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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

A Supramolecular Strategy for Selective Catalytic Hydrogenation Independent of Remote Chain Length

Performing selective transformations on complex substrates remains a challenge in synthetic chemistry. These difficulties often arise due to cross-reactivity, particularly in the presence of similar functional groups at multiple sites. Therefore, there is a premium on the ability to perform selective activation of these functional groups. Here we report a supramolecular strategy where encapsulation of a hydrogenation catalyst enables selective olefin hydrogenation, even in the presence of multiple sites of unsaturation. While the reaction requires at least one sterically nondemanding alkene substituent, the rate of hydrogenation is not sensitive to the distance between the alkene and the functional group, including a carboxylate, on the other substituent. This observation indicates that only the double bond has to be encapsulated to effect hydrogenation. Going further, we demonstrate that this supramolecular strategy can overcome the inherent allylic alcohol selectivity of the free catalyst, achieving supramolecular catalyst-directed regioselectivity as opposed to directing-group selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Molecular basis for the binding and selective dephosphorylation of Na + /H + exchanger 1 by calcineurin

Very little is known about how Ser/Thr protein phosphatases specifically recruit and dephosphorylate substrates. Here, we identify how the Na + /H + -exchanger 1 (NHE1), a key regulator of cellular pH homeostasis, is regulated by the Ser/Thr phosphatase calcineurin (CN). NHE1 activity is increased by phosphorylation of NHE1 residue T779, which is specifically dephosphorylated by CN. While it is known that Ser/Thr protein phosphatases prefer pThr over pSer, we show that this preference is not key to this exquisite CN selectivity. Rather a combination of molecular mechanisms, including recognition motifs, dynamic charge-charge interactions and a substrate interaction pocket lead to selective dephosphorylation of pT779. Our data identify T779 as a site regulating NHE1-mediated cellular acid extrusion and provides a molecular understanding of NHE1 substrate selection by CN, specifically, and how phosphatases recruit specific substrates, generally.

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

Microstrip patch antenna for simultaneous strain and temperature sensing

A patch antenna, consisting of a radiation patch, a dielectric substrate, and a ground plane, resonates at distinct fundamental frequencies that depend on the substrate dielectric constant and the dimensions of the radiation patch. Since these parameters change with the applied strain and temperature, this study investigates simultaneous strain and temperature sensing using a single antenna that has two fundamental resonant frequencies. The theoretical relationship between the antenna resonant frequency shifts, the temperature, and the applied strain was first established to guide the selection of the dielectric substrate, based on which an antenna sensor with a rectangular radiation patch was designed and fabricated. A tensile test specimen instrumented with the antenna sensor was subjected to thermo-mechanical tests. Experiment results validated the theoretical predictions that the normalized antenna resonant frequency shifts are linearly proportional to the applied strain and temperature changes. As a result, an inverse method was developed to determine the strain and temperature changes from the normalized antenna resonant frequency shifts, yielding measurement uncertainty of 0.4 °C and 17.22 μϵ for temperature and strain measurement, respectively.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS1980

Direct /TEM/ observation of the catalytic oxidation of amorphous carbon by Pd particles

The catalytic oxidation of amorphous carbon substrates by Pd particles is observed by in situ transmission electron microscopy. Various modes of selective attack of the carbon substrate in the immediate neighborhood of Pd particles are observed, which can be correlated with different degrees of particle mobility. Using amorphous substrates we have been able to demonstrate that the particle-substrate interaction is influenced by the structure of the particle. This has not previously been noted.

Moorhead, R. D.↗
DOE OSTI2024

Inhibition of atomic layer deposition of TiO 2 by functionalizing silicon surface with 4-fluorophenylboronic acid

As the size of the components in electronic devices decreases, new approaches and chemical modification schemes are needed to produce nanometer-size features with bottom-up manufacturing. Organic monolayers can be used as effective resists to block the growth of materials on non-growth substrates in area-selective deposition methods. However, choosing the appropriate surface modification requires knowledge of the corresponding chemistry and also a detailed investigation of the behavior of the functionalized surface in realistic deposition schemes. This study aims to investigate the chemistry of boronic acids that can be used to prepare such non-growth areas on elemental semiconductors. 4-Fluorophenylboronic acid is used as a model to investigate the possibility to utilize the Si(100) surface functionalized with this compound as a non-growth substrate in a titanium dioxide (TiO 2 ) deposition scheme based on sequential doses of tetrakis(dimethylamido)titanium and water. Here, a combination of X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry allows for a better understanding of the process. The resulting surface is shown to be an effective non-growth area to TiO 2 deposition when compared to currently used H-terminated silicon surfaces but to exhibit much higher stability in ambient conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Understanding of catalytic transformation of shale gas and development of catalysts with high activity and selectivity through experimental exploration and theoretical simulation

