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DOE OSTI2020

Metal-organic pulsed laser deposition for stoichiometric complex oxide thin films

Methods and systems for forming complex oxide films are provided. Also provided are complex oxide films and heterostructures made using the methods and electronic devices incorporating the complex oxide films and heterostructures. In the methods pulsed laser deposition is conducted in an atmosphere containing a metal-organic precursor to form highly stoichiometric complex oxides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2022

Metal-organic pulsed laser deposition for stoichiometric complex oxide thin films

Eom, Chang-Beom↗

DOE OSTI2023

Metal-organic pulsed laser deposition for stoichiometric complex oxide thin films

Eom, Chang-Beom↗

NASA NTRS1983

The diffusivity of hydrogen in Nb stabilized stainless steel

The evolution of hydrogen from 347 stainless steel has been studied by using a real time dynamic technique under ultrahigh vacuum conditions. Auger electron spectroscopy was used to determine the surface composition as a function of time and temperature. The surface film on the electropolished samples was found to be approximately 15 A thick and consisted of a carbon-oxygen complex and a metal oxide (FexOy). Upon heating to 400 C, the carbon-oxygen complex desorbed as CO and the remaining oxygen and carbon began to incorporate. Also at this temperature sulfur began to diffuse out of the bulk to the surface and at approximately 800 C formed a complete monolayer. At 900 C, carbon and oxygen virtually disappeared, leaving the monolayer of sulfur as the only surface contaminant. The hydrogen diffusivity was found to follow closely the equation D = 7.01 x 10 to the -7th exp(-48.0/RT) sq m per second over the entire temperature range studied, thus indicating that hydrogen evolution is not significantly affected by the changing surface composition. The somewhat higher value of the diffusivity obtained in this work compared to past measurements in austenitic stainless steels may indicate the importance of sample preprocessing and ultrahigh vacuum conditions in minimizing the effects of surface layers.

Outlaw, R. A.↗

DOE OSTI2020

Complexity and Opportunities in Liquid Metal Surface Oxides

Not provided.

Chemistry↗

DOE OSTI2021

Novel synthesis approach for “stubborn” metals and metal oxides

Significance Atomically precise complex oxides containing “stubborn” elements, such as ruthenium, iridium, and platinum, hold tremendous promise as designer quantum materials for exploring novel electronic, magnetic, superconducting, and topological phases owing to their strong spin–orbit interaction. This study shows a method to synthesize such materials by eliminating the major synthesis bottleneck of low vapor pressure and difficulty in oxidation. This study serves as a “proof-of-concept” allowing us to 1) grow Pt, RuO 2 , and SrRuO 3 thin films by supplying Pt and Ru precursors at 65 to 100 °C in a low-temperature effusion cell, as opposed to the several thousand degrees Celsius needed using electron beam evaporators; 2) reveal bulk-like room-temperature resistivity; and 3) ultimately provide pathways to creating atomically precise quantum structures.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Polyoxometalate-based complexes as ligands for the study of actinide chemistry

The complexation of actinide cations by polyoxometalates (POMs) has been extensively studied over the past 50 years. In this perspective article, we present the rich structural diversity of actinide-POM complexes and their contribution to the extension of our knowledges of actinide chemistry, especially regarding aspect of their redox chemistry, as well as application for the capture and separation of these cations in the context of nuclear fuel remediation. Furthermore, these heterometallic assemblies have also proven highly valuable as model for heterogeneous systems based on actinides supported by metal oxide surfaces. In particular, activation of the An–O bond of actinyl fragments upon complexation with lacunary POMs has been reported, creating opportunities for future developments regarding the reactivity of these heterometallic assemblies.

