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Results for “complex oxides”

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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

In situ electron microscopy: atomic-scale dynamics of metal oxidation and corrosion

Corrosion degrades metals through complex microscopic processes that traditional methods often fail to capture. In-situ transmission electron microscopy (TEM) bridges this gap by providing real-time atomic-scale imaging of oxidation and corrosion dynamics. Gas-phase TEM uncovers critical oxidation mechanisms like oxide nucleation and alloying effects, while liquid-phase TEM tracks corrosion initiation. Coupled with emerging techniques like ultrafast direct electron detection cameras, these advancements promise unprecedented resolution in understanding material degradation.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Pt Particles on a Dynamic TiO 2 Support in Near-Ambient Conditions−Disentangling Size, Pressure, and Support Effects

Platinum particles on reducible oxides are known to form complex and highly dynamic catalyst systems at elevated pressures and temperatures, often adopting active structures that differ from those found at room temperature and under ultrahigh vacuum (UHV). Here, we study the oxidation and structural evolution of subnanometer Pt clusters and nanoparticles supported on rutile TiO 2 (110) across an oxygen pressure range from UHV to 0.1 mbar, using near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), scanning tunneling microscopy (STM) under UHV and NAP conditions, and low-energy ion scattering (LEIS). Our results reveal distinct differences in oxidation behavior and thermal stability between Pt nanoparticles and clusters, which are further modulated by the support stoichiometry and oxygen pressure. Small Pt clusters become oxidized even at room temperature but are susceptible to accelerated sintering in 0.1 mbar O 2 at elevated temperatures. In contrast, well-crystallized Pt nanoparticles on near-stoichiometric TiO 2 show weaker oxidation. On a reduced, defective TiO 2 support, Pt instead quickly becomes deeply buried by new titania layers, which are formed during support reoxidation. This process appears to result primarily from interactions of the support with the gas phase, unlike the classical, selflimited encapsulation that is induced by the strong metal−support interaction (SMSI). Finally, we address the full complexity of real catalysts in a direct side-by-side comparison of the single-crystalline model system with a Pt-loaded TiO 2 powder catalyst (P25). We conclude that the stoichiometry of the model supports must be carefully chosen and controlled to accurately reproduce the expected state of powder supports during redox reactions.

metal nanoparticles↗
DOE OSTI2024

Mixed Valence {Ni 2+ Ni 1+ } Clusters as Models of Acetyl Coenzyme A Synthase Intermediates

Acetyl coenzyme A synthase (ACS) catalyzes the formation and deconstruction of the key biological metabolite, acetyl coenzyme A (acetyl-CoA). The active site of ACS features a {NiNi} cluster bridged to a [Fe4S4] n+ cubane known as the A-cluster. The mechanism by which the A-cluster functions is debated, with few model complexes able to replicate the oxidation states, coordination features, or reactivity proposed in the catalytic cycle. In this work, we isolate the first bimetallic models of two hypothesized intermediates on the paramagnetic pathway of the ACS function. The heteroligated {Ni 2+ Ni 1+ } cluster, [K(12-crown-4) 2 ][1], effectively replicates the coordination number and oxidation state of the proposed “A red ” state of the A-cluster. Addition of carbon monoxide to [1] - allows for isolation of a dinuclear {Ni 2+ Ni 1+ (CO)} complex, [K(12-crown-2) n ][2] (n = 1–2), which bears similarity to the “A NiFeC ” enzyme intermediate. Structural and electronic properties of each cluster are elucidated by X-ray diffraction, nuclear magnetic resonance, cyclic voltammetry, and UV/vis and electron paramagnetic resonance spectroscopies, which are supplemented by density functional theory (DFT) calculations. Calculations indicate that the pseudo-T-shaped geometry of the three-coordinate nickel in [1] – is more stable than the Y-conformation by 22 kcal mol –1 , and that binding of CO to Ni 1+ is barrierless and exergonic by 6 kcal mol –1 . UV/vis absorption spectroscopy on [2] - in conjunction with time-dependent DFT calculations indicates that the square-planar nickel site is involved in electron transfer to the CO π*-orbital. Further, we demonstrate that [2] - promotes thioester synthesis in a reaction analogous to the production of acetyl coenzyme A by ACS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1983

The oxidation behavior of a model molybdenum/tungsten-containing alloy in air alone and in air with trace levels of NaCl(g)