Catalysis on transition metal oxides is equivalently important in contrast to that on metal catalysts in chemical and energy transformations. Understanding of catalytic reactions on early transition metal oxide catalysts is fundamentally intriguing and of great practical interest in efficient production of chemical and fuel feedstocks. Fundamental understanding of catalysis on transition metal oxide-based catalysts has been lagged behind catalysis on metals due to the complexity of chemistry and structure of surface and bulk of oxide catalysts and their structural flexibility in reactive environment at high temperatures. The funded DOE project explored surface chemistry of a few reducible oxides including CeO 2 - based, Co 3 O 4 -based, and CoO-based which are significant for heterogeneous catalysis. Through in-situ studies using ambient pressure X-ray photoelectron spectroscopy and high pressure scanning tunneling microscopy, we revealed phase transformation, the accompanying changes of surface chemistry and structure, and uncovered their correlations with catalytic activity and selectivity in catalytic reactions including reduction of NO with CO, water-gas shift, and chemical transformations of methane to methanol and acetic acid under mild conditions. Driven by the following two facts, we propose to pursue fundamental understanding of oxidative dehydrogenation of ethane and oxidative coupling of methane on oxide catalysts through both in-situ studies of catalyst surfaces during catalysis and computational studies in the renewal proposal. One driving force is the significance of oxidative dehydrogenation of ethane and oxidative coupling of methane for utilization of earth-abundant, relatively inexpensive energy resource and the urgent needs of efficient chemical processes to generate ethylene from shale gas. The other is that exploration of surface chemistry of oxide catalysts during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide catalysts and developing oxide-based catalysts toward high selectivity and activity. Therefore, the overall objective of the renewal proposal is to mechanistically understand the oxidative dehydrogenation of ethane and oxidative coupling of methane at a molecular level through building correlations between surface chemistry of catalysts during catalysis and the corresponding catalytic performances, and thus design catalysts with high selectivity and activity for production of ethylene with the guidance achieved from these fundamental studies. Experiments were designed to explore the influences of electronic states of cations supported on substrate oxides, cations of surface of the substrate oxides, and surface lattice oxygen atoms of the substrate oxides on their catalytic selectivity and activity. Surface chemistry, including oxidation state of the surface monomers and cations of substrate oxides and density of oxygen vacancies during catalysis, will be tracked with AP-XPS during catalysis. A correlation between surface chemistry of these catalysts at different temperatures and their corresponding catalytic selectivity for production of ethylene and activity will be built. Computational studies will calculate adsorption energies of reactant molecules and their dissociated species and intermediates on the catalyst surface, search transition states, and simulate reaction pathway close to experimental studies. By integrating the computational studies into these correlations to be built from experimental studies, fundamental understanding of the catalytic mechanisms of oxidative dehydrogenation of ethane and oxidative coupling of methane at a molecular level will be achieved. With these insights, new catalysts with high selectivity and activity will be developed.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Electrochemical hydrogen isotope exchange of amines controlled by alternating current frequency

Here, we report an electrochemical protocol for hydrogen isotope exchange (HIE) at α-C(sp 3 )–H amine sites. Tetrahydroisoquinoline and pyrrolidine are selected as two model substrates because of their different proton transfer (PT) and hydrogen atom transfer (HAT) kinetics at the α-C(sp 3 )–H amine sites, which are utilized to control the HIE reaction outcome at different applied alternating current (AC) frequencies. We found the highest deuterium incorporation for tetrahydroisoquinolines at 0 Hz (i.e., under direct current (DC) electrolysis conditions) and pyrrolidines at 0.5 Hz. Analysis of the product distribution and D isotope incorporation at different frequencies reveals that the HIE of tetrahydroisoquinolines is limited by its slow HAT, whereas the HIE of pyrrolidines is limited by the overoxidation of its α-amino radical intermediates. Here, the AC-frequency-dependent HIE of amines can be potentially used to achieve selective labeling of α-amine sites in one drug molecule, which will significantly impact the pharmaceutical industry.

