a 0.1 M HClO 4 and KOH solution at 0.9 V, respectively, suggesting an enhanced ORR performance after Pt decoration. More interestingly, Pd 2 FeCo@Pt/C also shows a power density of ~308 mW cm -2 , which is much higher than that of Pt/C (175 mW cm -2 ), and excellent durability in a home-made Zn–air battery.

25 ENERGY STORAGE↗
DOE OSTI2018

Ultrafine Pd ensembles anchored-Au 2 Cu aerogels boost ethanol electrooxidation

Modification of the noble metal-based aerogels from the atomic scale is rarely being investigated despite the rapid development of various metallic aerogels. Recent studies have verified that Pd ensembles are more effective than isolated Pd atoms toward electrooxidation of ethanol. However, the electrocatalytic efficiency is still insufficient. Here, for the first time, we successfully anchored Pd-ensembles on the surface of Au 2 Cu metallic hydrogels via kinetically controlled galvanic displacement reaction. The atomic configuration optimized Au 2 Cu@Pd metallic aerogels exhibited significantly enhanced mass activity ~11.6 times of commercial Pd and excellent stability with remained 90 % of mass activity after 300 potential cycle test. The ligand effect and geometric effect generated by the finely tailored atomic configurations including Pd ensembles and core-shell structure are critical for enhancing electrocatalytic efficiencies. Furthermore, the Pd ensembles anchored-Au 2 Cu aerogels hold a great promise for being potentially applied in devices such as direct alcohol fuel cells, biosensors and electronics.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2019

Dopant-tuned stabilization of intermediates promotes electrosynthesis of valuable C3 products

The upgrading of CO 2 /CO feedstocks to higher-value chemicals via energy-efficient electrochemical processes enables carbon utilization and renewable energy storage. Substantial progress has been made to improve performance at the cathodic side; whereas less progress has been made on improving anodic electro-oxidation reactions to generate value. Here we report the efficient electroproduction of value-added multi-carbon dimethyl carbonate (DMC) from CO and methanol via oxidative carbonylation. We find that, compared to pure palladium controls, boron-doped palladium (Pd-B) tunes the binding strength of intermediates along this reaction pathway and favors DMC formation. We implement this doping strategy and report the selective electrosynthesis of DMC experimentally. We achieve a DMC Faradaic efficiency of 83 ± 5%, fully a 3x increase in performance compared to the corresponding pure Pd electrocatalyst.

42 ENGINEERING↗
NASA NTRS1985

Examination of coating failure by acoustic emission

Coatings of NiCrAlY bond coat with a zirconia - 12 wt percent yttria overlay were applied to disc-shaped specimens of U-700 alloy. A waveguide of 1 mm diameter platinum was TIG welded to the specimen and allowed it to be suspended in a tubular furnace. The specimen was thermally cycled to 1150 C, and the acoustic emission (AE) monitored. The weight gain per thermal cycle was also measured. A computer system based on the IBM-XT microcomputer was used extensively to acquire the AE data with respect to temperature. This system also controlled the temperature by using a PD software loop. Several different types of AE analyses were performed. A major feature of these tests, not addressed by previous work in this area, was that the coatings covered 100 percent of the specimen and also that the AE was amplified at two different levels. It is believed that this latter feature allows a qualitative appraisal of the relative number of cracks per AE event. The difference in AE counts between the two channels is proportional to the number of cracks per AE event, and this parameter may be thought of as the crack density. The ratio of the AE count difference to the AE count magnitude of one channel is inversely proportional to the crack growth. Both of these parameters allow the crack distribution and crack growth within each specimen to be qualitatively followed during the thermal cycling operation. Recent results which used these principles will be presented.

Berndt, Christopher C.↗