Thermogravimetric, metallographic, and X-ray studies of a model alloy, Ni-(17 a/o)Al-(10 a/o)Mo+W, oxidized in dry air at 600-1200 C and in air with 10 ppm NaCl gas at 900 C, are reported. The alloy was melted under Ar and pretreated in flowing H2 for 24 h at 1300 C. Polished 1.3 x 1.3 x 0.2-cm specimens were washed and degreased prior to oxidation in a quartz tube within a furnace for up to 120 hr. The oxidation activation energy of the alloy is determined to be about 30 kcal/mole. The specimens oxidized at 900 C and hotter exhibited oxidized and nitrided phases covered by complex NiMoO4, NiWO4, and NiAl2O4 scales and a porous, nonprotective outer layer of NiO. The oxidation behavior is found to be determined by the formation and growth of the scale, especially the (Mo,W)O2 component. Al2O3 scale layers were not formed, and further runs with pure O2 or Ar-(20 percent)O2 ruled out an explanation of this phenomenon based on aluminum nitride formation. The oxidation was accelerated by the addition of NaCl gas, a finding attributed to the reaction of NaCl with external locally protective Al2O3 scales and with the internal(Mo, W)O2 layers.

Smeggil, J. G.↗
NASA NTRS1978

Aquatic sources and sinks for nitrous oxide

Data are presented which suggest the complexity of the aquatic nitrogen cycle as it affects N2O. The data are from studies made in the central and south-east tropical regions of the Pacific Ocean and in Chesapeake Bay. The data indicate that oxidation of ammonium and amino nitrogen and nitrification form the principle source for marine N2O. It is estimated that the yearly global yield for oceanic N2O is less than about 10 to the 7th power tons. The consumption of atmospheric N2O by the open ocean has not been evidenced, although data from the south-east tropical Pacific and Chesapeake Bay show the consumption of dissolved N2O in low-oxygen conditions. Preliminary observations have also indicated the consumption of atmospheric N2O by aquatic systems such as freshwater pond and a tidal saltmarsh.

Elkins, J. W.↗
NASA NTRS1990

Oxidation characteristics of Ti-14Al-21Nb ingot alloy

Static oxidation kinetics of Ti14Al21Nb (wt pct) ingot alloy were studied in air over the temperature interval of 649 to 1093 C in a thermogravimetric apparatus. The oxidation products were characterized by x ray diffraction, electron microprobe analysis, energy dispersive x ray analysis, and Auger electron spectroscopy. Cross-sections of the oxidized samples were also examined using light and scanning electron microscopy. The oxidation rate was substantially lower than the conventional alloys of titanium, but the kinetics displayed a complex behavior involving two or more oxidation rates depending on the temperature and duration of exposure. The primary oxide formed was TiO2, but this oxide was doped with Nb. Small amounts of Al2O3 and TiN were also present in the scale. Diffusion of oxygen into the alloy was observed and the diffusivity seemed to be dependent on the microstructure of the metal. A model was presented to explain the oxidation behavior of the alloy in terms of the reduction in the oxygen diffusivity in the oxide caused by the modification of the defect structure of TiO2 by Nb ions.

Sankaran, Sankara N.↗
NASA NTRS1991

Surface activation of air oxidation of hydrazine on kaolinite. 2. Consideration of oxidizing/reducing entities in relationship to other compositional, structural, and energetic factors

The rates (previously reported) for the air oxidation of hydrazine on kaolinite and substituent oxides of kaolinite showed a complex dependence on the relative amounts of several structural oxidizing/reducing entities within the reaction-promoting solids. The rates indicated an important role of the clay but no dominant role of any one of the oxidizing/reducing entities. In this paper we review (a) the reaction-promoting activity of these centers as studied in other systems, (b) various spectroscopic results showing interaction between these entities in clays, and (c) reported spectroscopic studies of the complexation between hydrazine and aluminosilicate surfaces as a whole, in an effort to propose a mechanism for the reaction. Whereas some uncertainties remain, the present synthesis concludes that a mechanism operating through single electron/hole transfers and hydrogen atom transfers by discrete centers is adequate to explain the observed rate behaviors including the observed second order dependence of the oxidation rate on catalyst amount. The effects of these operations on the catalyst can result in no alteration of, or complete or partial electronic relaxation of its contingent of trapped separated charge pairs. The degree to which surface complexation as a whole, intercalation, or luminescent processes may also be associated with the reaction cannot be adequately assessed with the information in hand.

