Transition of surface phase of cobalt oxide during CO oxidation
Transition of surface phase of cobalt oxide nanoparticle catalyst during CO oxidation in 60–200 °C tracked through AP-XPS.
Chemistry↗
SEARCH · Engineering Papers
Results for “OXIDATION”
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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Cross dehydrogenative coupling of N -aryltetrahydroisoquinolines (sp 3 C–H) with indoles (sp 2 C–H) using a heterogeneous mesoporous manganese oxide catalyst [Mesoporous manganese oxide catalyzed cross dehydrogenative coupling of N -aryltetrahydroisoquinolines (sp 3 C–H) with indoles (sp 2 C–H)]
Here, we disclose a novel, heterogeneous catalytic approach for selective coupling of C1 of N -aryltetrahydroisoquinolines with C3 of indoles in the presence of mesoporous manganese oxides. Our work involves a detailed mechanistic investigation of the reaction on the catalyst surface, backed by DFT computational studies, to understand the superior catalytic activity of manganese oxides.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Confinement boosts CO oxidation on an Ni atom embedded inside boron nitride nanotubes
Because of the confinement effect, Ni embedded on the interior surface of BNNT exhibits a much higher catalytic activity for CO oxidation by comparing with that embedded in h-BN or on the outside surface of BNNT.
Chemistry↗
Origin of fast oxide ion diffusion along grain boundaries in Sr-doped LaMnO 3
Enhanced oxide ion diffusion by 3 to 5 orders of magnitude along grain boundary core in Sr-doped LaMnO 3 .
Chemistry↗
Flux crystal growth: a versatile technique to reveal the crystal chemistry of complex uranium oxides
Molten flux crystal growth is a thriving field for the discovery of uranium oxides.
Juillerat, Christian A.↗
Cobalt-substituted SrTi 0.3 Fe 0.7 O 3–δ : a stable high-performance oxygen electrode material for intermediate-temperature solid oxide electrochemical cells
A key need in the development of solid oxide cells (SOCs) is for electrodes that promote fast oxygen reduction and oxygen evolution reactions at reduced operating temperature (≤700 °C), with sufficient durability to allow operation over desired 40 000 h lifetimes. A wide range of electrode materials have been investigated, with some providing resistance low enough for cell operation below 700 °C, but it is generally found that the electrode performance degrades over time. Here we demonstrate an oxygen electrode material, Sr(Ti 0.3 Fe 0.7–x Co x )O 3–δ (STFC), that provides a unique combination of excellent oxygen electrode performance and long-term stability. The addition of a relatively small amount of Co to Sr(Ti 0.3 Fe 0.7 )O 3–δ , e.g., x = 0.07, reduces the electrode polarization resistance by >2 times. The STFC electrode yields stable performance in both fuel cell and electrolysis modes at 1 A cm –2 . The fundamental oxygen diffusion and surface exchange coefficients of STFC are determined, and shown to be substantially better than those of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3–δ , the most widely used SOC oxygen electrode material. Here, while other electrode materials have been shown to exhibit better oxygen transport coefficients than STFC, they do not match its stability.
25 ENERGY STORAGE↗
A comparative study of secondary depolymerization methods on oxidized lignins
DDQ oxidized lignins were used as substrates to assess the effectiveness of secondary depolymerization methods for the production of aromatics.
Song, Yang↗
Intracellular Dynamics of Superparamagnetic Iron Oxide Nanoparticles for Magnetic Partical Imaging
Superparamagnetic iron oxide nanoparticles (SPIONs) are a foundational platform for a variety of biomedical applications. Of particular interest is Magnetic Particle Imaging (MPI), which is a growing area of research and development due to its advantages including high resolution and sensitivity with positive contrast. There has been signicant work in the area of in vivo optimization of SPIONs for MPI as well as their biodistribution in and clearance from the body. However, little is known about the dynamics of SPIONs following cellular internalization which may limit their usefulness in a variety of potential imaging and treatment applications. This work shows a clear 20% decrease in magnetic performance of SPIONs, as observed by Magnetic Particle Spectroscopy (MPS), after internalization and systematic consideration of applicable factors that aect SPION signal generation, including microstructure, environment, and interparticle interactions. There is no observed change to SPION microstructure after internalization, and the surrounding environment plays little to no role in magnetic response for the SPIONs studied here. Interparticle interactions described by dipole-dipole coupling of SPIONs held close to one another after internalization are shown to be the dominant cause of decreased magnetic performance in cells. These conclusions were drawn from transmission electron microscopy (TEM) image analysis at relevant length scales, experimentally prepared and characterized SPIONs in varied environmental conditions, and theoretical modeling with Monte Carlo simulations.
Teeman, Eric M.↗
Conformal SnO x heterojunction coatings for stabilized photoelectrochemical water oxidation using arrays of silicon microcones
A protective tin oxide layer formed by atomic-layer deposition limits surface recombination at n-Si surfaces and produces ∼620 mV of photovoltage on planar n-Si photoanodes. The layer conformally coats structures such as Si microcone arrays.
