Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “PT”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Global Optimization of Adsorbate Covered Supported Cluster Catalysts: The Case of Pt 7 H 10 CH 3 on α-Al 2 O 3

Determining structures of supported sub-nanometer catalytic clusters is important for finding binding sites, active sites, and reaction mechanisms. In realistic conditions, the cluster may be covered with adsorbed reactants and intermediates, which strongly affect the structure of the cluster compared to the low coverage regime. The global optimization of supported adsorbate-covered clusters is not possible with existing methods. In this paper, we present a customized Basin Hopping (BH) approach, with a core (metal cluster) – shell (adsorbates) separation scheme, and perform first applications to the search of low-energy isomers of Pt 7 /α-Al 2 O 3 at high hydrogen coverage (10H). The presence of adsorbates significantly alters the low-energy isomers compared to bare Pt 7 /α-Al 2 O 3 . Molecular dynamics simulations additionally show the different time-scales associated with the mobility of H and Pt atoms. The revised BH method with core-shell separation presents key advantages for the structural exploration of adsorbate-covered supported catalysts, relevant to realistic catalytic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Designing Efficient Catalysts through Bimetallic Architecture: Rh@Pt Nanocubes as a Case Study

Bimetallic nanocatalysts often have increased activities and stabilities over their monometallic counterparts due to surface strain effects and electron transfer between the two metals. We demonstrate that the performance of a nanocatalyst can be precisely manipulated in shape-controlled nanocrystals through a bimetallic core@shell architecture. This ability is achieved in a model core@shell Rh@Pt nanocube system through control of shell thickness. The enhanced performance with thin-shelled nanocrystals is correlated with the weakening of surface–adsorbate interactions. In these thin-shelled Rh@Pt nanocubes, the maximum current density achieved during formic acid oxidation was over 2 times greater than that achieved with similarly sized Pt nanocubes, with a decreased CO poisoning ratio as well. Finally, the strategy employed here should also enhance the performance of many other bimetallic nanomaterials composed of more cost-effective metals too.

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

Surface analysis insight note: Illustrating the effect of adventitious contamination on Pt photoemission peak intensities

Adventitious carbon contaminations are not only omnipresent and used for charge referencing of XPS spectra but also can alter the apparent presence of the element peaks that span over the large spectral window of binding energies. This Insight note describes the effect of an adventitious contamination layer on Pt and presents, in brief, the approach whereby the component spectra are derived for ion beam cleaned Pt samples that can then utilize linear mathematics to peak fit said spectra thus quantifying the amount of each component including that assigned to the contamination itself of Pt metal.

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

Synthesis of Highly Dispersed and Highly Stable Supported Au–Pt Bimetallic Catalysts by a Two-Step Method

Highly dispersed and highly stable supported bimetallic catalysts were prepared using a two-step process. Pt nanoparticles (NPs) were first deposited on porous γ-Al2O3 particles by atomic layer deposition (ALD). Au NPs were synthesized by using gold(III) chloride as the Au precursor, and then immobilized on ALD Pt/γ-Al2O3 particles. The Au–Pt bimetallic catalysts were highly active and highly stable in a vigorously stirred liquid phase reaction of glucose oxidation.

Wang, Xiaofeng↗
DOE OSTI2018

Investigation of Pt and Pd Modified WO{sub 3} and ZnO Based Thin Film Sensors for Ethanol Sensing

Ethanol sensors based on different WO{sub 3} and ZnO structures are studied in the present work. The XRD and SEM processes are used to characterize the sensing layer’s surface morphology which reveals the presence of nanoparticle in sensing layer. Further reducing the nanoparticle diameter by the addition of palladium (Pd) and platinum (Pt) for both the sensors (ZnO and WO{sub 3}) gives good results on sensitivity, operating temperature, response time and recovery time. Nanoparticle diameter for undoped WO{sub 3}, Pd-modified WO{sub 3} and Pt-modified WO{sub 3} based sensors is 11.8, 6 and 5.4 nm, whereas nanoparticle diameter for undoped, Pd-modified and Pt-modified ZnO based sensors is 20, 14 and 11 nm, respectively. Analysis of dynamic response of the sensors when exposed to different concentrations of ethanol vapour (from 500 to 10,000 ppm) and various temperatures indicate the improvement in sensitivity up to 77.2% for WO{sub 3} and 74.6% for ZnO based sensors.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2012

Fuel Cells Catalyst for Start-up and Shutdown Conditions: Electrochemical, XPS, and TEM Evaluation of Sputter-Deposited Ru, Ir, and Ti on Pt-Nano-Structured Thin Film (NSTF) Support

