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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Constructing efficient CuO x -CeO 2 catalyst for NO reduction by CO: New insights into the structure–activity relationship

CuO-CeO 2 based materials have been recognized as promising substitutes for precious metal catalysts in emission control field due to their superior redox property and low cost. In this work, by optimizing the deposition process of CeO 2 and CuO onto γ-Al 2 O 3 , highly dispersed CuO clusters on unique CeO 2 -Al 2 O 3 support with small CeO 2 particles (7Cu-Ce/CeAl) were successfully constructed for efficient NO reduction by CO, which exhibited much higher NO removal efficiency and N 2 selectivity than CuO catalysts supported on γ-Al 2 O 3 (7Cu/Al) and conventional CeO 2 -Al 2 O 3 support (7Cu/CeAl). Moreover, H 2 O showed limited inhibition effect on the catalytic performance of 7Cu-Ce/CeAl catalyst. With the help of Raman spectra, X-ray absorption spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy, etc., it was clearly revealed that the abundant Cu + /Ce 3+ paired sites with surface synergetic oxygen vacancies (SSOV) on 7Cu-Ce/CeAl catalyst could effectively facilitate the adsorption and activation of CO and NO, thus significantly enhancing the NO removal efficiency.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Synchrotron X-ray-induced Synthesis of Copper Hydroxide Nitrate Nanoplates on Cu Thin Films in an Ambient Atmosphere

Synchrotron X-rays are widely used for material characterizations. However, they can also ionize atoms and molecules to damage and manipulate probed materials. We report here an X-ray-induced growth of copper hydroxide nitrate, Cu 2 (OH) 3 NO 3 , on copper thin films in the ambient atmosphere without solvents and thermal treatment. In situ synchrotron X-ray diffraction measurements showed that the time-dependent growth process of the Cu 2 (OH) 3 NO 3 is accompanied by the consumption of Cu metal and can be described by a sigmoidal model. The growth rate was reduced after the initial fast growth period. Scanning electron microscopy (SEM) images show that the isolated islands of Cu 2 (OH) 3 NO 3 nanoplates formed in the beginning, which grew together with new nanoplates formed under continued X-ray irradiation. The result demonstrated that high-flux synchrotron X-rays may provide an unconventional approach to synthesizing and manipulating materials, which will inspire future investigation both experimentally and theoretically.

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

Mechanistic insights into N 2 O formation as a side product in NH 3 -SCR over small pore Cu-zeolites

Here, the present contribution provides clarity to N 2 O formation mechanisms and key influencing factors during low temperature NH 3 -SCR, with the goal of enabling the rational design of advanced SCR catalysts with low greenhouse gas impact. By studying more than 50 small pore Cu-exchanged zeolite SCR catalyst samples, including model catalysts synthesized in our laboratories and state-of-the-art industrial catalysts, we explored a wide range of factors affecting N 2 O formation. These factors included Cu loading, support Si/Al ratio, support topology, catalyst aging, reaction temperature and reactant feed composition effects. We probed N 2 O formation under both steady-state SCR, and during NH 4 NO 3 decomposition via temperature programmed desorption (TPD). Finally, we used DFT to probe energetics of possible N 2 O formation pathways. Based on these studies, we confirm that low temperature N 2 O formation occurs via multiple reaction pathways that all involve NH 4 NO 3 and are supported by Cu moieties that facilitate in-situ NO oxidation to NO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

Solid metabolic waste transport and stowage investigation

The basic Waste Collection System (WCS) design under consideration utilized air flow to separate the stool from the WCS user and to transport the fecal material to a slinger device for subsequent deposition on a storage bowel. The major parameters governing stool separation and transport were found to be the area of the air inlet orifices, the configuration of the air inlet orifice and the transport air flow. Separation force and transport velocity of the stool were studied. The developed inlet orifice configuration was found to be an effective design for providing fecal separation and transport. Simulated urine tests and female user tests in zero gravity established air flow rates between 0.08 and 0.25 cu sm/min (3 and 9 scfm) as satisfactory for entrapment, containment and transport of urine using an urinal. The investigation of air drying of fecal material as a substitute for vacuum drying in a WCS breadboard system showed that using baseline conditions anticipated for the shuttle cabin ambient atmosphere, flow rates of 0.14 cu sm/min (5 cfm) were adequate for drying and maintaining biological stability of the fecal material.

