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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 847 records · Page 47
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 OSTI2021

New Opportunity for Carbon-Supported Ni-based Electrocatalysts: Gas-Phase CO 2 Methanation

The cost-effectiveness and excellent performance of conductive-carbon-supported Ni-based electrocatalysts make them attractive materials for hydrogen oxidation and evolution reactions. However, they were previously unused in gas-phase hydrogenation reactions. In this work, we have expanded the applicability of commercially available advanced Ni/C, NiMo/C and NiRe/C materials from electrocatalysis to heterogeneous catalysis of CO 2 methanation. Our catalytic testing efforts indicate that the monometallic Ni/C material demonstrates the best CO 2 methanation properties, achieving an excellent CO 2 conversion of 83 % at 400 °C with nearly complete selectivity to CH 4 of 99.7 %, plus exhibiting intact performance during 90 h of time-on-stream testing. Such catalytic properties are among the highest reported to date among carbon-supported Ni-based methanation catalysts. Finally, excellent performance of Ni/C stems from the good dispersion of the Ni nanoparticles over N-containing carbon support material.

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

Ionic Liquid Sheath Stabilizes Atomically Dispersed Reduced Graphene Aerogel‐Supported Iridium Complexes during Ethylene Hydrogenation Catalysis

Abstract An atomically dispersed reduced graphene aerogel (rGA)‐supported iridium catalyst having reactive ethylene ligands was synthesized at an iridium loading of 9.9 wt % and coated with an ionic liquid, 1‐ethyl‐3‐methylimidazolium acetate ([EMIM][OAc]). Continuous‐scan X‐ray absorption spectra demonstrated that the iridium remained site‐isolated in flowing equimolar C 2 H 4 and H 2 during a temperature ramp to 100 °C. The data further showed the lack of detectable iridium aggregation when the feed was H 2 ‐rich or even pure H 2 at 100 °C. An Arrhenius plot determined for ethylene hydrogenation catalysis with the sample in flowing equimolar ethylene and hydrogen showed no variation in the apparent activation energy at temperatures up to 100 °C, confirming that the active sites remained intact at the higher temperatures. The results point to opportunities for overcoming the stability limitations of atomically dispersed supported noble metal catalysts by choice of electron‐donor supports and ionic liquid sheaths.

Kurtoğlu‐Öztulum, Samira F.↗
DOE OSTI2025

Supported Single‐Atom Manganese Catalysts for the Trimerization of Ethylene

Selective ethylene oligomerization via oxidative cyclization, forming metallacyclic intermediates, is typically catalyzed by molecular titanium and chromium complexes to produce butenes, hexenes, or octenes, depending on the supporting ligand framework. However, this mechanism requires significant electron density at the metal active site and is not known to be generalizable to other first-row transition metals. In this work, we computationally investigate the electronic modulation of five transition metals (Mn, Fe, Co, Ni, and Cu) supported on titania (TiO₂) through reductive lithium intercalation to promote selective oligomerization via oxidative cyclization, using density functional theory (DFT). Our findings predict that Mn/LiTiO₂ exhibits high catalytic activity due to the exergonic nature of oxidative cyclization with two ethylene molecules. Additionally, lithium titanate (LiTiO₂) supports enhance catalytic performance compared to TiO₂. Experimental validation confirms that Mn/LiTiO₂ achieves higher conversion rates and improved selectivity toward hexene (C₄:C₆ = 1:2.6). The enhanced activity is attributed to lithiation, which alters the electronic environment around Mn active sites. Mechanistic studies reveal that the formation of a seven-membered ring, a key intermediate for hexene formation, is more favorable on LiTiO₂ than TiO₂. This work provides the first evidence of Mn catalyzing selective ethylene oligomerization via oxidative cyclization in either homogeneous or heterogeneous catalysis.

Kim, Yu Lim [Argonne National Laboratory (ANL), Ar↗
DOE OSTI2026

Influence of Polymer and Support Interactions on the Electrocatalytic Properties of Heterogenized Molecular Complexes

Heterogenized molecular catalysts have been the subject of increasing interest in the context of electrochemical small molecule activation due to the possibility of active site homogeneity and tunability, which can surpass many nanostructured materials. When molecular catalysts strongly interact with carbon supports through π–π interactions, they tend to show higher selectivity and activity during heterogeneous electrochemical reactions. Indeed, ligand modifications in the secondary sphere that allow for more π–π overlap between catalyst and carbon support often show improved performance. Interactions between catalyst and polymer binder are also a possible modulus of control in these reactions, either through coordinating moieties that interact with active sites or through control over substrate or product transport. Finally, the covalent linking of molecular complexes onto carbon materials has also been shown to result in high activity and stability. Recent advances in the use of carbon supports, both through covalent and non-covalent interactions, and polymers to alter small molecule activation by heterogenized molecular catalysts are summarized in this Perspective.

