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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Self-regenerative noble metal catalysts supported on high-entropy oxides

Discovery of anti-sintering noble metal catalysts is challenging, as supported noble metal species tend to aggregate at high temperatures, leading to severely deteriorated catalytic performances. Here we show that 1 wt% of noble metal species including Au, Pd and Ru can be incorporated into high-entropy oxides (HEOs) through entropy stabilization at 900 °C in air. A reversible temperature-dependent dissolution–exsolution process is observed for Au-HEO. Further correlation with distinct CO oxidation capabilities demonstrates the potential to utilize the entropy effect to access self-regenerative catalysts for catalytic reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Nickel foam supported porous copper oxide catalysts with noble metal-like activity for aqueous phase reactions

Contiguous metal foams offer a multitude of advantages over conventional powders as supports for nanostructured heterogeneous catalysts; most critically a preformed 3-D porous framework ensuring full directional coverage of supported catalyst, and intrinsic ease of handling and recyclability. Nonetheless, metal foams remain comparatively underused in thermal catalysis compared to more conventional supports such as amorphous carbon, metal oxides, zeolites and more recently MOFs. Herein, we demonstrate a facile preparation of highly-reactive, robust, and easy to handle Ni foam-supported Cu-based metal catalysts. The highly sustainable synthesis requires no specialized equipment, no surfactants or additive redox reagents, uses water as solvent, and CuCl 2 (H 2 O) 2 as precursor. The resulting material seeds as well-separated micro-crystalline Cu 2 (OH) 3 Cl evenly covering the Ni foam. Calcination above 400 °C transforms the Cu 2 (OH) 3 Cl to highly porous CuO. All materials display promising activity towards the reduction of 4-nitrophenol and methyl orange. Notably, our leading CuO-based material displays 4-nitrophenol reduction activity comparable with very reactive precious-metal based systems. Furthermore, recyclability studies highlight the intrinsic ease of handling for the Ni foam support, and our results point to a very robust, highly recyclable catalyst system.

36 MATERIALS SCIENCE↗
NASA NTRS2010

Power MOSFET Thermal Instability Operation Characterization Support

Metal-oxide semiconductor field-effect transistors (MOSFETs) are used extensively in flight hardware and ground support equipment. In the quest for faster switching times and lower "on resistance," the MOSFETs designed from 1998 to the present have achieved most of their intended goals. In the quest for lower on resistance and higher switching speeds, the designs now being produced allow the charge-carrier dominated region (once small and outside of the area of concern) to become important and inside the safe operating area (SOA). The charge-carrier dominated region allows more current to flow as the temperature increases. The higher temperatures produce more current resulting in the beginning of thermal runaway. Thermal runaway is a problem affecting a wide range of modern MOSFETs from more than one manufacturer. This report contains information on MOSFET failures, their causes and test results and information dissemination.

Shue, John L.↗
DOE OSTI2020

Elucidation of the Active Sites in Single-Atom Pd 1 /CeO 2 Catalysts for Low-Temperature CO Oxidation

Supported precious metals with atomic dispersion are of great interest in catalysis due to their potentials in achieving maximum atom efficiency and unique reactivities. Herein, the active sites for low-temperature CO oxidation are elucidated over single-atom Pd 1 /CeO 2 catalysts prepared via high-temperature atom trapping (AT). The increased oxygen vacancies on CeO 2 surface induced by 800 °C air calcination result in decreased Pd–CeO 2 coordinations, i.e., the coordination-unsaturated Pd 2+ on CeO 2 . Light-off and light-out measurements coupled with CO-DRIFTS and X-ray absorption characterization confirm that these coordination-unsaturated Pd 2+ on CeO 2 are much more reactive than the fully coordinated counterpart, evidenced by a decrease of T 90 (temperature to achieve 90% conversion) by ~100 °C in CO oxidation at a gas hourly space velocity of 300 L g –1 h –1 .