Burt, R. A.↗
DOE OSTI2023

Speciation and Reactivity Control of Cu-Oxo Clusters via Extraframework Al in Mordenite for Methane Oxidation

The stoichiometric conversion of methane to methanol by Cu-exchanged zeolites can be brought to highest yields by the presence of extraframework Al and high CH 4 chemical potentials. Here, combining theory and experiments, the differences in chemical reactivity of monometallic Cu-oxo and bimetallic Cu-Al-oxo nanoclusters stabilized in zeolite mordenite (MOR) are investigated. Cu-L 3 edge X-ray absorption near-edge structure (XANES), infrared (IR), and ultraviolet–visible (UV–vis) spectroscopies, in combination with CH 4 oxidation activity tests, support the presence of two types of active clusters in MOR and allow quantification of the relative proportions of each type in dependence of the Cu concentration. Ab initio molecular dynamics (MD) calculations and thermodynamic analyses indicate that the superior performance of materials enriched in Cu-Al-oxo clusters is related to the activity of two μ-oxo bridges in the cluster. Replacing H 2 O with ethanol in the product extraction step led to the formation of ethyl methyl ether, expanding this way the applicability of these materials for the activation and functionalization of CH 4 . We show that competition between different ion-exchanged metal-oxo structures during the synthesis of Cu-exchanged zeolites determines the formation of active species, and this provides guidelines for the synthesis of highly active materials for CH 4 activation and functionalization.

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

Reactivities of Interstitial Hydrides in a Cu 11 Template: En Route to Bimetallic Clusters

In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu + , Ag + , and Au + ), the stable CuI dihydride template [Cu 11 H 2 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 ] (H 2 Cu 11 ) generates surprisingly three very different compounds, namely [CuH 2 Cu 11 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 ] + (1), [AgH 2 Cu 14 {S 2 P(OiPr) 2 } 6 ((C≡CPh) 6 ] + (2), and [AuCu 11 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 Cl] (3). Compounds 1 and 2 are both MI species and maintain the same number of hydride ligands as their H 2 Cu 11 precursor. Neutron diffraction revealed the first time a trigonal-pyramidal hydride coordination mode in the AgCu 3 environment of 2. 3 has no hydride and exhibits a mixed-valent [AuCu 11 ] 10+ metal core, making it a two-electron superatom.

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

Materials Data on CuSn3F6 by Materials Project

Cu(SnF2)3 is Cyanogen Chloride-like structured and crystallizes in the triclinic P-1 space group. The structure is zero-dimensional and consists of one cuprum molecule and three tin difluoride molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2020

One-step transformation of biomass to fuel precursors using a bi-functional combination of Pd/C and water tolerant Lewis acid

Direct one-pot transformation of lignocellulosic biomass has been developed as an effective and sustainable strategy to produce fuel blend stocks and high value chemical building blocks. In this wok, a bi-functional catalyst system consisting of palladium supported on carbon (Pd/C) and metal triflates (i.e., Sm(OTf) 3 , La(OTf) 3 , and Cu(OTf) 2 ) were shown to promote the biomass liquefaction in both hot-compressed water and supercritical ethanol medium, converting fir wood into oxygenated compounds. We report the highest bio-oil yield from hydrothermal liquefaction (HTL) was 10.47 wt% over Pd/C whereas the highest bio-oil yield of 49.71 wt% was achieved from supercritical ethanol liquefaction (SCEL) over the bi-functional catalyst system of Pd/C and La(OTf) 3 . Higher heating values, carbon recovered values and boiling point distributions were further determined for elucidating the physical properties of the bio-oils. Gas chromatography mass spectrometry (GC–MS) analysis of the bio-oils revealed the chemical composition of the bio-oils. Substituted phenols and cyclopentenone/cyclopentanone type compounds consisted of more than 60 area% of the total products from HTL, whereas phenol and esters represented the major products from SCEL. The major reaction pathways are proposed based on the GC–MS results, which include depolymerizaton, isomerization, dehydration, condensation, and hydrogenation.