Johnson, Elizabeth K. [University of Virginia, Cha↗
DOE OSTI2017

High‐Energy‐Resolution X‐ray Absorption Spectroscopy for Identification of Reactive Surface Species on Supported Single‐Site Iridium Catalysts

Abstract We report high‐energy‐resolution X‐ray absorption spectroscopy detection of ethylene and CO ligands adsorbed on catalytically active iridium centers isolated on zeolite HY and on MgO supports. The data are supported by density functional theory and FEFF X‐ray absorption near‐edge modelling, together with infrared (IR) spectra. The results demonstrate that high‐energy‐resolution X‐ray absorption spectra near the iridium L III (2p 3/2 ) edge provide clearly ascribable, distinctive signatures of the ethylene and CO ligands and illustrate effects of supports and other ligands. This X‐ray absorption technique is markedly more sensitive than conventional IR spectroscopy for characterizing surface intermediates, and it is applicable to samples having low metal loadings and in reactive atmospheres and is expected to have an increasing role in catalysis research by facilitating the determination of mechanisms of solid‐catalyzed reactions through identification of reaction intermediates in working catalysts.

Hoffman, Adam S.↗
DOE OSTI2020

Controlled One‐pot Synthesis of Nickel Single Atoms Embedded in Carbon Nanotube and Graphene Supports with High Loading

Abstract Single‐atom catalysts (SACs) have attracted much attentions due to the advantages of high catalysis efficiency and selectivity. However, the controllable and efficient synthesis of SACs remains a significant challenge. Herein, we report a controlled one‐pot synthesis of nickel single atoms embedded on nitrogen‐doped carbon nanotubes (NiSA−N−CNT) and nitrogen‐doped graphene (NiSA−N−G). The formation of NiSA−N−CNT is due to the solid‐to‐solid rolling up mechanism during the high temperature pyrolysis at 800 °C from the stacked and layered Ni‐doped g‐C 3 N 4 , g‐C 3 N 4 −Ni structure to a tubular CNT structure. Addition of citric acid introduces an amorphous carbon source on the layered g‐C 3 N 4 −Ni and after annealing at the same temperature of 800 °C, instead of formation of NiSA−N−CNT, Ni single atoms embedded in planar graphene type supports, NiSA−N−G were obtained. The density functional theory (DFT) calculation indicates the introduction of amorphous carbon source substantially reduces the structure fluctuation or curvature of layered g‐C 3 N 4 ‐Ni intermediate products, thus interrupting the solid‐to‐solid rolling process and leading to the formation of planar graphene type supports for Ni single atoms. The as‐synthesized NiSA−N−G with Ni atomic loading of ∼6 wt% catalysts shows a better activity and stability for the CO 2 reduction reaction (CO 2 RR) than NiSA−N−CNT with Ni atomic loading of ∼15 wt% due to the open and exposed Ni single atom active sites in NiSA−N−G. This study demonstrates for the first time the feasibility in the control of the microstructure of carbon supports in the synthesis of SACs.

Zhao, Shiyong↗
DOE OSTI2024

Bringing HPE Slingshot 11 support to Open MPI

The Cray HPE Slingshot 11 network is used on the new exascale systems arriving at the U.S. Department of Energy (DoE) laboratories (e.g., Frontier, Aurora, Perlmutter). As such, the support of this network is an important capability to meet the needs of exascale applications. Here, this article highlights recent work to develop supporting infrastructure to enable Open MPI to efficiently support these new platforms. A key component of this effort involves development of a new Open Fabrics Interface (OFI) provider, LinkX. We discuss the design and development of enhancements that take advantage of the new Slingshot 11 network and AMD GPUs. We include performance data from tests on the Frontier supercomputer using synthetic communication benchmarks, and the vendor provided MPI as a baseline for comparison. The tests demonstrate full functionality of Open MPI on the system and initial results show favorable performance when compared to the highly tuned vendor implementation.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2014

The Role of Hydroxyl Group Acidity on the Activity of Silica-Supported Secondary Amines for the Self-Condensation of n -Butanal