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

Polyoxometalate-based complexes as ligands for the study of actinide chemistry

The complexation of actinide cations by polyoxometalates (POMs) has been extensively studied over the past 50 years. In this perspective article, we present the rich structural diversity of actinide-POM complexes and their contribution to the extension of our knowledges of actinide chemistry, especially regarding aspect of their redox chemistry, as well as application for the capture and separation of these cations in the context of nuclear fuel remediation. Furthermore, these heterometallic assemblies have also proven highly valuable as model for heterogeneous systems based on actinides supported by metal oxide surfaces. In particular, activation of the An–O bond of actinyl fragments upon complexation with lacunary POMs has been reported, creating opportunities for future developments regarding the reactivity of these heterometallic assemblies.

Auvray, Thomas↗
DOE OSTI2020

Catalytic properties of model supported nanoparticles

Nanoparticles of late transition metals are used as catalysts and electrocatalysts for industrial chemical reactions that produce fuels, convert chemical energy to electricity and clean up pollution associated with the generation and use of these fuels. For such applications, metals are usually bonded onto the surfaces of oxide or carbon support materials. To provide the energy needed for sustained economic development, we must develop new and improved solid catalysts and electrocatalysts for a variety of reactions that take better advantage of traditional and alternate energy sources (solar, wind, biomass, etc.) and avoid serious environmental problems. Additionally, since these metals are often expensive and in limited supply (e.g., Pt), we also need to develop catalysts that do not require precious metals. As a consequence, recent years have seen a dramatic increase in research aimed at providing the basic understanding needed to develop new and improved catalysts and electrocatalysts for a variety of reactions that involve nanoparticles of late transition metals supported on oxide or carbon materials. It is therefore timely to present a special issue that focusses on Catalytic Properties of Model Supported Nanoparticles. The collection highlights some of the most exciting new directions for research in this area, and provides in depth examples of some of the most cutting-edge methods, both experimental and theoretical, for studying this class of catalysts, which provide insights into structure, mechanisms, kinetics and energetics with unprecedented accuracy and detail. Finally, as Guest Editors, we present below a few of the many excellent papers published in the collection.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

The interaction of small metal particles with refractory oxide supports

Islands and continuous layers of Pd were grown in UHV on Mo and MoO subtrates. As-deposited Pd islands and layers exhibited bulk Pd adsorption properties for CO when the Pd had been deposited at RT and at thicknesses exceeding 3 ML. However, CO adsorption was drastically reduced upon annealing. This deactivation was interpreted in terms of substrate/support interaction involving the diffusion of substrate species toward the Pd surface, using AES, TPD, and work function measurement techniques. A study of the growth and annealing behavior of Pd on Mo(110) was made for thicknesses up to 12 monolayers and substrate temperatures up to 1300K, using AES, XPS, LEED, and work function measurements. At low tempertures Pd formed a monolayer without alloying. In thick layers (12 ML) annealed about 700 K, Mo diffusion into the Pd layer and alloying were noted. Such layers remained continuous up to 1100 K. Thinner Pd layers were less stable and started coalescing upon annealing to as little as 550 K. Significant changes in Pd Auger peak shape, as well as shifts of Pd core levels, were observed during layer growth and annealing.

Park, C.↗
DOE OSTI2026

Assessing metal nitrides and metal carbides as supports for thermally stable single-atom catalysts

Single-atom catalysts supported on metal oxides have been demonstrated to exhibit exceptional activity while also maintaining single-atom stability. However, alternative supports such as metal nitrides and carbides have received far less attention. Herein, we use density functional theory to systematically investigate the relative thermal stability of single-atom catalysts over a host of transition metal nitride and carbide supports. By considering the binding and dimerization energies of isolated transition metal atoms across various surface facets, we identify transition metal/support pairs that show the most promise for high-density single-atom catalysts. We find that transition metal atoms can be stabilized on both defect sites and pristine surfaces over transition metal nitrides and carbides. Furthermore, we identify promising metal/support pairings that may be suitable for achieving both stable and high-density single-atom catalysts. Furthermore, these results provide valuable insights to guide synthesis efforts towards achieving stable single-atom transition metal catalysts.