Moreno-Hernandez, Ivan A.↗
Identification of the acetaldehyde oxide Criegee intermediate reaction network in the ozone-assisted low-temperature oxidation of trans -2-butene
Uni- and bi-molecular reactions involving Criegee intermediates (CIs) have been the focus of many studies due to the role these molecules play in atmospheric chemistry. The reactivity of CIs is known to strongly depend on their structure. The reaction network of the second simplest CI, acetaldehyde oxide (CH 3 CHOO), is investigated in this work in an atmospheric pressure jet-stirred reactor (JSR) during the ozonolysis of trans-2-butene to explore the kinetic pathways relevant to atmospheric chemistry and low-temperature combustion. The mole fraction profiles of reactants, intermediates, and final products are determined by means of molecular-beam mass spectrometry in conjunction with single-photon ionization employing tunable synchrotron-generated vacuum ultraviolet radiation. A network of CI reactions is identified in the temperature region below 600 K, characterized by CI addition to trans-2-butene, water, formaldehyde, formic acid, and methanol. No sequential additions of the CH 3 CHOO CI are observed, in contrast with the reactivity of the simplest CI (H 2 COO) and the earlier observation of an extensive reaction network with up to four H 2 COO sequential additions (Phys. Chem. Chem. Phys., 2019, 21, 7341–7357). Experimental photoionization efficiency scans recorded at 300 K and 425 K and ab initio threshold energy calculations lead to the identification and quantification of previously elusive intermediates, such as ketohydroperoxide and hydroperoxide species. Specifically, the C 4 H 8 + O 3 adduct is identified as a ketohydroperoxide (KHP, 3-hydroperoxybutan-2-one, CH 3 C([double bond, length as m-dash]O)CH(CH 3 )OOH), while hydroxyacetaldehyde (glycolaldehyde, HCOCH 2 OH) formation is attributed to unimolecular isomerization of the CIs. Other hydroperoxide species such as methyl hydroperoxide (CH 3 OOH), ethyl hydroperoxide (C 2 H 5 OOH), butyl hydroperoxide (OOH), hydroperoxyl acetaldehyde (HOOCH 2 CHO), hydroxyethyl hydroperoxide (CH 3 CH(OH)OOH), but-1-enyl-3-hydroperoxide, and 4-hydroxy-3-methylpentan-2-one (HOCH(CH 3 )CH(CH 3 )C([double bond, length as m-dash]O)CH 3 ) are also identified. Detection of additional oxygenated species such as methanol, ethanol, ketene, and aldehydes suggests multiple active oxidation routes. Finally, these results provide additional evidence that CIs are key intermediates of the ozone-unsaturated hydrocarbon reactions providing critical inputs for improved kinetics models.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The dynamic behavior of dilute metallic alloy Pd x Au 1−x /SiO 2 raspberry colloid templated catalysts under CO oxidation
Dilute palladium-in-gold alloys have potential as efficient oxidation catalysts; controlling the Pd surface distribution is critical.
Filie, Amanda↗
Structural and reactive evolution of oxidatively grafted Pd catalysts on MnO 2 for the low-temperature oxidation of CO
We report Isolated Pd atoms supported on high surface area MnO 2 , prepared by the oxidative grafting of (bis(tricyclohexylphosphine-palladium(0)), catalyze (>50 turnovers, 17 h) the low temperature (≤325 K) oxidation of CO (7.7 kPa O 2 , 2.6 kPa CO) with results of in situ/operando and ex situ spectroscopic characterization signifying a synergistic role of Pd and MnO 2 in facilitating redox turnovers.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Effect of Ni content on the morphological evolution of Ni-YSZ solid oxide fuel cell electrodes
The coarsening of Ni in Ni–yttria-stabilized zirconia (YSZ) anodes is a potential cause of long term solid oxide fuel cells (SOFC) performance degradation. The specifics of the Ni-YSZ structure—including Ni/YSZ ratio, porosity, and particle size distributions—are normally selected to minimize anode polarization resistance, but they also impact long-term stability. A better understanding of how these factors influence long-term stability is important for designing more durable anodes. The effect of structural details, e.g., Ni-YSZ ratio, on Ni coarsening has not been quantified. Furthermore, prior measurements have been done by comparing evolved structures with control samples, such that sample-to-sample variations introduce errors. Here in this paper, we report a four dimensional (three spatial dimensions and time) study of Ni coarsening in Ni-YSZ anode functional layers with different Ni/YSZ ratios, using synchrotron x-ray nano-tomography. The continuous structural evolution was observed and analyzed at sub-100 nm resolution. It is shown quantitatively that increasing the Ni/YSZ ratio increases the Ni coarsening rate. This is due to both increased pore volume and a decrease in the YSZ volume fraction, such that there is more free volume and a less obtrusive YSZ network, both of which allow greater Ni coarsening. The results are shown to be in good agreement with a power-law coarsening model. In conclusion, the finding is critical for informing the design of SOFC electrode microstructures that limit coarsening and performance degradation.