Auvray, Thomas↗

DOE OSTI2023

Toward Understanding and Controlling Organic Reactions on Metal Oxide Catalysts

Metal oxides have structurally complex surfaces on which a variety of adsorption site types can occur, including cation sites, anion sites, oxygen vacancy sites, and Brønsted acid sites. These sites can catalyze the catalytic transformation of organic molecules via diverse routes, thus enabling H abstraction, O abstraction, C–C bond formation, and other reactions. This Perspective provides an update on recent advances and future directions for various organic reactions on metal oxide catalyst surfaces, particularly for C–H activation of alkanes and for C–C bond formation with organic oxygenate reactants. Here, we put emphasis on the molecular scale details, on the active site structures required to enable the formation of kinetically relevant transition states, energetic descriptors, as well as contemporary ideas to enable low activation energies. This progress has been enabled by specialized experiments and the increased capabilities of modern electronic structure calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Reprogrammable electro-chemo-optical devices and methods for using the same

Reconfigurable, active optical components can flexibly manipulate light. One example of these components is an electro-chemo-optical device that utilizes a metal oxide film with a complex refractive index that varies as a function of an oxygen vacancy concentration. The optical device may include a metal oxide film, a first electrode, and a second electrode. The first electrode and the second electrode may be used to supply a bias voltage to induce a change in the oxygen vacancy concentration in order to change the optical properties (absorbance, transmittance, and/or reflectance) of the optical device. The magnitude and spatial distribution of the oxygen vacancy concentration may be altered to affect the optical properties of the optical device. In some designs, the optical device may also include an ionic conductor and oxygen source to supply/receive oxygen ions to/from the metal oxide film.

Kalaev, Dmitri↗

DOE OSTI2025

Anisotropic structure and optical engineering of strontium titanate and zirconia responding to sequential hydrogen and helium irradiation

Unraveling the correlation between strain engineering with anisotropic optical properties via nanoscale defects gradually evolved into a strategy for fundamental studies and technological applications, yet it remains understudied in functional complex oxides compared to metals and semiconductors. Here, the methodology of strain engineering for the determination of the lattice parameters, parallel/normal to the sample surface, in the individual layers of single-crystalline superlattices is derived, which is based on analysis of high-angle X-ray diffraction measurements in combination with diffraction reciprocal space mapping. With modeling that takes into account the effect of elastic properties, two elastically anisotropic materials, SrTiO 3 and ZrO 2 , have been compared in terms of defect-induced elastic strain caused by individual and sequential H + and He 2+ irradiation. The anisotropic lattice swelling with corresponding refractive index, and obstructive behavior of elastic strain recovery are demonstrated in SrTiO 3 , while approaching strain behaviors accompanied by isotropic refractive index distribution in both orientations are confirmed in ZrO 2 . Under sequential He 2+ /H + irradiation, pre-existing He-vacancy complexes acted as vacancy traps, preferentially capturing H + clusters to induce lattice distortion and enhance absorption. Nanohardness increments (ΔH) calculated by the DBH model matched nanoindentation results, confirming that sequential irradiation generated higher indentation yield stress than individual irradiations.

Anisotropic expansion↗

DOE OSTI2024

Single-Atom Manganese-Based Catalysts for the Oxidative Dehydrogenation of Propane

Combinatorial screening of 150 supported metal oxide (manganese and additives) catalysts was carried out via a high-throughput synthesis platform and parallel reactors for the oxidative dehydrogenation (ODH) of propane to propylene. Specifically, an organomanganese (0.05-2.5 Mn atoms/nm 2 ) complex was grafted on metal oxide supports (Al 2 O 3 , SiO 2 , TiO 2 , and ZrO 2 ) premodified with either Lewis acid (Al, Ti, Zn, and Zr) or redox-active (Cu, Cr, Ga Ni, V) additives at various surface coverages (25, 50, and 75%). Catalysts were characterized by high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy, and UV-vis spectroscopy. Catalysts 0.05 Mn/V(50%)/Al 2 O 3 and 0.05 Mn/Ni(50%)/ZrO 2 showed the highest combined propane conversion and propylene selectivities (31/41% and 15/85%), with excellent stability at 500 degrees C for 25 h. The presence of Ni in Mn/Ni/ZrO 2 resulted in a 6-fold increase in turnover frequency (TOF) over the Mn/ZrO 2 . HRTEM identified single Mn atoms after 500 degrees C heat treatment. For the Mn/Ni/ZrO 2 system, Mn was incorporated into the support lattice due to the similar ionic radius of Mn 2+ and Zr 4+ , which was also enhanced by the presence of Ni. For the Mn/V/Al 2 O 3 system, highly active MnO was prevalent as observed by Raman. Both V and Mn contributed to an increase in mutual dispersion, but both species remained on the surface. Finally, it is proposed that the highly dispersed atom and interactions between Mn with either Ni or V are responsible for the ODH performance and stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Effects of surface species and homogeneous reactions on rates and selectivity in ethane oxidation on oxide catalysts