The catalytic activity of secondary amines supported on meso-porous silica for the self-condensation of n -butanal to 2-ethylhexenal can be altered significantly by controlling the Brønsted acidity of M - OH species present on the surface of the support. In this study, M - OH (M = Sn, Zr, Ti, and Al) groups were doped onto the surface of SBA-15, a mesoporous silica, prior to grafting secondary propyl amine groups on to the support surface. The catalytic activity was found to depend critically on the synthesis procedure, the nature and amount of metal species in-troduced and the spatial separation between the acidic sites and amine groups. DFT analysis of the reaction pathway indicates that, for weak Brønsted acid groups, such as Si - OH, the rate-limiting step is C - C bond formation, whereas for stronger Brønsted acid groups, such as Ti and Al, hydrolysis of iminium species produced upon C - C bond formation is the rate-limiting step. Finally, theoretical analysis shows further that the apparent activation energy decreases with increasing Brønsted acidity of the M - OH groups, consistent with experimental observation.

aldol reaction↗
DOE OSTI2016

Water oxidation by size selected Co 27 clusters supported on Fe 2 O 3

The complexity of the water oxidation reaction makes understanding the role of individual catalytic sites critical to improving the process. Here, size-selected 27-atom cobalt clusters (Co 27 ) deposited on hematite (Fe 2 O 3 ) anodes were tested for water oxidation activity. The uniformity of these anodes allows measurement of the activity of catalytic sites of well-defined nuclearity and known density. Grazing incidence X-ray absorption near-edge spectroscopy (GIXANES) characterization of the anodes before and after electrochemical cycling demonstrates that these Co 27 clusters are stable to dissolution even in the harsh water oxidation electrochemical environment. They are also stable under illumination at the equivalent of 0.4suns irradiation. The clusters show turnover rates for water oxidation that are comparable or higher than those reported for Pd- and Co-based materials or for hematite. The support for the Co 27 clusters is Fe 2 O 3 grown by atomic layer deposition on a Si chip. We have chosen to deposit a Fe2O3 layer that is only a few unit cells thick (2nm), to remove complications related to exciton diffusion. We find that the electrocatalytic and the photoelectrocatalytic activity of the Co 27 /Fe 2 O 3 material is significantly improved when the samples are annealed (with the clusters already deposited). Lastly, given that the support is thin and that the cluster deposition density is equivalent to approximately 5% of an atomic monolayer, we suggest that annealing may significantly improve the exciton diffusion from the support to the catalytic moiety.

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

Associations among hydrologic classifications and fish traits to support environmental flow standards

Classification systems are valuable to ecological management in that they organize information into consolidated units thereby providing efficient means to achieve conservation objectives. Of the many ways classifications benefit management, hypothesis generation has been discussed as the most important. However, in order to provide templates for developing and testing ecologically relevant hypotheses, classifications created using environmental variables must be linked to ecological patterns. Herein, we develop associations between a recent US hydrologic classification and fish traits in order to form a template for generating flow ecology hypotheses and supporting environmental flow standard development. Tradeoffs in adaptive strategies for fish were observed across a spectrum of stable, perennial flow to unstable intermittent flow. In accordance with theory, periodic strategists were associated with stable, predictable flow, whereas opportunistic strategists were more affiliated with intermittent, variable flows. We developed linkages between the uniqueness of hydrologic character and ecological distinction among classes, which may translate into predictions between losses in hydrologic uniqueness and ecological community response. Comparisons of classification strength between hydrologic classifications and other frameworks suggested that spatially contiguous classifications with higher regionalization will tend to explain more variation in ecological patterns. Despite explaining less ecological variation than other frameworks, we contend that hydrologic classifications are still useful because they provide a conceptual linkage between hydrologic variation and ecological communities to support flow ecology relationships. Mechanistic associations among fish traits and hydrologic classes support the presumption that environmental flow standards should be developed uniquely for stream classes and ecological communities, therein.

aquatic conservation↗
DOE OSTI2014

The development of poly(vinyl chloride) [PVC] extrusions for a 14,000-ton self-supporting structure for the detection of neutrinos