NASA Program Exobiology↗
NASA NTRS1994

Transmission measurements (4000-400 cm(exp -1), 2.5-25 microns) of crystalline ferric oxides and ferric oxyhydroxides: Implications for Mars

Transmission spectra of three ferric oxides (two alpha-Fe2O3 samples and one gamma-Fe2O3 sample) and two ferric oxyhydroxides (alpha-FeOOH and gamma-FeOOH) were measured. This preliminary study has demonstrated that crystalline ferric oxides and ferric oxyhydroxides exhibit complex spectral features at thermal wavelengths. Some of these features suggest that thermal infrared observations of Mars can provide significant insight into the ferric mineralogy of that planet. The results of this study suggest that emissivity spectra of crystalline ferric oxides and ferric oxyhydroxides may prove quite important for the interpretation of thermal infrared spectral observations of Mars.

Roush, Ted L.↗
DOE OSTI2024

Vibrational properties of heme-nitrosoalkane complexes in comparison with those of their HNO analogs, and reactivity studies towards nitric oxide and Lewis acids

C-Nitroso compounds (RNO, R = alkyl and aryl) are byproducts of drug metabolism and bind to heme proteins, and their heme-RNO adducts are isoelectronic to ferrous nitroxyl (NO-/HNO) complexes. Importantly, heme-HNO compounds are key intermediates in the reduction of NO to N 2 O and nitrite to ammonium in the nitrogen cycle. Ferrous heme-RNO complexes act as stable analogs of these species, potentially allowing for the investigation of the vibrational and electronic properties of unstable heme-HNO intermediates. In this paper, a series of six-coordinate ferrous heme-RNO complexes (where R = iPr and Ph) were prepared using the TPP 2- and 3,5-Me-BAFP 2- co-ligands, and tetrahydrofuran, pyridine, and 1-methylimidazole as the axial ligands (bound trans to RNO). These complexes were characterized using different spectroscopic methods and X-ray crystallography. The complex [Fe(TPP)(THF)(iPrNO)] was further utilized for nuclear resonance vibrational spectroscopy (NRVS), allowing for the detailed assignment of the Fe–N(R)O vibrations of a heme-RNO complex for the first time. The vibrational properties of these species were then correlated with those of their HNO analogs, using DFT calculations. Our studies support previous findings that RNO ligands in ferrous heme complexes do not elicit a significant trans effect. In addition, the complexes are air-stable, and do not show any reactivity of their RNO ligands towards NO. So although ferrous heme-RNO complexes are suitable structural and electronic models for their HNO analogs, they are unsuitable to model the reactivity of heme-HNO complexes. We further investigated the reaction of our heme-RNO complexes with different Lewis acids. Here, [Fe(TPP)(THF)(iPrNO)] was found to be unreactive towards Lewis acids. In contrast, [Fe(3,5-Me-BAFP)(iPrNO) 2 ] is reactive towards all of the Lewis acids investigated here, but in most cases the iron center is simply oxidized, resulting in the loss of the iPrNO ligand. In the case of the Lewis acid B 2 (pin) 2 , the reduced product [Fe(3,5-Me-BAFP)(iPrNH 2 )(iPrNO)] was identified by X-ray crystallography.

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

Praseodymium in the formal +5 oxidation state

Praseodymium in the +5 oxidation state is a long-sought connection between lanthanide, early-transition and actinide metal redox chemistries. Unique among the lanthanide series, evidence for molecular pentavalent praseodymium species has been observed in the gas phase and noble gas matrix isolation conditions. Here we report the low-temperature synthesis and characterization of a molecular praseodymium complex in the formal +5 oxidation state, [Pr 5+ (NP t Bu 3 ) 4 ][X − ] (where t Bu = tert -butyl and X − = tetrakis(pentafluorophenyl)borate or hexafluorophosphate). Single-crystal X-ray diffraction, solution-state spectroscopic, solution magnetometric, density functional theory and multireference wavefunction-based methods indicate a highly multiconfigurational singlet ground state. Finally, an inverted ligand field drives this unique electronic structure, which establishes a critical link in understanding the bonding of high-valent metal complexes across the periodic table.

chemical bonding↗
DOE OSTI2025

Redistribution of Ru in Fe 2 O 3 –Ru Nanocatalysts through an Oxidative Pretreatment Improves Reverse Water–Gas Shift Activity