36 MATERIALS SCIENCE↗
Patterning of graphene oxide with optoelectronic tweezers
Optoelectronic tweezers (OET) offer a means for parallel trapping and dynamic manipulation of micro-scale particles using low-intensity light. Such capabilities can facilitate the formation of bulk materials with a precisely tailored microstructure. Here, we report the use of OET to vertically align, trap, and reposition sheets of graphene oxide (GO) in liquids, paving the way for textured and patterned graphene macroassemblies that could offer superior performance for applications in energy storage, catalysis, and electronic devices. Trapping can be achieved with low-power light from inexpensive digital projectors and diode lasers, making it simple for users to create and apply patterns while avoiding undesirable photothermal heating effects. To give users a quantitative idea of trap stiffness, we also present a theoretical framework for predicting the maximum achievable speed of a GO platelet in an OET trap.
Lim, Matthew B. (ORCID:0000000161299876)↗
High temperature characteristics of nitric oxide annealed p-channel 4H-SiC metal oxide semiconductor field effect transistors
In this work, p-channel 4H-SiC MOSFETs were fabricated and analyzed at high temperature. It is demonstrated that nitridation of the gate oxide enables enhancement mode operation in these devices. Nitrogen incorporation at the 4H-SiC/SiO2 interface by nitric oxide annealing reduces the interface trap density energetically located in the lower half of the 4H-SiC bandgap, resulting in viable high temperature p-channel devices. In the 27–300 °C temperature range, the threshold voltage decreases with increasing temperature, consistent with the reduction of occupied interface traps at higher temperatures. The hole channel mobility is weakly temperature dependent under strong inversion conditions. Hall measurements support that above the threshold voltage, the mobility is limited by surface roughness scattering. In weaker inversion, the channel conductivity is limited by interface hole trapping and Coulomb scattering. In addition, high temperature bias stress measurements confirm a temperature activated hole trapping under negative gate bias, which requires further investigations.
Das, Suman (ORCID:0000000317146287)↗
The Ehrlich–Schwoebel barrier on an oxide surface: a combined Monte-Carlo and in situ scanning tunneling microscopy approach
The controlled growth of epitaxial films of complex oxides requires an atomistic understanding of key parameters determining final film morphology, such as termination dependence on adatom diffusion, and height of the Ehrlich–Schwoebel (ES) barrier. In this study, through an in situ scanning tunneling microscopy study of mixed-terminated La 5/8 Ca 3/8 MnO 3 (LCMO) films, we image adatoms and observe pile-up at island edges. Image analysis allows determination of the population of adatoms at the edge of islands and fractions on A-site and B-site terminations. A simple Monte-Carlo model, simulating the random walk of adatoms on a sinusoidal potential landscape using Boltzmann statistics is used to reproduce the experimental data, and provides an estimate of the ES barrier as ~0.18 ± 0.04 eV at T = 1023 K, similar to those of metal adatoms on metallic surfaces. In conclusion, these studies highlight the utility of in situ imaging, in combination with basic Monte-Carlo methods, in elucidating the factors which control the final film growth in complex oxides.
36 MATERIALS SCIENCE↗
Oxidation and crystal field effects in uranium
An in-depth exploration of oxidation in uranium has been pursued. This includes the utilization of soft x-ray absorption spectroscopy, hard x-ray absorption near-edge structure, resonant (hard) x-ray emission spectroscopy, cluster calculations, and a branching ratio analysis founded on atomic theory. The samples utilized were uranium dioxide (UO 2 ), uranium trioxide (UO 3 ), and uranium tetrafluoride (UF 4 ). A report on the role of nonspherical perturbations, i.e., crystal or ligand field effects, will be presented.
36 MATERIALS SCIENCE↗
Comparison of the high-pressure behavior of the cerium oxides C e 2 O 3 and Ce O 2
We studied the high-pressure behavior of Ce 2 O 3 using angle-dispersive x-ray diffraction to 70 GPa and compared with that of CeO 2 . Up to the highest pressure Ce 2 O 3 remains in the hexagonal phase (space group 164, P ¯32/m1) typical for the lanthanide sesquioxides. We did not observe a theoretically predicted phase instability for 30 GPa. The isothermal bulk modulus and its pressure derivative for the quasihydrostatic case are B 0 = 111 ± 2 GPa, B' 0 = 4.7 ± 0.3, and for the case without pressure-transmitting medium B 0 = 104 ±4 GPa, B' 0 = 6.5 ± 0.4. Starting from ambient-pressure magnetic susceptibility measurements for both oxides in highly purified form,we find that the Ce atom in Ce 2 O 3 behaves like a trivalent Ce 3+ ion (2.57μB per Ce atom) in contrast to previously published data. Since x-ray emission spectroscopy of the Lγ (4d 3/2 → 2p 1/2 ) transition is sensitive to the 4f -electron occupancy, we also followed the high-pressure dependence of this line for both oxides up to 50 GPa. We observed no change of the respective line shape, indicating that the 4f -electron configuration is stable for both materials. We posit from this data that the 4f electrons do not drive the volume collapse of CeO 2 from the high-symmetry, low-pressure fluorite structure to the lower-symmetry orthorhombic phase.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