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

Aging of Concrete for the Evaluation of Repair Materials to Protect the Walls of the HCAEX Tunnel at Savannah River - 20301

H-Canyon, located in the Savannah River site, is a unique facility for chemical reprocessing of plutonium, highly-enriched uranium, and other radioactive materials. The exhaust gases of the H-Canyon are sent through the H-Canyon Exhaust (HCAEX) tunnel for contamination removal. Robotic inspections of the tunnel revealed significant degradation of the reinforced concrete structure that was associated with acid attack, and could compromise the structural stability of the tunnel. Thus, the identification and evaluation of potential repair materials that could be applied on the degraded walls to mitigate and prevent further degradation is of significant interest to the Department of Energy and the Savannah River representatives. This research effort has been divided into two phases: 1) Development and evaluation of aged concrete under accelerated aging conditions (which is the focus of this paper) and 2) Evaluation of potential repair materials applied on aged and non-aged concrete under simulated aggressive conditions. In order to develop and evaluate concrete samples exposed to accelerated aging conditions in simulated aggressive environments, a literature review of the HCAEX tunnel was conducted that included 1) characterization and extent of the concrete damage, 2) environmental conditions inside the tunnel and 3) primary deterioration mechanisms. In addition, potential coatings and/or repair materials for degraded concrete surfaces exposed to aggressive environments (primarily acidic) were selected from the literature review and the most common testing and measurements for evaluating acid attack phenomena, erosion, etc. were reviewed. From the literature review findings, a preliminary bench-scale test plan for the concrete aging was developed, including accelerated aging tests with aggressive conditions (acid fumes, humidity, etc.). Concrete samples were exposed to the aging accelerated conditions (e.g. immersion in acid solutions) and visual inspection, mass loss and pH change (acid solution) were recorded over time. Correlations between the visual inspection, mass loss and pH changes results and the aging time or the aging conditions were developed. Specimens submitted to the highest acid concentration showed the fastest and most intense degradation. The type of coarse aggregate (limestone) used for the concrete seemed to be the cause of the fastest aging observed, compared to the cement paste. The research findings created the foundation for the ongoing investigation, in which new concrete samples with a mix design similar to the HCAEX tunnel will be tested and will serve as the substrate for testing the selected coatings and /or repair materials. In this paper, the literature review and preliminary results from the aging tests are provided. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS1992

Quartz/fused silica chip carriers

The primary objective of this research and development effort was to develop monolithic microwave integrated circuit (MMIC) packaging which will operate efficiently at millimeter-wave frequencies. The packages incorporated fused silica as the substrate material which was selected due to its favorable electrical properties and potential performance improvement over more conventional materials for Ka-band operation. The first step towards meeting this objective is to develop a package that meets standard mechanical and thermal requirements using fused silica and to be compatible with semiconductor devices operating up to at least 44 GHz. The second step is to modify the package design and add multilayer and multicavity capacity to allow for application specific integrated circuits (ASIC's) to control multiple phase shifters. The final step is to adapt the package design to a phased array module with integral radiating elements. The first task was a continuation of the SBIR Phase 1 work. Phase 1 identified fused silica as a viable substrate material by demonstrating various plating, machining, and adhesion properties. In Phase 2 Task 1, a package was designed and fabricated to validate these findings. Task 2 was to take the next step in packaging and fabricate a multilayer, multichip module (MCM). This package is the predecessor to the phased array module and demonstrates the ability to via fill, circuit print, laminate, and to form vertical interconnects. The final task was to build a phased array module. The radiating elements were to be incorporated into the package instead of connecting to it with wire or ribbon bonds.

Source record↗
NASA NTRS1991

Advances in silicon carbide Chemical Vapor Deposition (CVD) for semiconductor device fabrication

Improved SiC chemical vapor deposition films of both 3C and 6H polytypes were grown on vicinal (0001) 6H-SiC wafers cut from single-crystal boules. These films were produced from silane and propane in hydrogen at one atmosphere at a temperature of 1725 K. Among the more important factors which affected the structure and morphology of the grown films were the tilt angle of the substrate, the polarity of the growth surface, and the pregrowth surface treatment of the substrate. With proper pregrowth surface treatment, 6H films were grown on 6H substrates with tilt angles as small as 0.1 degrees. In addition, 3C could be induced to grow within selected regions on a 6H substrate. The polarity of the substrate was a large factor in the incorporation of dopants during epitaxial growth. A new growth model is discussed which explains the control of SiC polytype in epitaxial growth on vicinal (0001) SiC substrates.