The NOvA Neutrino Experiment has built a one of a kind self-supporting plastic structure, potentially the largest ever built. The PVC structure serves as a neutrino detector and is composed of 28 individual blocks that measure 15.5 m (51 feet) high by 15.5 m (51 feet) wide by 2.1 m (7 feet) deep. The primary parts in the detector construction are 15.5m (51 foot), 15-cell PVC extrusions. These extrusions from the basis of the detector modules which are laminated together in a crossed pattern to form the individual blocks and then filled with mineral oil based liquid scintillator. The self-supporting nature of the detector places important structural requirements on both the PVC formulation and the extrusions. Block assembly requirements impose narrow geometric tolerances. Due to the method of detecting neutrinos, the extrusions must possess exceptionally high reflectivity over a particular wavelength range. The requirement places additional restrictions on the components of the PVC formulation. Altogether, the PVC extrusions have to maintain important reflectivity characteristics, provide structural support to the detector, and meet relatively tight geometric requirements for assembly. In order to meet these constraints, a custom PVC formulation had to be created and extruded. Here, we describe the purpose and requirements of the NOvA detector leading to the production of our unique PVC extrusion, summarize the R&D process, and discuss the lessons learned.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2016

Scenario analysis for techno-economic model development of U.S. offshore wind support structures

Challenging bathymetry and soil conditions of future US offshore wind power plants might promote the use of multimember, fixed-bottom structures (or 'jackets') in place of monopiles. Support structures affect costs associated with the balance of system and operation and maintenance. Understanding the link between these costs and the main environmental design drivers is crucial in the quest for a lower levelized cost of energy, and it is the main rationale for this work. Actual cost and engineering data are still scarce; hence, we evaluated a simplified engineering approach to tie key site and turbine parameters (e.g. water depth, wave height, tower-head mass, hub height and generator rating) to the overall support weight. A jacket-and-tower sizing tool, part of the National Renewable Energy Laboratory's system engineering software suite, was utilized to achieve mass-optimized support structures for 81 different configurations. This tool set provides preliminary sizing of all jacket components. Results showed reasonable agreement with the available industry data, and that the jacket mass is mainly driven by water depth, but hub height and tower-head mass become more influential at greater turbine ratings. A larger sensitivity of the structural mass to wave height and target eigenfrequency was observed for the deepest water conditions (>40 m). Thus, techno-economic analyses using this model should be based on accurate estimates of actual metocean conditions and turbine parameters especially for deep waters. Finally, the relationships derived from this study will inform National Renewable Energy Laboratory's offshore balance of system cost model, and they will be used to evaluate the impact of changes in technology on offshore wind lower levelized cost of energy.

17 WIND ENERGY↗
DOE OSTI2016

Infrared spectroscopy investigation of Fe-promoted Rh catalysts supported on Titania and Ceria for CO hydrogenation

The nature of the promotional effect of Fe addition to Rh/TiO 2 and Rh/CeO 2 catalysts for CO hydrogenation was investigated using FT-IR spectroscopy in an ultrahigh vacuum compatible transmission IR cell. CO adsorption experiments on Rh and FeRh showed vibrational signatures characteristic of linear and bridge bound CO on Rh0 as well as geminal-dicarbonyl species associated with Rh + . Compared to TiO 2 , the CeO 2 -supported catalysts show increased dispersion, reflected by decreased particle size, and a lower signal for linear versus geminal-dicarbonyl bonded CO. The absorption frequencies for CO on Rh/CeO 2 are also redshifted relative to Rh/TiO 2 , which results from a weaker Rh–CO interaction, likely due to the increased reducibility of the CeO 2 support. Upon addition of Fe, a new spectral feature is observed and attributed to CO bound to Rh in close contact with Fe, likely as a surface alloy. CO hydrogenation on (Fe)Rh catalysts on both supports was also studied. Compared to bare Rh, Fe containing catalysts promote formate and methoxy species on the surface at lower temperature (180 °C), which suggests an enhancement in methanol selectivity by Fe addition. Furthermore, at higher temperatures (220 °C), the spectral features appear similar, further confirming the role of Fe as a disrupter of large Rh o crystallites and regulator of CO dissociation and CH 4 formation.

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

Do agrivoltaics improve public support for solar? A survey on perceptions, preferences, and priorities

Abstract Agrivoltaic systems integrate agricultural production with solar photovoltaic electricity generation. Given the proven technical, economic, and environmental co-benefits provided by agrivoltaic systems, increased proliferation is anticipated, which necessitates accounting for the nuances of community resistance to solar development on farmland and identifying pathways for mitigation. Minimizing siting conflict and addressing agricultural communities’ concerns will be key in continued deployment of agrivoltaics, as localized acceptance of solar is a critical determinant of project success. This survey study assessed if public support for solar development increases when energy and agricultural production are combined in an agrivoltaic system. Results show that 81.8% of respondents would be more likely to support solar development in their community if it integrated agricultural production. This increase in support for solar given the agrivoltaic approach highlights a development strategy that can improve local social acceptance and the deployment rate of solar. Survey respondents prefer agrivoltaic projects that a) are designed to provide economic opportunities for farmers and the local community b) are not located on public property c) do not threaten local interests and d) ensure fair distribution of economic benefits. Proactively identifying what the public perceives as opportunities and concerns related to agrivoltaic development can help improve the design, business model, and siting of systems in the U.S.