Selective alkane oxidations on metal oxide catalysts involve complex mechanisms with multiple reactions in series and parallel, different types of reduced and oxidized surface species, and potential contributions from gas-phase reactions. We report kinetics and thermodynamics of elementary steps involved in C 2 H 6 -O 2 reactions on SiO 2 -supported small vanadium oxide domains are determined using density functional theory. These surface reactions together with gas-phase mechanisms are incorporated in kinetic simulations to determine how surface and gaseous reactions interact and contribute to rates and selectivity. The results show that gas-phase reactions within pore volumes in contact with the catalyst contribute significantly to C 2 H 6 activation rates, even at conditions where gas-phase reactions in empty volumes without catalyst are negligible. The majority of C 2 H 6 activations occur on the surface, via H abstraction by vanadium oxo species present at terminal lattice oxygens. The gas-phase activations via H-abstraction by OH radicals also exhibit significant contributions. The reduced centers formed by reactions at vanadium oxo species are re-oxidized rapidly and, therefore, are present in very small concentrations at reaction conditions. The re-oxidation steps lead to the formation of HO 2 radicals and surface peroxo species that are also rapidly consumed and are present in small concentrations. The peroxo species preferentially convert C 2 H 4 to its epoxide product and influence selectivity even at low concentrations. The gas-phase reactions decrease the concentrations of peroxo species and improve selectivity slightly. The effects of reaction conditions and catalyst site density provide further insights into how factors beyond conversions at lattice oxygens influence rates and selectivity in alkane oxidation reactions of significant industrial importance.

42 ENGINEERING↗

DOE OSTI2024

2024 roadmap on magnetic microscopy techniques and their applications in materials science

Considering the growing interest in magnetic materials for unconventional computing, data storage, and sensor applications, there is active research not only on material synthesis but also characterisation of their properties. In addition to structural and integral magnetic characterisations, imaging of magnetisation patterns, current distributions and magnetic fields at nano- and microscale is of major importance to understand the material responses and qualify them for specific applications. In this roadmap, we aim to cover a broad portfolio of techniques to perform nano- and microscale magnetic imaging using superconducting quantum interference devices, spin centre and Hall effect magnetometries, scanning probe microscopies, x-ray- and electron-based methods as well as magnetooptics and nanoscale magnetic resonance imaging. The roadmap is aimed as a single access point of information for experts in the field as well as the young generation of students outlining prospects of the development of magnetic imaging technologies for the upcoming decade with a focus on physics, materials science, and chemistry of planar, three-dimensional and geometrically curved objects of different material classes including two-dimensional materials, complex oxides, semi-metals, multiferroics, skyrmions, antiferromagnets, frustrated magnets, magnetic molecules/nanoparticles, ionic conductors, superconductors, spintronic and spinorbitronic materials.