We have synthesized Fe–Ru nanoparticles via a solvothermal method to create catalysts for the reverse water–gas shift reaction and demonstrated the impact of reductive and oxidative pretreatments on both catalytic performance and structure. Catalytic testing showed improved activity after exposure to O 2 at 600 °C. In contrast, the activity became lower if then exposed to H 2 at 600 °C. Environmental scanning transmission electron microscopy and scanning electron microscopy showed that exposure to O 2 at 600 °C changes the morphology and completely oxidizes Fe into Fe 2 O 3 . Exposure to H 2 at elevated temperature caused Ru coalescence at the surface of the nanoparticle, forming clusters which decreased the optimization of Ru. Reoxidation of the particles exposed to H 2 , however, caused a redistribution of Ru that appears beneficial in maximizing Ru exposure and synergy with Fe oxide, with no major changes in the morphology and oxide structure. Furthermore, our diagnostics demonstrate the complex and reversible rearrangements possible in these multicomponent particles and the benefits of oxidative pretreatment to enhance or regenerate Fe–Ru catalysts in other important catalytic reactions such as Fischer–Tropsch synthesis.

Fe−Ru nanoparticles↗
NASA NTRS1999

Thermal Studies of New Precursors to Indium-tin Oxides for Use as Sensor Materials in the Detection of NO(x)

Control of combustion product emissions in both sub and super-sonic jet engines can be facilitated by measurement of NO(x) levels with metal oxide sensors, In2O3, metal-doped SnO2, and SnO, (as well as other materials) show resistivity changes in the presence of NO(x), but often their sensitivity, stability, and selectivity are low. This study was designed to develop new synthetic pathways to precursors that produce high purity, two phase In2O3-SnO2. The precursors were formed by complexation of tin with any oxide ligands to give the ammonium salt (NH4). Thermal studies of these precursors were carried out by thermal gravimetry (TG) and differential scanning calorimetry (DSC). Further studies by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR) were also conducted.

Goldsby, J. C.↗
DOE OSTI2025

Four-electron oxidation and one-electron reduction of the bis(terphenylthiolate) U( II ) complex, U(SAr iPr6 ) 2 [Ar iPr6 = C 6 H 3 -2,6-(C 6 H 2 -2,4,6- i Pr 3 ) 2 ]

Here, the utility of the sterically bulky terphenylthiolate ligand, (SAr iPr6 ) 1− in expanding uranium reductive chemistry has been explored. Reduction of U(SAr iPr6 ) 2 I forms the U(II) complex, U(SAr iPr6 ) 2 , in which the metal is protected by the flanking arene rings of the ligand, but they move out of the way to accommodate the four electron reduction of PhN=NPh to form the U(VI) bis(imido) product U(SAr iPr6 ) 2 (=NPh) 2 (THF) 2 . Here, the KC 8 reduction of U(SAr iPr6 ) 2 generates a more reduced complex, KU(μ-SAr iPr6 ) 2 , initially identified by a −2.55 V vs. Fc + /Fc electrochemical reduction event in THF.

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

CO oxidation over a ligand coordinated single site Rh catalyst: identification of the active complex

Single atom catalysis has evolved as a promising strategy to enhance atom utilization efficiency, lower reaction temperatures, and control reaction pathways in heterogeneous catalytic reactions. An important challenge using supported single atom catalysts is the stability of metal single atoms during reactions. Here, we present an approach to stabilize single rhodium atoms on a titania support via a metal–ligand coordination strategy. We explore the reaction activity and mechanism of CO oxidation, as well as the stability under oxidative reaction conditions. Kinetic studies suggest that, with an excess of oxygen in the feed gas, oxygen activation is more facile on defective titania surfaces than on pristine titania surfaces. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis shows that on the pristine titania surface, the 1,10-phenanthroline-5,6-dione (PDO) coordinated Rh catalyst (Rh–PDO/TiO 2 ) catalyzes CO oxidation via the formation of carbonate-like species, which is similar to what occurs on Rh nanoparticle catalysts. However, on the defective titania surface, no carbonate species form for Rh–PDO/def-TiO 2 . The supported Rh–ligand catalysts are also shown to be very stable in such a reaction environment at elevated temperatures, potentially allowing for wide applications.

