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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Application of thiolate self-assembled monolayers in selective alcohol oxidation for suppression of Pd catalyst deactivation

Rapid deactivation often reduces the effectiveness of Pt-group catalysts in the low-temperature aerobic oxidation of alcohols. We report the use of thiolate self-assembled monolayers (SAMs) as activity promoters in the liquid-phase oxidation of trans-2-hexen-1-ol (HOL) under low air pressure; the oxidation rate was significantly improved, particularly at high conversion, in contrast to the frequently observed activity decrease induced by SAM modification in hydrogenation reactions. Reaction studies indicated that in the regime of low air pressure, catalyst deactivation was mainly caused by the carbonaceous poisons generated from the reaction product 2-hexenal (HAL). Infrared spectroscopy revealed that HAL produced surface residues on Pd that poisoned the catalyst, hypothetically through decarbonylation and dimerization. This poisoning can be suppressed by the SAM modifiers, in a manner that was controllable by varying thiolate surface coverage through use of either 1-adamantanethiol (AT) or 1-octadecanethiol (C18) SAMs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Swellable Organically Modified Silica (SOMS) as a Catalyst Scaffold for Catalytic Treatment of Water Contaminated with Trichloroethylene

The properties of a swellable organically modified silica (SOMS) scaffold allowed us to synthesize “smart” catalysts with tunable accessibility of the active sites induced by organic swelling agents. Pd nanoparticles (NPs) deposited inside the swollen matrix of SOMS were shown to be selectively located on the interior surface, a surface which is only available through swelling. Techniques such as near ambient-pressure X-ray photoelectron spectroscopy (NAP–XPS) and cryogenic scanning electron microscopy (SEM) were employed to characterize Pd/SOMS in its swollen as well as unswollen state because their conventional counterparts do not preserve the swollen state of Pd/SOMS during spectral acquisition. The results obtained depicted significant differences between the unswollen and swollen state of Pd/SOMS. The most important difference is that Pd NPs became accessible on the surface after exposure to an organic compound. This indicates that the accessibility of the active sites can be controlled by changing the reaction environment, hence allowing a tunable accessibility induced by organic swelling agents. The effects of the extent of swelling on the catalytic activity were investigated by performing catalytic activity experiments in the presence of an organic swelling agent. Hydrodechlorination (HDC) of trichloroethylene (TCE), an important method of catalytic water abatement, was chosen as a model reaction. The catalytic performance was found to be proportional to the concentration of the organic swelling agent, indicating that the accessibility of active sites is related to the concentration of organic compounds. While the unavoidable reaction product HCl inhibited the commonly used HDC catalyst 1%Pd/Al 2 O 3 , 1%Pd/SOMS was able to maintain its rate throughout the reaction under the same conditions, indicating its resistance to the inhibition. Overall, a silica-based catalyst with tunable accessibility of the active sites induced by changes in the reaction environment can have significant implications for heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Fermi-level pinning, charge transfer, and relaxation of spin-momentum locking at metal contacts to topological insulators

Topological insulators are of interest for many applications in electronics and optoelectronics, but harnessing their unique properties requires detailed understanding and control of charge injection at electrical contacts. Here we present large-scale ab initio calculations of the electronic properties of Au, Ni, Pt, Pd, and graphene contacts to Bi 2 Se 3 . We show that regardless of the metal, the Fermi level is located in the conduction band, leading to n-type Ohmic contact to the first quintuplet. Furthermore, we find strong charge transfer and band-bending in the first few quintuplets, with no Schottky barrier for charge injection even when the topoplogical insulator is undoped. Our calculations indicate that Au and graphene leave the spin-momentum locking mostly unaltered, but on the other hand, Ni, Pd, and Pt strongly hybridize with Bi 2 Se 3 and relax spin-momentum locking. In conclusion, our results indicate that judicious choice of the contact metal is essential to reveal the unique surface features of topological insulators.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Directing reaction pathways via in situ control of active site geometries in PdAu single-atom alloy catalysts

Abstract The atomic scale structure of the active sites in heterogeneous catalysts is central to their reactivity and selectivity. Therefore, understanding active site stability and evolution under different reaction conditions is key to the design of efficient and robust catalysts. Herein we describe theoretical calculations which predict that carbon monoxide can be used to stabilize different active site geometries in bimetallic alloys and then demonstrate experimentally that the same PdAu bimetallic catalyst can be transitioned between a single-atom alloy and a Pd cluster phase. Each state of the catalyst exhibits distinct selectivity for the dehydrogenation of ethanol reaction with the single-atom alloy phase exhibiting high selectivity to acetaldehyde and hydrogen versus a range of products from Pd clusters. First-principles based Monte Carlo calculations explain the origin of this active site ensemble size tuning effect, and this work serves as a demonstration of what should be a general phenomenon that enables in situ control over catalyst selectivity.