Density functional theory↗
NASA NTRS2011

Two Catalysts for Selective Oxidation of Contaminant Gases

Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to nitrogen at temperatures up to 400 C, without producing nitrogen oxides. This catalyst converts ammonia completely to nitrogen, even when the concentration of ammonia is very low. No other catalyst is known to oxidize ammonia selectively at such a high temperature and low concentration. Both the metal oxide and the support contribute to the activity and selectivity of this catalyst.

Wright, John D.↗
DOE OSTI2024

Electrocatalytic alkene epoxidation at disrupted metal ensembles in blended electrolytes

The project aims to achieve a molecular understanding of oxygen-atom transfer from water to alkenes at electrocatalytic interfaces. Molecular oxygen is the most common oxygen-atom source for epoxidations, and our group is developing sustainable routes through which epoxidation of olefins is achieved using water as the oxygen source. This route can improve the safety of the reaction while also co-producing hydrogen, demonstrating the relevance of this reaction to the energy transition. If successful in our efforts, we may enable oxygen-atom transfer reactions at the anode of water electrolyzers in the place of conventional oxygen evolution, allowing for the synthesis of sustainable value-added co-products. In this vein, we explore several approaches to acquiring high selectivity toward epoxidation over competing reactions, such as oxygen evolution. One of our aims is to allow for rational control of epoxide selectivity by disrupting contiguous metal ensembles at the surface of catalytic metal oxide nanoparticles. Specifically, we aim to synthesize single-atom, few-atom, and many-atom clusters supported on metal oxides and study the mechanism of oxygen evolution and alkene epoxidation on these materials. Thus, this approach will determine the impact of disrupting metal ensembles on the selectivity for alkene epoxidation versus oxygen evolution in blended electrolytes. Another aim is to develop a molecular-level understanding of how a blended electrolyte (i.e., a mixture of aqueous and organic solvents) influences rates of alkene epoxidation versus oxygen evolution. In other words, we are interested in understanding the catalytic influence of the solvent, as our preliminary work shows that the selectivity and reactivity of epoxidation depend strongly on the solvent composition. This investigation includes blended electrolytes and electrolytes containing redox mediator species that improve selectivity toward the desired epoxidation reaction. Overall, our proposed work will help to provide a detailed molecular-level picture of how solvents interact with substrates at the electrode-electrolyte interface, including their involvement in proton transfer reactions and screening of electric fields.

14 SOLAR ENERGY↗
DOE OSTI2024

Reevaluation of XPS Pt 4f peak fitting: Ti 3s plasmon peak interference and Pt metallic peak asymmetry in Pt@TiO2 system

The structural, electronic, and electrochemical properties of noble metals supported on transition metal oxides, such as Pt nanoparticles (NPs) supported on TiO2 (Pt@TiO2), have been extensively studied for their relevance to energy technologies, including photocatalysis, electrocatalysis, and electrochemical energy conversion. As the need to lower the amount of Pt and other noble metals used in energy conversion systems becomes urgent, it is essential to accurately quantify the loading of these metals and electronic density redistribution between them and their supports. X-ray photoelectron spectroscopy (XPS) is widely used for the identification and quantification of chemical species. In particular, fitting of the Pt 4f spectra for Pt@TiO2 is frequently performed to determine the chemical environment and oxidation state of Pt, which strongly affect the physical behavior and catalytic performance of this system. Here, we show that neglecting contributions due to the Pt surroundings and the asymmetry of the Pt metal peak in the line shape fitting can lead to severe mischaracterization of the oxidation state of Pt. We quantify the effects of background contributions that stem from the TiO2 support and discuss how factoring in the strong asymmetry of Pt 4f doublets, which stems from the shake-up type processes, affects the interpretation of Pt 4f XPS line shape.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Atomically dispersed supported metal species as catalysts for alcohol conversion, and hydrogen and chemicals production