Powell, J. Anthony↗
DOE OSTI2023

Self‐Propelling Macroscale Sheets Powered by Enzyme Pumps

Abstract Nanoscale enzymes anchored to surfaces act as chemical pumps by converting chemical energy released from enzymatic reactions into spontaneous fluid flow that propels entrained nano‐ and microparticles. Enzymatic pumps are biocompatible, highly selective, and display unique substrate specificity. Utilizing these pumps to trigger self‐propelled motion on the macroscale has, however, constituted a significant challenge and thus prevented their adaptation in macroscopic fluidic devices and soft robotics. Using experiments and simulations, we herein show that enzymatic pumps can drive centimeter‐scale polymer sheets along directed linear paths and rotational trajectories. In these studies, the sheets are confined to the air/water interface. With the addition of appropriate substrate, the asymmetric enzymatic coating on the sheets induces chemically driven, buoyancy flows that controllably propel the sheet's motion on the air/water interface. The directionality and speed of the motion can be tailored by changing the pattern of the enzymatic coating, type of enzyme, and nature and concentration of the substrate. This work highlights the utility of biocompatible enzymes for generating motion in macroscale fluidic devices and robotics and indicates their potential utility for in vivo applications.

Song, Jiaqi↗
DOE OSTI2023

Self‐Propelling Macroscale Sheets Powered by Enzyme Pumps

Nanoscale enzymes anchored to surfaces act as chemical pumps by converting chemical energy released from enzymatic reactions into spontaneous fluid flow that propels entrained nano‐ and microparticles. Enzymatic pumps are biocompatible, highly selective, and display unique substrate specificity. Utilizing these pumps to trigger self‐propelled motion on the macroscale has, however, constituted a significant challenge and thus prevented their adaptation in macroscopic fluidic devices and soft robotics. Using experiments and simulations, we herein show that enzymatic pumps can drive centimeter‐scale polymer sheets along directed linear paths and rotational trajectories. In these studies, the sheets are confined to the air/water interface. With the addition of appropriate substrate, the asymmetric enzymatic coating on the sheets induces chemically driven, buoyancy flows that controllably propel the sheet's motion on the air/water interface. The directionality and speed of the motion can be tailored by changing the pattern of the enzymatic coating, type of enzyme, and nature and concentration of the substrate. This work highlights the utility of biocompatible enzymes for generating motion in macroscale fluidic devices and robotics and indicates their potential utility for in vivo applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Metal–Organic-Framework-Supported and -Isolated Ceria Clusters with Mixed Oxidation States

The formation of oxygen vacancies via reversible transitions between Ce(IV) and Ce(III) plays a crucial role in the propensity of cerium oxide to act as a supporting promoter in oxidative heterogeneous catalysis. An open challenge is, however, preparation of high-porosity, supported arrays of isolated ceria(IV, III) clusters with high porosity. In this article, we report two examples of oxy-Ce(IV, III) clusters supported and spatially isolated on an oxy-zirconium MOF, NU-1000. The clusters are introduced using either of two Ce complexes (precursors): Ce IV (tmhd) 4 (tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionate) or Ce III (iPrCp) 3 (iPrCp = tris(isopropyl-cyclopenta-dienyl), via SIM (solvothermal installation in MOFs). The prepared materials are named Ce-l-SIM-NU-1000 and Ce-n-SIM-NU-1000, respectively. X-ray photoelectron spectroscopy characterization shows that the ratio of Ce(III) to Ce(IV) oxidation states can be modulated. Difference envelope density analyses of X-ray scattering show that Ce x O y H z clusters in Ce-n-SIM-NU-1000 are located between pairs of Zr6 nodes, whereas in Ce-l-SIM-NU-1000, they are sited on MOF linkers throughout the micropores of NU-1000. Cluster size differences were further evaluated by pair function distribution (PDF) analyses of total X-ray scattering reveal that the node sited clusters contain of only a few cerium ions, whereas the linker-sited clusters each contain ~90 cerium ions. The observed size appears to be defined by the size of NU-1000s triangular pores, that is, cluster formation appears to be pore templated. The Ce-SIM functionalized materials are catalytically active for hydrolysis of DMNP (dimethyl 4-nitrophenyl phosphate), a nerve-agent simulant. Conversion of a small fraction of the Ce(IV) ions in which the presence of small fractions of the cerium(IV) ions in Ce-l-SIM-NU-1000 to cerium(III) significantly enhances catalytic activity-perhaps by labilizing aqua ligands and facilitating simulant binding to the clusters Lewis-basic metal ions. While not explored here, the larger clusters, when partially reduced, are, we believe, candidate catalysts for O 2 activation and subsequent selective oxidation of organic substrates.