Minute amounts of Ru, Ir and Ti (2 and 10 g/cm2) sputter-deposited over 3M Pt-coated nano-structured thin film (NSTF) substrate were evaluated as oxygen evolution reaction (OER) catalysts in a polymer electrolyte membrane (PEM) environment. The purpose of the study was to explore the suitability of these elements for modifying both the anode and the cathode catalysts in order to lower the overpotential for the oxidation of water during transient conditions. By keeping the electrode potential as close as possible to the thermodynamic potential for OER, other components in the fuel cell, such as platinum, the gas diffusion layer and the bipolar plates, will be less prone to degradation. While Ru and Ir were chosen due to their high OER activity in aqueous environment, Ti was also included due to its ability to stabilize the OER catalysts. The 3M Pt-NSTF was selected as a stable, carbon-free substrate. The surface chemistry and the morphology of OER catalysts on Pt-NSTF were examined by x-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM). The OER catalytic activity of Ru and Ir in PEMs compares well with their behavior in aqueous environment. It was found that Ru is more active than Ir, that Ir is considerably more stable, while the mass activity of both is higher in comparison with similar OER catalyst.

OER↗
DOE OSTI2022

Characterization of the atomic-level structure of γ-alumina and (111) Pt/γ-alumina interfaces

The atomic-level structure of platinum/γ-alumina interfaces is characterized in a model system of dense γ-alumina embedded with faceted Pt NPs produced by implantation of platinum ions into sapphire followed by thermal annealing in air at 800 °C. Aberration-corrected scanning transmission electron microscopy (STEM) was used to collect atomic-resolution images, which are compared to STEM image simulations of two experimentally-based bulk models of γ-alumina by Smrčok et al. and Zhou and Snyder. A density functional theory (DFT) based model of (111) interfaces with different chemical terminations (O, Al 1 , Al 2 ) of the γ-alumina developed by Oware Sarfo et al. is also compared to experimental STEM data from Pt/γ-alumina interfaces. Further, the Smrčok γ-alumina model provides a better fit than the Zhou structure to the bulk of the γ-alumina. The oxygen-terminated Oware Sarfo model best fits the experimental data and is a very good model close to the interface. However, the fit of the interface model to the experimental data is poorer beyond the third atomic layer in the γ-alumina. This is attributed to compromises required in the design of the model to limit the cell size and computational time for DFT calculations. Understanding the accuracy and limits of the structural models of γ-alumina and Pt/γ-alumina interfaces is important to further the understanding of the structure/property relationships in this system.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Comment on 'Supersymmetry, PT-symmetry and spectral bifurcation'

We demonstrate that the recent paper by Abhinav and Panigrahi entitled 'Supersymmetry, PT-symmetry and spectral bifurcation' [K. Abhinav, P.K. Panigrahi, Ann. Phys. 325 (2010) 1198], which considers two different types of superpotentials for the PT-symmetric complexified Scarf II potential, fails to take into account the invariance under the exchange of its coupling parameters. As a result, they miss the important point that for unbroken PT-symmetry this potential indeed has two series of real energy eigenvalues, to which one can associate two different superpotentials. This fact was first pointed out by the present authors during the study of complex potentials having a complex sl(2) potential algebra.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Boosting catalytic propane oxidation over PGM-free Co 3 O 4 nanocrystal aggregates through chemical leaching: A comparative study with Pt and Pd based catalysts

Rational modification of interfacial structure and chemistry can help effectively tailor the reactivity and stability of heterogeneous catalysts regardless of their elemental or compound natures. In this work, a diluted acidic treatment was designed and utilized to modify the surface structure and chemistry of spinel Co 3 O 4 nanoparticles. Such a chemical leaching strategy has significantly promoted the propane oxidation activity of the PGM-free Co 3 O 4 nanocrystal aggregates. With a much higher activity than the commercial Al 2 O 3 supported Pt and Pd catalysts, these leached nanoparticle aggregates exhibited much more abundant defects, surface Co 2+ and chemisorbed oxygen species. Such surface-modified Co 3 O 4 nanocatalysts have displayed excellent and stable propane oxidation efficiency independent of both O 2 and C 3 H 8 concentrations, where the activities of both commercial Pt (or Pd)/Al 2 O 3 and self-made Pt (or Pd)/CeO 2 catalysts were greatly affected by different O 2 and C 3 H 8 concentrations. Meanwhile, the Co 3 O 4 nanocrystal aggregates catalyst exhibited good performance in presence of water or sulfur dioxide. This facile chemical leaching based technique provides a potential means to make highly active and stable oxide catalysts.

