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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Transformation of atomically dispersed platinum in SAPO-37 into platinum clusters: catalyst for ethylene hydrogenation

Atomically dispersed supported platinum catalysts were synthesized by the reaction of Pt(acac) 2 (acac = acetylacetonato) with the silicoaluminophosphate molecular sieve SAPO-37, with infrared spectra showing that the reaction involved SAPO OH groups. Extended X-ray absorption fine structure (EXAFS) spectra show that, after heating in air to 623 K, each platinum atom on average was bonded to approximately two oxygen atoms of the SAPO support, with no evidence of platinum clusters. X-ray absorption near edge spectra (XANES) indicate a platinum formal oxidation state of approximately +2. Here, these supported mononuclear species lacked catalytic activity for ethylene hydrogenation at 1 bar and room temperature, but activity arose during catalysis in a once-through flow reactor/X-ray absorption spectroscopy cell, as the XANES white line intensity decreased, indicating reduction of the platinum, and the EXAFS-determined Pt–Pt coordination number (CN) increased from essentially zero to 2.7 ± 0.5 after 2 h, indicating the formation of platinum clusters of only a few atoms each. The data indicate the almost instantaneous formation of the clusters and identify them as the catalytically active species. Subsequent exposure of the catalyst to ethylene as in situ EXAFS and XANES data were recorded led to a decrease in the Pt–Pt coordination number to 1.6 ± 0.3 and an increase in the white line intensity, indicating partial oxidative fragmentation of the clusters by ethylene. Platinum clusters in SAPO-37 formed in separate experiments by exposure to H 2 prior to catalysis were also catalytically active for ethylene hydrogenation. Here, the data thus show how to dial in the catalytic activity by forming platinum clusters by exposure of mononuclear platinum to H 2 and how to dial back the activity by oxidative fragmentation of the clusters by reaction with ethylene, all under mild conditions; the ethylene : H 2 ratio of the reactant gas determines the average platinum nuclearity and thus the catalytic activity.

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

Optical and photophysical properties of platinum benzoporphyrins with C 2v and D 2h symmetry

Platinum(II) mono- and di-benzoporphyrins carrying either ester or imide peripheral groups have been successfully synthesized. These benzoporphyrins possessing C 2v and D 2h symmetry were investigated using a range of techniques including UV-Vis and phosphorescence spectroscopy, differential pulse voltammetry, and transient absorption spectroscopy covering wide spatial and temporal ranges. Up to three oxidation and three reductions within the accessible potential window of dichlorobenzene were observed. Facile reductions for both mono- and dibenzoporphyrin derivatives, more so with imide peripheral substituents were witnessed. Computational studies were supportive of push-pull type interactions within these molecular systems. Here, the formation of triplet excited states within 5 ps after laser excitation was confirmed by femtosecond transient absorption studies. Nanosecond transient absorption studies coupled with phosphorescence lifetime studies revealed relatively rapid relaxation of the triplet excited states as compared to a controlled platinum porphyrin suggesting push-pull type interactions on a slower time scale.

DFT calculations↗
DOE OSTI2021

Not all platinum surfaces are the same: Effect of the support on fundamental properties of platinum adlayer and its implications for the activity toward hydrogen evolution reaction

The adsorption of atomic hydrogen on a platinum monolayer supported on orthorhombic Mo 2 C(100) surface has been investigated, considering different hydrogen surface coverages. Calculations have been performed using density functional theory with the Perdew-Burke-Ernzerhof exchange correlation functional and a D3 Van der Waals corrections. The theoretical insight has been gained into atomic hydrogen interaction with Pt monolayer, supported on both molybdenum and well-studied tungsten carbide, and considering hydrogen surface coverage. Fundamental properties of Pt adlayer depend on the support, affecting hydrogen evolution activity of the resulting systems. At low hydrogen coverage all systems, with the exception of Pt supported on the molybdenum-terminated Mo 2 C, adsorb H comparably to a pristine Pt(111) surface and their high activity for the hydrogen evolution reaction is predicted. Additionally, at higher coverages supported Pt monolayers interact with atomic hydrogen unlike the Pt(111), suggesting that the activity of the supported and unsupported platinum toward hydrogen evolution reaction have different origins. Furthermore, the position of the supported platinum monolayers on the volcano curve is a function of the surface coverage, more so than for extended metal surfaces. Therefore, hydrogen surface coverage is a key variable to understand the catalytic potential, approaching towards an improved model for screening of electrocatalytic systems.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Oxygen Reduction on Platinum-Nickel and Platinum-Cobalt Alloy Based Catalysts for High Temperature Proton Exchange Membrane Fuel Cells