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

Highly active Au/δ-MoC and Au/β-Mo 2 C catalysts for the low-temperature water gas shift reaction: effects of the carbide metal/carbon ratio on the catalyst performance

In this paper, the water gas shift (WGS) reaction catalyzed by orthorhombic β-Mo 2 C and cubic δ-MoC surfaces with and without Au clusters supported thereon has been studied by means of a combination of sophisticated experiments and state-of-the-art computational modeling. Experiments evidence the importance of the metal/carbon ratio on the performance of these systems, where Au/δ-MoC is presented as a suitable catalyst for WGS at low temperatures owing to its high activity, selectivity (only CO 2 and H 2 are detected), and stability (oxycarbides are not observed). Periodic density functional theory-based calculations show that the supported Au clusters and the Au/δ-MoC interface do not take part directly in water dissociation but their presence is crucial to switch the reaction mechanism, drastically decreasing the effect of the reverse WGS reaction and favoring the WGS products desorption, thus leading to an increase in CO 2 and H 2 production. Finally, the present results clearly display the importance of the Mo/C ratio and the synergy with the admetal clusters in tuning the activity and selectivity of the carbide substrate.

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

Unraveling the Role of Transport, Electrocatalysis, and Surface Science in the Solid Oxide Fuel Cell Cathode Oxygen Reduction Reaction

This final report for project FE0009656 covers the period from 10/01/2012 to 09/30/2015 and covers research accomplishments on the effects of carbon dioxide on the surface composition and structure of cathode materials for solid oxide fuel cells (SOFCs), specifically La1-xSrxFeyCo1- yO3-δ (LSCF). Epitaxially deposited thin films of LSCF on various single-crystal substrates have revealed the selective segregation of strontium to the surface thereby resulting in a surface enrichment of strontium. The near surface compositional profile in the films have been measured using total x-ray fluorescence (TXRF), and show that the kinetics of strontium segregation are higher at higher partial pressures of carbon dioxide. Once the strontium segregates to the surface, it leads to the formation of precipitates of SrO which convert to SrCO3 in the presence of even modest concentrations of carbon dioxide in the atmosphere. This has important implications for the performance of SOFCs which is discussed in this report. These experimental observations have also been verified by Density Functional Theory calculations (DFT) which predict the conditions under which SrO and SrCO3 can occur in LSCF. Furthermore, a few cathode compositions which have received attention in the literature as alternatives to LSCF cathodes have been studied in this work and shown to be thermodynamically unstable under the operating conditions of the SOFCs.

25 ENERGY STORAGE↗
NASA NTRS1976

Industrialization of the ion plating process

A new process referred to as ion plating by induction heating (IPIH) is described, which combines the advantages of both ion plating and induction heating. The IPIH apparatus consists of the specimen (cathode) to be coated and the evaporation heating source, which is a ceramic crucible containing the metal to be heated. The specimen is an internal part of the high-voltage ceramic-metal vacuum feedthrough and is connected to the negative terminal of the high-voltage power supply, the positive terminal of the power supply being grounded. The plating conditions are the same as those most commonly used in industrial ion plating. A number of metals - such as nickel, iron, platinum - which were practically impossible to deposit by resistance heating evaporation can now be effectively evaporated and deposited to any desired thickness. Excellent adherence is observed for many metals deposited on various metal surfaces in thicknesses from 0.15 to 50 microns, regardless of the materials selected for coating and substrate.

Spalvins, T.↗
NASA NTRS1978

Process for utilizing low-cost graphite substrates for polycrystalline solar cells

Low cost polycrystalline silicon solar cells supported on substrates were prepared by depositing successive layers of polycrystalline silicon containing appropriate dopants over supporting substrates of a member selected from the group consisting of metallurgical grade polycrystalline silicon, graphite and steel coated with a diffusion barrier of silica, borosilicate, phosphosilicate, or mixtures thereof such that p-n junction devices were formed which effectively convert solar energy to electrical energy. To improve the conversion efficiency of the polycrystalline silicon solar cells, the crystallite size in the silicon was substantially increased by melting and solidifying a base layer of polycrystalline silicon before depositing the layers which form the p-n junction.

Chu, T. L.↗