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

Electrocatalytic decarboxylation of carboxylic acids over RuO 2 and Pt nanoparticles

Here, we report electrocatalytic decarboxylation (ECDX) of valeric acid into paraffins, olefins, and alcohols via (non-)Kolbe electrolysis on electrodes with RuO 2 and Pt nanoparticles (NPs) as a greener alternative to thermocatalytic decarboxylation. The turnover frequency of ECDX increases, while the specific activity peaks as RuO 2 NP size increases. These opposing trends make the particle size of ∼ 12 nm the optimum size for ECDX on RuO 2 . Bulk Pt was active for ECDX, while Pt NPs were only active for the oxygen evolution reaction under our conditions. ECDX current efficiency remained constant in the studied potential range on RuO 2 NPs. Esterification was the favored reaction at 2.5 V vs. RHE; however, Kolbe electrolysis was the favored reaction at the expense of the esterification at 4.5 V vs. RHE. This work highlights the performance of nanostructured materials as an alternative to bulk materials as anodes for oxidative upgrading of carboxylic acids.

Kolbe electrolysis↗
DOE OSTI2025

Nuclear excitation functions for medical isotope production: Targeted radionuclide therapy via nat IR$(d, x)$ 193m Pt

193m Pt is an Auger emitting radionuclide which may have therapeutic potential, particularly when labeled to the chemotherapeutic drug cisplatin. One challenge to broader explorations of its clinical potential is the need for production routes with high specific activity. As part of a larger campaign to address gaps in reaction data for emerging medical radionuclides, this work seeks to characterize the nat Ir(d,x) reactions as a potential production pathway for 193m Pt. A stacked target irradiation, consisting of natural iridium, iron, nickel, and copper foils, was performed using a 33 MeV deuteron beam at the Lawrence Berkeley National Laboratory 88-Inch Cyclotron. This measurement, along with previous experimental data, suggests an energy window between 11 to 18 MeV to maximize the production and radiopurity of 193m Pt. This experiment has yielded cross sections for 43 channels of deuteron-induced reactions from threshold to 30 MeV, including the first experimental results of nat Ir(d,x) 188m1+g,190m1+g Ir (cumulative), nat Ni(d,x) 56,57,58 m,58g Co (independent), nat Cu(d,x) 61 Co (cumulative) and nat Fe(d,x) 53 Fe, 48 V (cumulative). The results were compared with literature data, the TENDL-2023 database, and default theoretical calculations from the TALYS-2.04, CoH-3.6.0, EMPIRE 3.2.3, and ALICE-2020 reaction modeling codes. Here, this work presents another example of the lack of predictive capabilities for this set of modern nuclear-reaction modeling codes, and highlights the unsatisfactory modeling of experimental cross sections. Experimental data are important to improve the codes in general, and new experimental results can be used to improve the models. Finally, this measurement has revealed the need for an updated evaluation of the nat Cu(d,x) 63 Zn deuteron monitor reaction.

193mPt↗
DOE OSTI2018

Effect of hydrogen coverage on hydrogenation of o -cresol on Pt(111)

The conversion of phenolics over metal catalysts is an important process for upgrading biofuels. With density functional calculations, hydrogenation of o-cresol on the hydrogen-covered Pt(111) surface was investigated. Here, the results show that the coverage of hydrogen plays a significant role in the reaction rate while it does not affect the reaction selectivity. The reaction barriers of the hydrogenation process leading to the formation of both 2-methyl-cyclohexanone (the intermediate product) and 2-methyl-cyclohexanol (the final product) at high H coverages (~ 1 ML) are found to be smaller by 0.14–0.69 eV than those at lower H coverages (~ 1/25 ML). After both hydrogen and cresol are adsorbed on Pt(111) from their initial gas phase state, the reaction energy of each hydrogenation step on the surface is also dependent on the hydrogen coverage. On the H-covered Pt(111) surface, most steps of hydrogenation involve exothermic reactions when the hydrogen coverage is high while they are endothermic reactions at low hydrogen coverages. The differences in reaction rate and reaction energy between high and low H coverages can be understood with the coverage-dependent bonding strength and configurations.