Catalyst layers, with commercial PtNi/TKK (TECNiE52; platinum 46.5 wt%), PtCo/TKK (TEC36E52; platinum 45.8 wt%) catalysts, and an in-house catalyst PtNi-NC (platinum 38.4 wt%), synthesised using acoustic mixer and a tube furnace, are prepared using three different ionomers: 20 wt% Nafion®, 60 wt% polytetrafluoroethylene (PTFE), and an in-house 5 wt% ionomer (‘Ionomer X’). These inks are bar-coated onto carbon paper gas diffusion layers (GDLs), which are cut into 3 cm × 5 cm pieces. The coated layers are tested for oxygen reduction in a commercial gas diffusion electrode (GDE) test cell, FlexCell® (Gaskatel GmbH, Germany), using 85 wt% phosphoric acid at both room temperature and at 155°C. This study evaluates the polynorbornene (PNB)-based in-house ionomer performance as binder and in-house catalyst oxygen reduction reaction (ORR) activity in comparison to commercial products. The catalyst layers are characterised using X-ray diffraction (XRD) analysis, X-ray photoelectron spectroscopy (XPS), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). Among the catalyst layers prepared with PTFE ionomer and tested at 155°C, the in-house catalyst demonstrates the highest ORR activity. Ionomer X proves to be a good candidate to be used as a per- and polyfluoroalkyl-free binder for high-temperature (HT) proton exchange membrane fuel cell (PEMFC) applications.

85 wt% phosphoric acid↗
DOE OSTI2023

Modeling the Effect of Surface Platinum–Tin Alloys on Propane Dehydrogenation on Platinum–Tin Catalysts

Uncertainty analysis, reported experimental literature data, and density functional theory were synthesized to model the effect of surface tin coverage on platinum-based catalysts for nonoxidative propane dehydrogenation to propylene. Here, this study tests four different platinum–tin skin surface models as potential catalytic sites, Pt 3 Sn/Pt(100), PtSn/Pt(100), Pt 3 Sn/Pt(111), and Pt 2 Sn/Pt(211), and compares them to the corresponding pure Pt surface sites using an uncertainty analysis methodology that uses BEEF-vdW with its ensembles (BMwE) to generate the uncertainty for the energies of the intermediates and transition states. One experimental data set with two experimental observations, selectivity to propylene and turnover frequency of propylene, was used as a calibration data set to evaluate the impact of the experimental data on informing the models. This study finds that the prior model for Pt 3 Sn/Pt(100) is the most active and Pt 2 Sn/Pt(211) is the most selective toward propylene. Active sites on the (100) facet have the highest probability of being responsible for C 1 and C 2 product formations (C–C bond cleavage). Increasing the Sn coverage on the (100) surface facet to a PtSn/Pt(100) active site leads to a significantly reduced rate and might explain the experimentally observed higher selectivity of Sn-doped catalysts relative to pure Pt catalysts. Next, this study finds that for all surfaces, except PtSn/Pt(100), the rate-controlling steps are the initial dehydrogenation steps alongside some partially rate-controlling second dehydrogenation steps. For PtSn/Pt(100), only the initial terminal dehydrogenation step to CH 3 CH 2 CH 2 * and second dehydrogenation steps are rate-controlling. Next, the calibrated models for all surfaces were found to be selective toward propylene production and model the reported turnover frequency successfully. Nevertheless, Pt 2 Sn/Pt(211) emerges as the active site with some (minor) evidence as the main active site based on Jeffreys’ scale interpretation of Bayes factors. This observation agrees with prior studies that also found step sites to be most likely the most relevant active sites for pure Pt catalysts. Overall, the results indicate that tin, in addition to affecting the binding strength of the adsorbed species, prevents deeper dehydrogenation (reducing coking) and cracking reactions through increasing activation barriers for unwanted side reactions.

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

Standardized protocols for evaluating platinum group metal-free oxygen reduction reaction electrocatalysts in polymer electrolyte fuel cells

Platinum group metal (PGM)-free electrocatalysts for the oxygen reduction reaction at the polymer electrolyte fuel cell cathode have shown substantial improvements in activity—especially those derived from transition metals, nitrogen and carbon. However, their stability and durability remain insufficient. A key to enabling future improvements and performance comparisons lies in the development of test protocols that are relevant to the operating conditions of the fuel cell cathode, can be completed within a reasonable time and are ubiquitously adopted. Here we propose and validate such protocols, designed with special attention to typical catalyst degradation mechanisms of PGM-free catalysts. The results of the cross-laboratory validation study using two different catalysts attest to the strength and feasibility of the proposed approach. We hope that the information provided here can serve as a broad and effective platform for assessing the performance and durability of PGM-free catalysts for polymer electrolyte fuel cells.