09 BIOMASS FUELS↗
DOE OSTI2021

Isolated copper single sites for high-performance electroreduction of carbon monoxide to multicarbon products

Electrochemical carbon monoxide reduction is a promising strategy for the production of value-added multicarbon compounds, albeit yielding diverse products with low selectivities and Faradaic efficiencies. Here, copper single atoms anchored to Ti 3 C 2 T x MXene nanosheets are firstly demonstrated as effective and robust catalysts for electrochemical carbon monoxide reduction, achieving an ultrahigh selectivity of 98% for the formation of multicarbon products. Particularly, it exhibits a high Faradaic efficiency of 71% towards ethylene at -0.7 V versus the reversible hydrogen electrode, superior to the previously reported copper-based catalysts. Besides, it shows a stable activity during the 68-h electrolysis. Theoretical simulations reveal that atomically dispersed Cu–O 3 sites favor the C–C coupling of carbon monoxide molecules to generate the key *CO-CHO species, and then induce the decreased free energy barrier of the potential-determining step, thus accounting for the high activity and selectivity of copper single atoms for carbon monoxide reduction.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Counterintuitive Trend of Intrusion Pressure with Temperature in the Hydrophobic Cu 2 (tebpz) MOF

Liquid porosimetry experiments reveal a peculiar trend of the intrusion pressure of water in hydrophobic Cu 2 (3,3',5,5'-tetraethyl-4,4'-bipyrazolate) MOF. At lower temperature (T) range, the intrusion pressure (P i ) increases with T. For higher T values, P i first reaches a maximum and then decreases. This is at odds with the Young–Laplace law, which for systems showing a continuous decrease of contact angle with T predicts a corresponding reduction of the intrusion pressure. Though the Young–Laplace law is not expected to provide quantitative predictions at the subnanoscale of Cu 2 (tebpz) pores, the physical intuition suggests that to a reduction of their hydrophobicity corresponds a reduction of the P i . Molecular dynamics simulations and sychrothron experiments allowed to clarify the mechanism of the peculiar trend of P i with T. At increasing temperatures the vapor density within the MOF’ pores grows significantly, bringing the corresponding partial pressure to ≈5 MPa. This pressure, which is consistent with the shift of P i observed in liquid porosimetry, represents a threshold to be overcame before intrusion takes place. Beyond some value of temperature, the phenomenon of reduction of hydrophobicity (and water surface tension) dominated over the opposite effect of increase of vapor pressure and P i inverts its trend with T.

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

A redox model for NO oxidation, NH 3 oxidation and high temperature standard SCR over Cu-SSZ-13

A kinetic model is developed to predict the influence of temperature and hydrothermal aging on the redox of active Cu sites under standard SCR, NO oxidation and NH 3 oxidation conditions over a practically relevant fully-formulated Cu-SSZ-13 catalyst. NO 2 /N 2 production during NO/NH 3 titration of Cu II sites is utilized to identify rate parameters associated with NO-only RHC (reduction half cycle) and NH 3 -only RHC respectively. Integral N 2 formation during subsequent NO + NH 3 titration is consistent with the production of one NO 2 per two CuII sites reduced during NO-only RHC and one N 2 per six Cu II sites reduced during NH 3 -only RHC. Decreased reduction of Cu II sites by NO/NH 3 upon hydrothermal aging, along with the production of one NO 2 per two CuII sites during NO-only RHC, is accordant with the involvement of proximal ZCuOH and oxygen-bridged dimeric Cu II sites. Oxidation of partially solvated and framework coordinated ZCu (Cu I ) sites occurs in presence of O 2 , does not produce N 2 and can lead to the consumption of Brønsted acid sites. A global OHC kinetic model is developed to predict transient and integral N 2 formation during exposure of CuI sites to a mixture of NO and O 2 . The resulting redox kinetic model quantitatively predicts NO and NH 3 consumption during isothermal transient response Cu redox (TRCR) protocols, along with temperature and age dependent steady-state standard SCR and oxidation conditions. The redox model presented in this work synthesizes recent kinetic, spectroscopic and computational findings to provide a foundational description of active site redox during standard SCR, NO oxidation and NH3 oxidation over Cu-SSZ-13.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Precision Structure Engineering of High-Entropy Oxides under Ambient Conditions