08 HYDROGEN↗
DOE OSTI2024

Tunable amorphous carbon films formed on ultralow wear, Pt–Au alloys

The mechanocatalytic formation of carbonaceous films at the interface between sliding metallic contacts is simultaneously advantageous for reducing friction and adhesion in several tribological applications and detrimental for electrical contacts as they can induce device failure by increasing the contact resistance. Yet, remarkably little is still known about the chemistry, structural and mechanical properties, and tunability of these interfacial layers. In this study, we performed contact pressure-dependent tribological experiments in dry nitrogen containing trace organics on four, nanocrystalline Pt–Au alloys ([Au] from 0 at.% to 10 at.%) – a promising class of alloys for ultralow wear and electrical contact applications. The ex-situ, multi-technique characterization results did not only provide insights into the chemical nature and mechanical behavior of the mechanocatalytic, carbon-rich films formed on Pt–Au surfaces, but also revealed the interplay between catalytic and mechanochemical tribofilm formation controlled by the composition-dependent electronic structure of the Pt–Au substrate and the applied contact pressure. The results of this work provide guidelines for tailoring nanocrystalline alloys to control their mechanocatalytic activity on the basis of variations of the alloy mechanical properties and element's electronic structure with the alloy stoichiometry.

AFM↗
DOE OSTI2020

First-principle investigation on catalytic hydrogenation of benzaldehyde over Pt-group metals

We report that understanding the hydrogenation of organic compounds in the aqueous phase has always been fundamentally important for improving carbon neutral pathways to fuels and value-added chemicals. In this study, we investigated both thermodynamic and kinetic profiles of benzaldehyde hydrogenation over the Pd(111) and Pt(111) metal surfaces using density functional theory (DFT) and ab initio molecular dynamic (AIMD) simulations. The adsorption of H 2 shows the mixed preference of H adsorption sites on the Pt(111), while the fcc adsorption site is dominant for H on the Pd(111). When benzaldehyde is added to the systems, we observe a strong reduction of benzaldehyde on charged Pd (111) surface compared with that on neutral surface. In contrast, charged state of the Pt(111) surface does not change their interaction. Subsequent hydrogenation reaction of benzaldehyde over Pd(111), proceeding via Langmuir-Hinshelwood mechanism, is affected by two major factors: the presence of H 2 O solvent and surface charge. The presence of H 2 O solvent greatly reduces the activation energy of C-H and O-H bond formation during the hydrogenation process. Furthermore, the hydrogenation step via C-H bond formation is preferred thermodynamically and kinetically over O-H bond formation during thermocatalytic hydrogenation, while the opposite trend holds true during electrocatalytic hydrogenation.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2023

CO 2 -mediated oxidative dehydrogenation of propane enabled by Pt-based bimetallic catalysts

The greenhouse gas CO 2 is a promising soft oxidant for the oxidative dehydrogenation of light alkanes. However, the occurrence of side reactions including cracking, hydrogenolysis, and reforming results in lower olefin yields compared with direct dehydrogenation. Here, we report that Pt-M (M = Sn/In/Zn) bimetallic catalysts on non-redox-active silica support can break the equilibrium limit of direct propane dehydrogenation using CO 2 as a co-reactant to consume the hydrogen formed in propane dehydrogenation. Unlike the commonly postulated direct CO 2 -assisted dehydrogenation mechanism, we confirm that CO 2 -oxidative dehydrogenation of propane (ODHP) proceeds in two tandem steps on these bimetallic catalysts, i.e., propane dehydrogenation and reverse water-gas shift, with the latter being the rate-determining step. In situ X-ray absorption studies and density functional theory calculations suggest that the Pt m M n -MO x (e.g., Pt 3 Sn-SnO x ) interfaces are likely active sites.

03 NATURAL GAS↗
DOE OSTI2022

Carbon nanotubes decorated with Pt as a viable electrocatalyst system using electrochemical atomic layer deposition

Surface limited redox replacement (SLRR) is an electrochemical deposition method designed to deposit metal thin films, typically onto other metals, that are mere monolayers in thickness, where such low dimensions allows catalyst-support interactions to affect catalyst efficiency. Here we explore the growth of Pt, using iterative Cu-mediated SLRR cycles, directly onto carbon nanotubes (CNTs) which are potentially good candidates as electrocatalyst supports due to their electrical conductivity and chemical resistance. Here scanning electron microscope images showed that Pt grew as nanoparticles, and hydrogen underpotential deposition from cyclic voltammetry showed that the active surface area approached an asymptotic value around eight iterations. Catalytic activity, measured using the oxygen reduction reaction, reached a maximum at ten iterations. Both are shown to be influenced by the growth mode, but electrochemical modeling indicates that the trend in activity is also due to a change in activation energy, possibly due to changes in Pt electronic structure due to interactions with the CNTs. Durability cycling showed a greater than 85% retention of surface area for the first 10,000 cycles of accelerated stress testing but decayed steadily to about 50% after 30,000 cycles. This performance may be related to the phenomenon that limits surface area growth.