Pascaris, Alexis S. (ORCID:0000000253806927)↗
DOE OSTI2014

An Experimental Test Facility to Support Development of the Fluoride Salt Cooled High Temperature Reactor

The need for high-temperature (greater than 600 C) energy exchange and delivery systems is significantly increasing as the world strives to improve energy efficiency and develop alternatives to petroleum-based fuels. Liquid fluoride salts are one of the few energy transport fluids that have the capability of operating at high temperatures in combination with low system pressures. The Fluoride Salt-Cooled High-Temperature Reactor design uses fluoride salt to remove core heat and interface with a power conversion system. Although a significant amount of experimentation has been performed with these salts, specific aspects of this reactor concept will require experimental confirmation during the development process. The experimental facility described here has been constructed to support the development of the Fluoride Salt Cooled High Temperature Reactor concept. The facility is capable of operating at up to 700 C and incorporates a centrifugal pump to circulate FLiNaK salt through a removable test section. A unique inductive heating technique is used to apply heat to the test section, allowing heat transfer testing to be performed. An air-cooled heat exchanger removes added heat. Supporting loop infrastructure includes a pressure control system; trace heating system; and a complement of instrumentation to measure salt flow, temperatures, and pressures around the loop. The initial experiment is aimed at measuring fluoride salt heat transfer inside a heated pebble bed similar to that used for the core of the pebble bed advanced high-temperature reactor. This document describes the details of the loop design, auxiliary systems used to support the facility, the inductive heating system, and facility capabilities.

fluoride salt reactor FLiNaK↗
DOE OSTI2011

Reverse Micelle Synthesis and Characterization of Supported Pt/Ni Bimetallic Catalysts on gamma-Al2O3

Reverse micelle synthesis was used to improve the nanoparticle size uniformity of bimetallic Pt/Ni nanoparticles supported on {gamma}-Al{sub 2}O{sub 3}. Two impregnation methods were investigated to optimize the use of the micelle method: (1) step-impregnation, where Ni nanoparticles were chemically reduced in microemulsion and then supported, followed by Pt deposition using incipient wetness impregnation, and (2) co-impregnation, where Ni and Pt were chemically reduced simultaneously in microemulsion and then supported. Transmission electron microscopy (TEM) was used to characterize the particle size distribution. Atomic absorption spectroscopy (AAS) was used to perform elemental analysis of bimetallic catalysts. Extended X-ray absorption fine structure (EXAFS) measurements were utilized to confirm the formation of the Pt-Ni bimetallic bond in the step-impregnated catalyst. CO pulse chemisorption and Fourier transform infrared spectroscopy (FTIR) studies of 1,3-butadiene hydrogenation in a batch reactor were performed to determine the catalytic activity. Step-impregnated Pt/Ni catalyst demonstrated enhanced hydrogenation activity over the parent monometallic Pt and Ni catalysts due to bimetallic bond formation. The catalyst synthesized using co-impregnation showed no enhanced activity, behaving similarly to monometallic Ni. Overall, our results indicate that reverse micelle synthesis combined with incipient wetness impregnation produced small, uniform nanoparticles with bimetallic bonds that enhanced hydrogenation activity.

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

Assessment and comparison of ordered & non-ordered supported metal oxide catalysts for upgrading propane to propylene

Propylene is an important chemical feedstock that is largely produced via cracking of oil-derived naphtha. Direct conversion of propane into propylene may be a more attractive alternative. Specifically, propane dehydrogenation (DH) and oxidative dehydrogenation (ODH) are promising for this transformation, albeit only DH has been industrially implemented. However, even the best DH catalysts (Pt-based) still suffer from deactivation. VO x - and BO x -based ODH catalysts result in significant over-oxidation and lack a mechanistic understanding. A common challenge in developing these catalysts is the broad distribution of surface species caused by the use of non-ordered catalyst supports. This hampers clear structure-performance correlations. Recent progress in the preparation of well-defined active sites on ordered supports has brought about improved catalysts, as well as fundamental insight into the working mechanism. This review will highlight recent advancements in the development of these catalysts and provide direction on the use of ordered supports for propane upgrading.

03 NATURAL GAS↗