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

Xenon–metal pair formation in UO 2 investigated using DFT + U

A recent experimental study on a spent uranium dioxide (UO 2 ) fuel sample from Belgium Reactor 3 identified a unique pair structure formed by the noble metal phase (NMP) and fission gas [xenon (Xe)] precipitate. However, the fundamental mechanism behind this structure remains unclear. The present study aims to provide an understanding of the interaction between five different metal precipitates [molybdenum (Mo), ruthenium (Ru), palladium (Pd), technetium (Tc), and rhodium (Rh)] and the Xe fission gas atoms in UO 2 , by using density functional theory (DFT) in combination with the Hubbard U correction to compute the formation energies involved. All DFT + U calculations were performed with occupation matrix control to ensure antiferromagnetic ordering of UO 2 . The calculated formation and binding energies of the Xe and solid fission products in the NMP reveal that these metal precipitates form stable pair structures with Xe. Notably, the formation energy of Xe–metal pairs is lower than that of the isolated single defects in all instances, with Pd and Mo showing the most favorable binding energy, likely accounting for the observed pair structure formation.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Effect of CO on alcohol oxidation over commercial oxidation catalysts for control of emissions from lean-burn engines

For commercialization, alcohol-based net-zero carbon fuels in diesel-driven internal combustion engines must meet emissions standards set by the U.S. Environmental Protection Agency. Here, a series of aged commercial oxidation catalysts, Pt diesel oxidation catalyst (DOC), Pd+Pt DOC, and Pt oxidation catalyst (Pt OC), were studied using an automated flow reactor and in situ DRIFTS techniques to investigate the impact of CO on alcohol oxidation. Surface formate and acetate intermediates were formed due to partial oxidation of methanol and ethanol, respectively. Sequential introduction of alcohol and CO experiments using in situ DRIFTS on all three catalysts showed that CO inhibited low temperature methanol oxidation. Mutual inhibition effects between CO and ethanol were observed during co-oxidation. Acetate species shifted CO oxidation to higher temperatures on Pt DOC and Pt OC, whereas CO pre-exposure inhibited acetate formation. CO oxidation occurred at lower temperatures during ethanol and CO co-oxidation on Pd+Pt DOC.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2026

ML-AMD/exa-pd

Exa-pd is a highly parallelizable workflow for constructing multi-element phase diagrams (PDs). It uses standard sampling techniques—molecular dynamics (MD) and Monte Carlo (MC)—as implemented in the LAMMPS package, to simultaneously sample multiple phases on a fine temperature–composition mesh for free-energy calculations. The workflow uses Parsl as a global controller to manage the MD/MC jobs to achieve massive parallelization with almost ideal scalability. The resulting free energies of both liquid and solid phases (including solid solutions) are then fed to CALPHAD modeling using the PYCALPHAD package for the construction of a multi-element PD.

Zhang, Feng [Ames Laboratory (AMES), Ames, IA (Uni↗
DOE OSTI2025

Engineering PdAu/CeO 2 Alloy/Oxide Interfaces for Selective Methane‐to‐Methanol Conversion with Water

The direct conversion of methane-to-methanol remains a critical challenge in methane valorization. In this study, we unveil the crucial role of PdAu/CeO 2 catalysts in enabling selective methane transformation under mild conditions, using only water as the sole oxidant. Through a combination of experimental techniques, including XPS and catalytic testing, alongside density functional theory (DFT) calculations, we demonstrate that a Pd 0.3 Au 0.7 /CeO 2 catalyst, which predominantly exposes isolated Pd atoms, achieves remarkable methanol selectivity (∼80%) at 500 K with a 1:1 methane-to-water ratio. While Pd/CeO 2 efficiently activates methane, its tendency for overreaction leads to complete methanol decomposition, thereby limiting selectivity. Alloying Pd with Au on ceria mitigates this over-reactivity, preventing methanol degradation while maintaining sufficient catalytic activity. The PdAu/CeO 2 composite exhibits a synergistic effect: Pd in contact with the ceria support facilitates methane activation and water dissociation, while Au fine-tunes reactivity to promote methanol formation. DFT calculations confirm that isolated Pd sites at the PdAu/CeO 2 interface play a key role in balancing activity and selectivity. This work underscores the importance of alloy/oxide interfaces in controlling selective methane conversion with water and offers valuable insights for designing highly efficient catalysts for methanol synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Methanol Decomposition over Palladium Particles Supported on Silica: Role of Particle Size and Co-Feeding Carbon Dioxide on the Catalytic Properties