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

Activity model for 36 elements in Fe-Ni-Si-S-C liquids with application to terrestrial planet accretion and mantle geochemistry: New data for Ru, Re, Pt, Os, Ti, Nb, and Ta

Understanding siderophile element partitioning between metal and silicate melts under diverse conditions can be used to place important constraints on the materials and conditions of planetary accretion and core formation, as well as post core formation processes. However, the effects of Si on the partitioning and activity coefficients for these elements are not well known, despite Si likely being one of the dominant light elements in Earth’s core. To address this gap in understanding, we have undertaken a systematic study of the highly siderophile elements Re, Pt, Os, and Ru, and the refractory lithophile elements Nb, Ta and Ti at 1600 °C and 1 GPa, to derive epsilon interaction parameters for these elements in FeSi metallic liquids. Positive epsilon interaction parameters were measured for Nb, Ta, Ti, Ru, Re, Pt, and Os, indicating that dissolved Si in Fe liquids causes a decrease in their metal/silicate partition coefficients (or ‘silicophobic’ behavior). Furthermore, ε$_{Re, Os, or Ru}^{Si}$ > ε$_{Re, Os, or Ru}^{S}$ which means Si causes a larger decrease in D(metal/silicate) than S, and the chalcophile behavior expected from some elements will be completely masked by the presence of Si in a metallic liquid. The new parameters are used to update an activity model that now includes 36 siderophile elements in Fe-Ni-Si-S-C liquids (27 trace elements considered here). Systematic assessment of these 27 elements shows which have the strongest affinity for Si, C, and S, and also how activity coefficients for these elements would vary during accretion and core formation in Earth, Mars, and Mercury of widely differing fO 2 and core compositional conditions. The activity model is combined with new partitioning expressions for Mo, W, Cr, Re Ru, Pt, and Os and applied to aspects of post core formation mantle geochemistry of Earth, Mars, and Mercury. Our updated expressions show that the BSE Mo/W ratio can easily be achieved with metal/silicate partitioning during growth of the Earth, whereas Re, Os and Ru become lower than and highly fractionated compared with BSE values during core formation and accretion, and thus nearly 99% of their BSE abundances are likely contributed by late accretion. Ru isotopes should be a very good indicator of the source material for the late accretion. The high Pt/Os and Re/Os developed in a deepening magma ocean during the growth of the Earth, indicates 186 Os and 187 Os isotopes could be coupled if this ancient material remained isolated and subsequently became entrained in mantle plumes and measured in surficial lavas. The extent to which this occurred will be limited by the low Os content of this ancient material, thus requiring mixing as a major component in plume sources. Martian mantle Hf/W ratio stays low during accretion and core formation modelling, suggesting that W isotope anomalies are more likely due to solid/liquid silicate fractionation than to core formation. Finally, Ti contents measured by MESSENGER at Mercury’s surface can be explained by segregation of either a metallic core (IW-6 to -8) or metallic core + sulfide (IW-4 to -7.5) followed by mantle melting.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2019

In-situ and ex-situ comparison of the electrochemical oxidation of SO 2 on carbon supported Pt and Au catalysts

Electrochemical characterizations are performed using thin films and commercial carbon supported platinum and gold catalysts for sulfur dioxide oxidation, the primary electrochemical oxidation reaction in the Hybrid-sulfur (HyS) thermochemical process. Electrochemical evaluation of metal thin films qualitatively confirms the higher activity of Au over Pt, AuPt, Pd, and Ir for the electrochemical oxidation of SO 2 . Ex-situ testing, using rotating disk electrode (RDE), shows an earlier onset potential for Au/C at low sulfuric acid concentrations (C ≤ 3.5 M) and a higher turnover frequency than Pt/C at sulfuric acid concentrations ranging from 3.5 M to 9 M. In-situ electrolysis experiments using low catalyst loadings (0.1 mg Au cm –2 , a factor of ≥5 lower than typical loadings) confirm that Au nanoparticles exhibit higher current densities and greater stability than Pt nanoparticles. This is consistent with the thin film screening studies, which showed higher activity with increasing gold content in AuPt thin films. Here, this work reveals an alternative material to state-of-the-art Pt to lower the energy needs and aid the HyS cycle in reaching the target of $2/kg H 2 set forth by the Department of Energy to achieve economic feasibility of large-scale hydrogen generation.

08 HYDROGEN↗