25 ENERGY STORAGE↗
DOE OSTI2021

Critical Review of Platinum Group Metal-Free Materials for Water Electrolysis: Transition from the Laboratory to the Market : Earth-abundant borides and phosphides as catalysts for sustainable hydrogen production

To combat the global problem of carbon dioxide emissions, hydrogen is the desired energy vector for the transition to environmentally benign fuel cell power. Water electrolysis (WE) is the major technology for sustainable hydrogen production. Despite the use of renewable solar and wind power as sources of electricity, one of the main barriers for the widespread implementation of WE is the scarcity and high cost of platinum group metals (pgms) that are used to catalyse the cathodic hydrogen evolution reaction (HER) and the anodic oxygen evolution reaction (OER). Hence, the critical pgm-based catalysts must be replaced with more sustainable alternatives for WE technologies to become commercially viable. This critical review describes the state-of-the-art pgm-free materials used in the WE application, with a major focus on phosphides and borides. Several emerging classes of HER and OER catalysts are reviewed and detailed structure-property correlations are comprehensively summarised. The influence of the crystallographic and electronic structures, morphology and bulk and surface chemistry of the catalysts on the activity towards OER and HER is discussed.

Chemistry↗
NASA NTRS1954

Some Effects of Exposure to Exhaust-gas Streams on Emittance and Thermoelectric Power of Bare-wire Platinum Rhodium - Platinum Thermocouples

Thermocouples were exposed to exhaust gases from the combustion of propane, 72-octane gasoline, and JP-4 fuel. Exposure increased the emissivity of the thermocouple wire, which increased its radiation error. Two methods are presented for determining the emittance of the wires. The emissivity of a clean platinum rhodium-platinum thermocouple was approximately 0.2 in the temperature range investigated, while the emittance of an exposed thermocouple coated with exhaust residue was about 0.5. The exposure caused negligible change in the thermoelectric power of the thermocouples.

Glawe, George E↗
NASA NTRS2003

Preparation of low-sulfur platinum and platinum aluminide layers in thermal barrier coatings

A method for preparing a coated nickel-base superalloy article reduces the sulfur content of the surface region of the metallic coating layers to low levels, thereby improving the adhesion of the coating layers to the article. The method includes depositing a first layer of platinum overlying the surface of a substrate, depositing a second layer of aluminum over the platinum, and final desulfurizing the article by heating the article to elevated temperature, preferably in hydrogen, and removing a small amount of material from the surface that was exposed during the step of heating. A ceramic layer may be deposited over the desulfurized article. The article may also be similarly desulfurized at other points in the fabrication procedure.

Spitsberg, Irene T.↗
DOE OSTI2023

Excited-State Charge Transfer in Push–Pull Platinum(II) π-Extended Porphyrins Fused with Pentacenequinone

Platinum(II) π-extended porphyrins fused with pentacenequinone and dihydropentacene have been successfully synthesized. These porphyrins were investigated using various techniques including absorption, steady-state, and time-resolved phosphorescence spectroscopy and differential pulse voltammetry. UV–vis absorption spectra of pentacenequinone-fused porphyrins (SW-Pt1 and SW-Pt2) showed unusually broad and nontypical absorption patterns. Phosphorescence spectra of SW-Pt1, SW-Pt2, and SW-Pt3 displayed similar emissions in the 704–706 nm region indicating electronic transitions of similar origin; however, the triplet lifetimes were found to be quenched in the case of both SW-Pt1 and SW-Pt2, suggesting the occurrence of excited-state events. Facile reductions were obtained for both the pentacene-quinone-fused monomer (SW-Pt2) and dimer (SW-Pt1) and were identified to be located at the pentacenequinone components. Here, the observed orbital segregations for SW-Pt2 and SW-Pt1 from DFT calculations supported the possibility of charge transfer in these push–pull systems. Interestingly, the established energy level diagram revealed that the charge transfer from the triplet excited Pt porphyrin is thermodynamically an uphill process. Systematic studies involving both femtosecond and nanosecond transient absorption techniques revealed that the singlet excited Pt porphyrins undergo an intermediate charge transfer state prior to populating the triplet state, providing a plausible explanation for phosphorescence quenching. The lifetime of the intermediate charge transfer states was found to be 25.9 and 5.68 ps, respectively, for SW-Pt1 and SW-Pt2.