High-entropy oxides (HEOs) have unveiled a unique frontier in the realm of heterogeneous catalysis, taking advantage of the entropic effect and increased complexities to deliver ultrahigh stability and large tuning capability. However, current HEO synthesis mainly relies on high-temperature annealing approaches affording HEOs possessing no or low surface area, inferior active site exposure efficiency, and low controllability over the structure tuning. The grand challenge lies in producing high-quality HEO catalysts with high active site utilization efficiency, which relies on precision structure engineering, preferably under mild conditions. In this work, an in situ lattice engineering approach was developed to afford a supported HEO catalyst under ambient conditions. The HEO compositions (CuCoFeNiMnO x ) were uniformly integrated into the lattice of CeO 2 driven by cavitation-induced nucleation being generated via ultrasonication. The as-afforded catalysts were featured by high surface area, atomically dispersed HEO compositions, active redox properties, abundant oxygen vacancies (O V ), antiagglomeration, and high phase stability under harsh conditions. Compared with the ex situ introduction of HEO on the surface, the in situ method provides dual benefits to maintain the dispersity of HEO via entropic and lattice confinement effects. Engineering the complex HEO within the lattice of fluorite-structured CeO 2 also yields abundant defects (e.g., O V ) and active metal sites with strong reducing properties (e.g., Ce 3+ and Cu + ), which greatly improves the activity of the lattice oxygen and tunability of the adsorption behavior of the guest molecules, especially in the presence of impurities (e.g., water and propane). The catalytic performance of the supported HEO catalyst in oxidative procedures surpasses the pure dense phase HEO as well as the ex situ-generated catalysts. Further, the synthesis approach being developed in this work, together with the fundamental understanding in structure evolution and reaction mechanism, showcases a facile pathway under ambient conditions to generate stable catalysts capable of maintaining structural robustness in high-temperature conditions while delivering enhanced catalytic performance.

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

Expanding the Ambient-Pressure Phase Space of CaFe 2 O 4 -Type Sodium Postspinel Host–Guest Compounds

CaFe 2 O 4 -type sodium postspinels (Na-CFs), with Na + occupying tunnel sites, are of interest as prospective battery electrodes. While many compounds of this structure type require high-pressure synthesis, several compounds are known to form at ambient pressure. Here we report a large expansion of the known Na-CF phase space at ambient pressure, having successfully synthesized NaCrTiO 4 , NaRhTiO 4 , NaCrSnO 4 , NaInSnO 4 , NaMg 0.5 Ti 1.5 O 4 , NaFe 0.5 Ti 1.5 O 4 , NaMg 0.5 Sn 1.5 O 4 , NaMn 0.5 Sn 1.5 O 4 , NaFe 0.5 Sn 1.5 O 4 , NaCo 0.5 Sn 1.5 O 4 , NaNi 0.5 Sn 1.5 O 4 , NaCu 0.5 Sn 1.5 O 4 , NaZn 0.5 Sn 1.5 O 4 , NaCd 0.5 Sn 1.5 O 4 , NaSc 1.5 Sb 0.5 O 4 , Na 1.16 In 1.18 Sb 0.66 O 4 , and several solid solutions. In contrast to earlier reports, even cations that are strongly Jahn–Teller active (e.g., Mn 3+ and Cu 2+ ) can form Na-CFs at ambient pressure when combined with Sn 4+ rather than with the smaller Ti 4+ . Order and disorder are probed at the average and local length-scales with synchrotron powder X-ray diffraction and solid-state NMR spectroscopy. Strong ordering of framework cations between the two framework sites is not observed, except in the case of Na 1.16 In 1.18 Sb 0.66 O 4 . This compound is the first example of an Na-CF that contains Na + in both the tunnel and framework sites, reminiscent of Li-rich spinels. Trends in the thermodynamic stability of the new compounds are explained on the basis of crystal-chemistry and density functional theory (DFT). Further DFT calculations examine the relative stability of the CF versus spinel structures at various degrees of sodium extraction in the context of electrochemical battery reactions.