Monodisperse palladium particles of six distinct and controlled sizes between 4-16 nm were synthesized in a one-pot polyol process by varying the molar ratios of the two palladium precursors used, which contained palladium in different oxidation states. This difference permitted size control by regulation of the nucleation rate because low oxidation state metals ions nucleate quickly relative to high oxidation state ions. After immobilization of the Pd particles on silica by mild sonication, the catalysts were characterized by X-ray absorption spectroscopy and applied toward catalytic methanol decomposition. This reaction was determined as structure sensitive with the intrinsic activity (turnover frequency) increasing with increasing particle size. Moreover, observed catalytic deactivation was linked to product (carbon monoxide) poisoning. Co-feeding carbon dioxide caused the activity and the amount of deactivation to decrease substantially. A reaction mechanism based on the formation of the {pi}-bond between carbon and oxygen as the rate-limiting step is in agreement with antipathetic structure sensitivity and product poisoning by carbon monoxide.

10 SYNTHETIC FUELS↗
DOE OSTI2023

Synthesis of core/shell nanocrystals with ordered intermetallic single-atom alloy layers for nitrate electroreduction to ammonia

Structurally ordered intermetallic nanocrystals (NCs) and single-atom catalysts (SACs) are two emerging catalytic motifs for sustainable chemical production and energy conversion. However, both have synthetic limitations which can lead to the aggregation of NCs or metal atoms. Single-atom alloys (SAAs), which contain isolated metal atoms in a host metal, can overcome the aggregation concern because of the thermodynamic stabilization of single atoms on host metal surfaces. We report a direct solution-phase synthesis of Cu/CuAu core/shell NCs with tunable SAA layers. This synthesis can be extended to other Cu/CuM (M = Pt, Pd) systems, in which M atoms are isolated in the copper host. Using this method, the density of SAAs on a copper surface can be controlled, resulting in both low and high densities of single atoms. Alloying gold into the copper matrix introduced ligand effects that optimized the chemisorption of *NO 3 and *N. As a result, the densely packed Cu/CuAu material demonstrated a high selectivity toward NH 3 from the electrocatalytic nitrate reduction reaction with an 85.5% Faradaic efficiency while maintaining a high yield rate of 8.47 mol h -1 g -1 . This work advances the design of atomically precise catalytic sites by creating core/shell NCs with SAA atomic layers, opening an avenue for broad catalytic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2016

The Role of Citric Acid in Perfecting Platinum Monolayer on Palladium Nanoparticles during the Surface Limited Redox Replacement Reaction

Cu-mediated-Pt-displacement method that involves the displacement of an underpotentially deposited (UPD) Cu monolayer by Pt has been extensively studied to prepare core-shell catalysts. It has been found that Pt clusters instead of a uniform Pt monolayer were formed in the gram batch synthesis. With a suitable surfactant, such as citric acid, the Pt shell could be much more uniform. In this study, the role of citric acid in controlling the Cu-Pt displacement reaction kinetics was studied by electrochemical techniques and theoretical approaches. It was found that citric acid strongly adsorbed on Pd, Pt, Cu/Pd, and Pt/Pd surfaces, especially in the double layer region in acid solutions. The strong adsorption of citric acid slowed down the Cu-Pt displacement reaction. The main characteristics of such strong interaction most likely arises from the OH groups in the citric acid molecule according to the molecular dynamics simulation results.