Charge transfer↗
DOE OSTI2022

Colloidal Platinum–Copper Nanocrystal Alloy Catalysts Surpass Platinum in Low-Temperature Propene Combustion

Low-temperature removal of noxious environmental emissions plays a critical role in minimizing the harmful effects of hydrocarbon fuels. Emission-control catalysts typically consist of large quantities of rare, noble metals (e.g., platinum and palladium), which are expensive and environmentally damaging metals to extract. Alloying with cheaper base metals offers the potential to boost catalytic activity while optimizing the use of noble metals. In this work, we show that Pt x Cu 100–x catalysts prepared from colloidal nanocrystals are more active than the corresponding Pt catalysts for complete propene oxidation. By carefully controlling their composition while maintaining nanocrystal size, alloys with dilute Cu concentrations (15–30% atomic fraction) demonstrate promoted activity compared to pure Pt. Complete propene oxidation was observed at temperatures as low as 150 °C in the presence of steam, and five to ten times higher turnover frequencies were found compared to monometallic Pt catalysts. Additionally, through DFT studies and structural and catalytic characterization, the remarkable activity of dilute Pt x Cu 100–x alloys was related to the tuning of the electronic structure of Pt to reach optimal binding energies of C* and O* intermediates. This work provides a general approach toward investigation of structure–property relationships of alloyed catalysts with efficient and optimized use of noble metals.

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

High-Temperature RF Transmission Loss Characteristics of Platinum–Inconel 600 and Platinum–304 Steel Interconnects

Radio frequency (RF) transmission losses that occur at electronic interconnects is currently an important limitation of wireless sensors and other electronic device packages that must operate in high-temperature environments. Herein, in-situ RF transmission losses were measured for two types of interconnects: platinum (Pt) wire bonded to an Inconel 600 coaxial cable; and Pt-wire bonded to a block of 304 steel. Heating the Pt wire/Inconel interconnects at 800 °C for up to 200 hours were found to be very stable with no measurable transmission losses. In contrast, Pt wire/304 steel block interconnects examined over similar test periods at 800 °C exhibited gradual increases in transmission losses leveling off at 10, 38 and 85 mdB at 400 MHz, 700 MHz, and 1 GHz, respectively. Increasing the test temperature to 900 °C caused further elevated transmission losses of 30, 70 and 108 mdB at the same reported frequencies. By comparison, temperature cycling of the Pt wire/304 steel interconnects between room temperature and 900 °C was found to cause more significant degradation. In particular, four thermal cycles from room temperature to 900 °C resulted in losses of 75, 271, and 482 mdB at the same reported frequencies. Parabolic oxidation relative to the RF skin depth in the 304 steel block at the tested frequencies are discussed as possible reasons for the transmission losses during the isothermal soaks, whereas interconnect degradation due to differences in thermal expansion between Pt and 304 steel are primarily responsible for transmission losses caused by high temperature cycling.

304 steel↗
DOE OSTI2021

Spot the difference: hydrogen adsorption and dissociation on unsupported platinum and platinum-coated transition metal carbides

Hydrogenation reactions are involved in several processes in heterogeneous catalysis. Platinum is the best-known catalyst; however, there are limitations to its practical use. Therefore, it is necessary to explore alternative materials and transition metal carbides (TMCs) have emerged as potential candidates. We explore the possibility of using cheap TMCs as supports for a Pt monolayer, aiming to reduce the amount of the noble metal in the catalyst without a significant loss of its activity towards H 2 dissociation. Hence, analyzing H 2 dissociation from a fundamental point of view is a necessary step towards a further practical catalyst. By means of periodic DFT calculations, we analyze H 2 adsorption and dissociation on Pt/β-Mo 2 C and Pt/α-WC surfaces, as a function of hydrogen surface coverage ( Θ H ), resembling a more realistic model of a catalyst. H 2 dissociation rates were analyzed as a function of the reaction temperature. Overall, the results show that Pt/C-WC and Pt/Mo-Mo 2 C have a Pt-like behavior for H 2 dissociation at Θ H > 1/2 ML. At a particular temperature of 298 K, Pt/C-WC and Pt/Mo-Mo2C have low energy barriers for H 2 * → 2H* (0.13 and 0.11 eV, respectively), close to the value of Pt (0.06 eV). For the highest coverage, i.e. Θ H = 1, Pt/C-WC has a lower activation energy and a higher reaction rate than Pt. Finally, the H 2 dissociation rate is higher in Pt/Mo-Mo 2 C than in Pt when increasing the temperature above 298 K. Our results put Pt/C-WC and Pt/Mo-Mo 2 C under the spotlight as potential catalysts for H 2 dissociation, with a similar performance to Pt, paving the way for further experimental and/or theoretical studies, addressing the capability of Pt/TMC as practical catalysts in hydrogenation reactions.

36 MATERIALS SCIENCE↗