Supported single metal atoms are a new class of catalyst in which precious metals can be used at the ultimate limit of atom efficiency. While great strides have been made in demonstrating the potential of single-atom catalysts for many industrial reactions, there remains much debate in the literature over the nature of the active sites and the reaction mechanisms. The major goal of this project was to elucidate how atomic dispersions of metals on oxide supports enable catalytic reactions and how to stabilize such active sites for practical catalyst development. This is particularly important for the reactions of interest to fuel reforming for hydrogen generation in which atomically-dispersed metal ions on various oxide surfaces have been identified as the active sites. Working with trace amounts of precious metals is both fundamentally intriguing and of great practical interest in our continual search for low-cost, efficient and stable catalysts for the conversion of fuels to hydrogen under highly demanding operating conditions. A second major goal of the project was to rationally design and prepare single atom alloy (SAA) catalyst compositions based on information gathered from surface science studies on model catalysts and by catalytic evaluation of nanoparticle SAA analogs under realistic conditions. The overarching goal was to use the knowledge garnered from this project to design and develop new catalysts at the single atom limit, which can be applied to selective hydrogenation reactions (alkynes and dienes to alkenes) and the dehydrogenation of methanol and ethanol to value-added products at near-ambient conditions. Detailed information about the results of the project are given below.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Reduction-Controlled Atomic Migration for Single Atom Alloy Library

Here, picturing the atomic migration pathways of catalysts in a reactive atmosphere is of central significance for uncovering the underlying catalytic mechanisms and directing the design of high-performance catalysts. Here, we describe a reduction-controlled atomic migration pathway that converts nanoparticles to single atom alloys (SAAs), which has remained synthetically challenging in prior attempts due to the elusive mechanism. We achieved this by thermally treating the noble-metal nanoparticles M (M = Ru, Rh, Pd, Ag, Ir, Pt, and Au) on metal oxide (CuO) supports with H2/Ar. Atomic-level characterization revealed such conversion as the synergistic consequence of noble metal-promoted H2 dissociation and concomitant CuO reduction. The observed atomic migration pathway offers an understanding of the dynamic mechanisms study of nanomaterials formation and catalyst design.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Dilute Alloys Based on Au, Ag, or Cu for Efficient Catalysis: From Synthesis to Active Sites

The development of new catalyst materials for energy-efficient chemical synthesis is critical as over 80% of industrial processes rely on catalysts, with many of the most energy-intensive processes specifically using heterogeneous catalysis. Catalytic performance is a complex interplay of phenomena involving temperature, pressure, gas composition, surface composition and structure over multiple length and time scales. In response to this complexity, the integrated approach to heterogeneous dilute-alloy catalysis reviewed here brings together materials synthesis, mechanistic surface chemistry, reaction kinetics, in-situ and operando characterization, and theoretical calculations in a coordinated effort to develop design principles to predict and improve catalytic selectivity. Dilute alloy catalysts—in which isolated atoms or small ensembles of the minority metal on the host metal lead to enhanced reactivity while retaining selectivity—are particularly promising as selective catalysts. Several dilute alloy materials using Au, Ag and Cu as the majority host element, including more recently introduced support-free nanoporous metals and oxide-supported nanoparticle "raspberry colloid templated (RCT)" materials, are reviewed for selective oxidation and hydrogenation reactions. Progress in understanding how such dilute alloy catalysts can be used to enhance selectivity of key synthetic reactions is reviewed, including quantitative scaling from model studies to catalytic conditions. The dynamic evolution of catalyst structure and composition studied in surface science and catalytic conditions and their relationship to catalytic function are also discussed, followed by advanced characterization and theoretical modeling that have been developed to determine the distribution of minority metal atoms at or near the surface. Furthermore, the integrated approach demonstrates the success of bridging the divide between fundamental knowledge and design of catalytic processes in complex catalytic systems, which can accelerate the development of new and efficient catalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