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

Aircraft in-situ measurements from SOCRATES constrain the anthropogenic perturbations of cloud droplet number

Aerosol-cloud interactions (ACI) in warm clouds alter reflected shortwave radiation by influencing cloud microphysical and macrophysical properties. The variable of state controlling ACI is the cloud droplet number concentration (N d ). Here, we examine the perturbations in N d due to anthropogenic aerosols (ΔN d, PD-PI ) using a perturbed parameter ensemble (PPE) hosted in the sixth Community Atmosphere Model (CAM6). Surrogate models are created for the CAM6 PPE outputs and are used to generate 1 million model variants of CAM6 by sampling 45 sources of parameter uncertainty. The range of uncertain physical parameters related to ACI are constrained with observations of aerosol and cloud properties from SOCRATES. The likely range of uncertain parameters and the associated range of ΔN d, PD-PI are more strongly constrained with observations of N d relative to observations of cloud condensation nuclei. We conduct sensitivity tests of how constraints on ΔN d, PD-PI are affected by systematic uncertainties in observations and our limitations in our surrogate models created for CAM6 PPE outputs. Based on this, we provide guidance on the impact of reducing systematic uncertainty in airborne microphysical observations and in surrogate models.

Song, Ci [Univ. of Wyoming, Laramie, WY (United St↗
DOE OSTI2017

Charting the relationship between phase type-surface area-interactions between the constituent atoms and oxygen reduction activity of Pd–Cu nanocatalysts inside fuel cells by in operando high-energy X-ray diffraction

The activity and stability of nanoalloy catalysts for chemical reactions driving devices for clean energy conversion, in particular the oxygen reduction reaction (ORR), depend critically on optimizing major structural characteristics of the nanoalloys, such as the phase composition, surface area and bonding interactions between the constituent atoms, for the harsh operating conditions inside the devices. The effort requires good knowledge of the potential effect of changes in these characteristics on the catalytic functionality of the nanoalloys and, hence, on the devices' performance. We present the results from an in operando high-energy X-ray diffraction (HE-XRD) study on the concurrent changes in the structural characteristics and ORR activity of Pd–Cu nanoalloy catalysts as they function at the cathode of a proton exchange membrane fuel cell (PEMFC). We find that the as-prepared Pd–Cu nanoalloys with a chemical composition close to Pd1Cu1 are better ORR catalysts in comparison with Pd1Cu2, i.e. Pd-poor, and Pd3Cu1, i.e. Pd-rich, nanoalloys. Under operating conditions though, the former suffers a big loss in ORR activity appearing as a slow-mode oscillation in the current output of the PEMFC. Losses in ORR activity suffered by the latter also exhibit sudden drops and rises during the PEMFC operation. Through atomic pair distribution function (PDF) analysis of the in operando HE-XRD data, we identify the structural changes of Pd–Cu alloy NPs that are behind the peculiar decay of their ORR activity. The results uncover the instant link between the ever-adapting structural state of ORR nanocatalysts inside an operating PEMFC and the performance of the PEMFC. Besides, our results indicate that, among others, taking control over the intra-particle diffusion of metallic species in nanoalloy catalysts may improve the performance of PEMFCs significantly and, furthermore, in operando HE-XRD can be an effective tool to guide the effort. Finally, we argue that, though showing less optimal ORR activity in the as-prepared state, monophase Pd–Cu alloy catalysts with a composition ranging between Pd1Cu1 and Pd3Cu1 may deliver optimal performance inside operating PEMFCs.

Maswadeh, Yazan↗
DOE OSTI2020

Controlled Release of Hydrogen Isotopes from Hydride-Magnetic Nanomaterials

In this work, hydrogen isotopes in the form of protium and deuterium were rapidly desorbed from magnetic-hydride iron oxide-palladium (Fe 2 O 3 -Pd) hybrid nanomaterials using an alternating magnetic field (AMF). Palladium, a hydride material with a well-known hydrogen isotope effect, was deposited on Fe 2 O 3 magnetic nanoparticle support by solution chemistries and used as a hydrogen isotope storage component. The morphological, structural, optical, and magnetic studies reveal that the Fe 2 O 3 -Pd nanoparticles (NPs) are hybrid structures exhibiting both hydrogen isotope storage (Pd) and magnetic (Fe 2 O 3 ) properties. The hydrogen isotope sorption/desorption behavior of metal hydride-magnetic nanomaterials was assessed by isothermal pressure-composition response curves (isotherms). The amount and rate of hydrogen isotope gas release was tuned by simply adjusting the strength of the magnetic field strength applied. Protium and deuterium displayed a similar loading capacity, namely H/M 0.55 and H/M=0.45, but different plateau pressures. Significant differences in the kinetics of release for protium and deuterium during magnetic heating were observed. A series of magnetically induced charge-discharge cycling experiments were conducted showing that this is a highly reproducible and robust process