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

Cryo-EM structures of Escherichia coli cytochrome bo 3 reveal bound phospholipids and ubiquinone-8 in a dynamic substrate binding site

Two independent structures of the proton-pumping, respiratory cytochrome bo3 ubiquinol oxidase (cyt bo 3 ) have been determined by cryogenic electron microscopy (cryo-EM) in styrene–maleic acid (SMA) copolymer nanodiscs and in membrane scaffold protein (MSP) nanodiscs to 2.55- and 2.19-Å resolution, respectively. The structures include the metal redox centers (heme b, heme o 3 , and Cu B ), the redox-active cross-linked histidine–tyrosine cofactor, and the internal water molecules in the proton-conducting D channel. Each structure also contains one equivalent of ubiquinone-8 (UQ8) in the substrate binding site as well as several phospholipid molecules. The isoprene side chain of UQ8 is clamped within a hydrophobic groove in subunit I by transmembrane helix TM0, which is only present in quinol oxidases and not in the closely related cytochrome c oxidases. Both structures show carbonyl O1 of the UQ8 headgroup hydrogen bonded to D75I and R71 I . In both structures, residue H98 I occupies two conformations. In conformation 1, H98 I forms a hydrogen bond with carbonyl O4 of the UQ8 headgroup, but in conformation 2, the imidazole side chain of H98 I has flipped to form a hydrogen bond with E14 I at the N-terminal end of TM0. We propose that H98 I dynamics facilitate proton transfer from ubiquinol to the periplasmic aqueous phase during oxidation of the substrate. Computational studies show that TM0 creates a channel, allowing access of water to the ubiquinol headgroup and to H98 I .

bioenergetics↗
DOE OSTI2023

{sup 58}Ni({sup 3}He,t){sup 58}Cu*({gamma}) Measurements with GODDESS to Constrain the Astrophysical Rate of {sup 57}Ni(p,{gamma}){sup 58}Cu

The observation of γ rays from the decay of 44Ti in the remnants of core-collapse supernovae (CCSNe) provides crucial information regarding the nucleosynthesis occurring in these events, as 44Ti production is sensitive to CCSNe conditions. The final abundance of 44Ti is also sensitive to specific nuclear input parameters, one of which is the 57Ni(p,γ) 58Cu reaction rate. A precise rate for 57Ni(p,γ) 58Cu is thus critical if 44Ti production is to be an effective probe into CCSNe. To experimentally constrain the 57Ni(p,γ) 58Cu rate, the structure properties of 58Cu were measured via the 58Ni(3He,t)58Cu*(γ) reaction using GODDESS (GRETINA ORRUBA Dual Detectors for Experimental Structure Studies) at Argonne National Laboratory’s ATLAS facility. Details of the experiment, ongoing analysis, and plans are presented.

Carmichael, S. R.↗
DOE OSTI2020

Resonant Soft X-Ray Scattering from Stripe-Ordered La 2 - x Ba x Cu O 4 Detected by a Transition-Edge Sensor Array Detector

Resonant soft x-ray scattering (RSXS) is a leading probe of valence-band order in materials best known for detecting charge-density-wave order in copper-oxide superconductors. One of the biggest limitations on the RSXS technique is the presence of a severe fluorescence background, which, like the RSXS cross section itself, is enhanced under resonant conditions. This background prevents the study of weak signals such as diffuse scattering from glassy or fluctuating order that is spread widely over momentum space. Recent advances in superconducting transition-edge-sensor (TES) detectors have led to major improvements in energy resolution and detection efficiency in the soft x-ray range. Here, we perform a RSXS study of stripe-ordered La 2 - x Ba x Cu O 4 at the Cu L 3 / 2 edge (932.2 eV) using a TES detector with 1.5-eV resolution, to evaluate its utility for mitigating the fluorescence-background problem. We find that, for suitable degree of detuning from the resonance, the TES rejects the fluorescence background, leading to a five to ten times improvement in the statistical quality of the data compared to an equivalent, energy-integrated measurement. We conclude that a TES introduces a promising method to reducing background in RSXS studies and may lead to discoveries in materials exhibiting valence-band order that is fluctuating or glassy.

36 MATERIALS SCIENCE↗