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

Multiple oxidation states of uranium stabilized by an O , N , O -ligand

Elements of the 5f row maintain a wide variety of oxidation states that have been exploited in synthesis, catalysis, and separations. Herein, we describe the complexation of an O,N,O chelator, ExPh, with uranium in the (IV) and (VI) (uranyl) oxidation states. These two uranium complexes, U(IV)ExPh and UO 2 ExPh, respectively, were characterized in the solid state via single-crystal X-ray diffraction (SC-XRD) analysis. Electrochemical studies using cyclic voltammetry were employed to investigate the multiple redox events associated with the U(IV) complex. Spectro-electrochemical analysis of U(IV)ExPh provided spectroscopic evidence of a stable U(V) species. Chemical oxidation of U(IV)ExPh allowed isolation of the U(V) complex, U(V)ExPh. All three stable uranium complexes produced in this study were characterized via IR, UV-vis and NMR spectroscopies, and micro-spectrophotometry. On the other hand, efforts to reduce U(IV)ExPh to the corresponding U(III) species or produce this putative complex directly from ExPh failed to yield an isolable product. The stabilization of three formal oxidation states of uranium, coupled with previous lanthanide-row results, paves the way for studies of ExPh and its analogues in minor actinide chemistry.

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

Electrocatalytic Ammonia Oxidation with Coordinatively Saturated Ruthenium Catalyst

This communication describes the investigation of a coordinatively saturated complex [Ru(tpy)(dmabpy)Cl] + ([Ru(Cl)] + ) as an ammonia oxidation catalyst. Cyclic voltammetry measurements show an ideal S-shaped wave, indicating total catalysis conditions with a k obs (TOF max ) of 9360 h −1 . The reaction was found to be first-order in [Ru(Cl)] + and third-order in [NH 3 ]. Stoichiometric reactions of the one-electron oxidized species, [Ru(Cl)] 2+ , were monitored following the addition of 15 NH 3 using 1 H and 15 N NMR spectroscopy. These experiments showed that the chloride-coordinated complex rapidly converts NH 3 to N 2 . NMR spectroscopy and electrochemistry results definitively show that NH 3 does not substitute the Cl − ligand to form the previously reported [Ru(NH 3 )] 2+ catalyst which operates by a different mechanistic pathway. Taken together these results indicate outersphere electron transfer mediated ammonia oxidation reaction.

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

Single Component Dye-Sensitized Solar Cells Enabled by Copper Chemistry: Introduction of the Retro Cell

The possibility of utilizing a single molecule to act as both a chromophore and a redox shuttle in a new configuration of a dye-sensitized solar cell (DSSC) is investigated. This design, termed a retro cell, exploits the copper chromophore, [Cu(dsbtmp) 2 ] + (dsbtmp = bis(2,9-di(sec-butyl)-3,4,7,8- tetramethyl-1,10-phenanthroline), which has been shown to have excited state lifetimes in excess of a microsecond, enabling sensitization of TiO 2 while dissolved in solution. The oxidized chromophore can then diffuse to the counter electrode to be regenerated. This concept simplifies the device components and fabrication and eliminates a charge transfer step compared to that of traditional DSSCs. Initial investigations show the concept is viable; however, the performance is suboptimal. We have found the addition of 4-tertbutylpyridine (TBP) to the electrolyte plays a crucial role in enabling solar energy conversion. Evidence of TBP displacing one of the dsbtmp ligands in the oxidized [Cu(dsbtmp) 2 ] 2+ complex has been presented, which likely plays an important role in reducing recombination and enabling charge collection. The performance-limiting steps and routes to improved performance and viability of a retro cell are further discussed.

14 SOLAR ENERGY↗
NASA NTRS1989

Measurements of complex permittivity of microwave substrates in the 20 to 300 K temperature range from 26.5 to 40.0 GHz

A knowledge of the dielectric properties of microwave substrates at low temperatures is useful in the design of superconducting microwave circuits. Results are reported for a study of the complex permittivity of sapphire (Al2O3), magnesium oxide (MgO), silicon oxide (SiO2), lanthanum aluminate (LaAlO3), and zirconium oxide (ZrO2), in the 20 to 300 Kelvin temperature range, at frequencies from 26.5 to 40.0 GHz. The values of the real and imaginary parts of the complex permittivity were obtained from the scattering parameters, which were measured using a HP-8510 automatic network analyzer. For these measurements, the samples were mounted on the cold head of a helium gas closed cycle refrigerator, in a specially designed vacuum chamber. An arrangement of wave guides, with mica windows, was used to connect the cooling system to the network analyzer. A decrease in the value of the real part of the complex permittivity of these substrates, with decreasing temperature, was observed. For MgO and Al2O3, the decrease from room temperature to 20 K was of 7 and 15 percent, respectively. For LaAlO3, it decreased by 14 percent, for ZrO2 by 15 percent, and for SiO2 by 2 percent, in the above mentioned temperature range.

Miranda, Felix A.↗