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Palladium-Percolated Networks Enabled by Low Loadings of Branched Nanorods for Enhanced H 2 Separations

Nanoparticles (NPs) at high loadings are often used in mixed matrix membranes (MMMs) to improve gas separation properties, but they can lead to defects and poor processability that impede membrane fabrication. Herein, it is demonstrated that branched nanorods (NRs) with controlled aspect ratios can significantly reduce the required loading to achieve superior gas separation properties while maintaining excellent processability, as demonstrated by the dispersion of palladium (Pd) NRs in polybenzimidazole for H 2 /CO 2 separation. Increasing the aspect ratio from 1 for NPs to 40 for NRs decreases the percolation threshold volume fraction by a factor of 30, from 0.35 to 0.011. An MMM with percolated networks formed by Pd NRs at a volume fraction of 0.039 exhibits H 2 permeability of 110 Barrer and H 2 /CO 2 selectivity of 31 when challenged with simulated syngas at 200 °C, surpassing Robeson's upper bound. In conclusion, this work highlights the advantage of NRs over NPs and nanowires and shows that right-sizing nanofillers in MMMs is critical to construct highly sieving pathways at minimal loadings. In conclusion, this work paves the way for this general feature to be applied across materials systems for a variety of chemical separations.

36 MATERIALS SCIENCE↗
DOE OSTI2016

The catalytic behavior of precisely synthesized Pt–Pd bimetallic catalysts for use as diesel oxidation catalysts

The demands of stricter diesel engine emission regulations have created challenges for current exhaust systems. With advances in low-temperature internal combustion engines and their operations, advances must also be made in vehicle exhaust catalysts. Most current diesel oxidation catalysts use heavy amounts of precious group metals (PGMs) for hydrocarbon (HC), CO, and NO oxidation. These catalysts are expensive and are most often synthesized with poor bimetallic interaction and dispersion. In this paper, the goal was to study the effect of aging on diesel emission abatement of Pt–Pd bimetallic nanoparticles precisely prepared with different morphologies: well dispersed core–shell vs. well dispersed homogeneously alloyed vs. poorly dispersed, poorly alloyed particles. Alumina and silica supports were studied. Particle morphology and dispersion were analyzed before and after hydrothermal treatments by XRD, EDX, and STEM. Reactivity as a function of aging was measured in simulated diesel engine exhaust. While carefully controlled bimetallic catalyst nanoparticle structure has a profound influence on initial or low temperature catalytic activity, the differences in behavior disappear with higher temperature aging as thermodynamic equilibrium is achieved. The metallic character of Pt-rich alumina-supported catalysts is such that behavior rather closely follows the Pt–Pd metal phase diagram. Nanoparticles disparately composed as well-dispersed core–shell (via seq-SEA), well-dispersed homogeneously alloyed (via co-SEA), and poorly dispersed, poorly alloyed (via co-DI) end up as well alloyed, large particles of almost the same size and activity. With Pd-rich systems, the oxidation of Pd also figures into the equilibrium, such that Pd-rich oxide phases appear in the high temperature forms along with alloyed metal cores. Finally, the small differences in activity after high temperature aging can be attributed to the synthesis methods, sequential SEA and co-DI which give rise, after aging, to a bimetallic surface enriched in Pd.

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

Strain‐Enhanced Metallic Intermixing in Shape‐Controlled Multilayered Core–Shell Nanostructures: Toward Shaped Intermetallics

Abstract Controlling the surface composition of shaped bimetallic nanoparticles could offer precise tunability of geometric and electronic surface structure for new nanocatalysts. To achieve this goal, a platform for studying the intermixing process in a shaped nanoparticle was designed, using multilayered Pd‐Ni‐Pt core–shell nanocubes as precursors. Under mild conditions, the intermixing between Ni and Pt could be tuned by changing layer thickness and number, triggering intermixing while preserving nanoparticle shape. Intermixing of the two metals is monitored using transmission electron microscopy. The surface structure evolution is characterized using electrochemical methanol oxidation. DFT calculations suggest that the low‐temperature mixing is enhanced by shorter diffusion lengths and strain introduced by the layered structure. The platform and insights presented are an advance toward the realization of shape‐controlled multimetallic nanoparticles tailored to each potential application.

Williams, Benjamin P.↗