2D materials↗

NASA NTRS2000

Nonprotective Alumina Growth in Sulfur-Doped NiAl(Zr)

The 1200 C oxidation behavior of NiAl was examined at various levels of sulfur and zirconium dopants to test the possibility of a critical S/Zr ratio required for adhesion. Cyclic furnace testing for 200 1 -hr cycles and interrupted testing for 500 hr were used as screening tests. Pure NiAl and NiAl(Zr) with 0. 14 at.% Zr were chosen as model base compositions; they exhibited normal, slow-growing scales (3 Mg/sq cm) with excellent adhesion for the Zr-doped alloys. NiAl with about 120 ppma S exhibited a substantial weight loss (-20 Mg/sq cm) in cyclic tests and a very large weight gain (+60 Mg/sq cm) in interrupted tests. The major surface phase remained as alpha -Al2O3. Sulfur doping the NiAl(Zr) alloy caused massive weight gains of 80 - 100 Mg/sq cm, swelling, cracking, and nearly complete conversion into NiAl2O4, and alpha- Al2O3. The initial objective of determining critical S/Zr ratios for adhesion was therefore unattainable. Initiation of the catastrophic attack was examined after a 10 hr exposure, revealing a few sites of broad, raised, and cracked ridges. In cross-section, the ridges appeared as modular intrusions, with a complex, fractal, oxide-metal interface. They were primarily alumina (with occasional entrapped islands of NiAl2O4 or pure Ni metal). They possessed a unique microstructure consisting of 0.3 microns lamellae, separated by 0.1 microns open channels. This allowed for rapid growth controlled by gaseous diffusion. The microstructure is discussed in terms of SO2 evolution and a sulfur-driven de-passivation process.

Smialek, James L.↗

DOE OSTI2021

Molecularly Functionalized Electrodes for Efficient Electrochemical Water Remediation

Here, the development and investigation of materials that leverage unique interfacial effects on electronic structure and redox chemistry are likely to play an outstanding role in advanced technologies for wastewater treatment. Here, the use of surface functionalization of metal oxides with a Ru(II)poly(pyridyl) complex was reported as a way to create hybrid assemblies with optimized electrochemical performance for water remediation, superior to those that could be achieved with the molecular catalyst or metal-oxide electrodes used individually. Mechanistic analysis demonstrated that the molecularly functionalized electrodes could suppress the formation of hydroxyl radicals (i. e., the dominant remediation pathway for bare metal-oxide electrodes), allowing the water remediation to proceed through the highly oxidizing Ru 3+ ions in the surface-bound complexes. Furthermore, the underlying metal-oxide substrates played a crucial role in altering the electronic structure and electrochemical properties of the surface-bound catalyst, such that the competing side reaction (i. e., water splitting) was largely inhibited.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Facing the Challenges of Borderline Oxidation State Assignments Using State-of-the-Art Computational Methods.

The oxidation state (OS) of metals and ligands in inorganic complexes may be defined by carefully curated rules, such as from IUPAC, or by computational procedures such as the effective oxidation state (EOS) or localized orbital bonding analysis (LOBA). Such definitions typically agree for systems with simple ionic bonding and innocent ligands but may disagree as the boundary between ionic and covalent bonds is approached, or as the role of ligand noninnocence becomes nontrivial, or high oxidation states of metals are supported by heavy dative bonding, and so on. This work systematically compares IUPAC, EOS, and LOBA across a series of complexes where OS assignment is challenging. These systems include high-valent transition metal oxides, transition metal complexes with noninnocent ligands such as dithiolate and nitrosyl, metal sulfur dioxide adducts, and two transition metal carbene complexes. The differences in OS assignment by the three methods are carefully discussed, demonstrating the synergy between EOS and LOBA. In addition, a clarity index for LOBA OS assignments is introduced that provides an indication of whether or not its predictions are close to the ionic-covalent boundary.

Gimferrer, Martí↗

DOE OSTI2024

Uranium Chemistry: Identifying the Next Frontiers

While uranium is the most extensively studied actinide in terms of chemical properties, there remains much to be explored about its fundamental chemistry. Organometallic and organoactinide chemistry first emerged in the 1950s with research that found inspiration from transition-metal chemistry with the synthesis and characterization of uranocene, expanding new opportunities for organoactinide chemistry. Since then, a significant amount of research has pursued many avenues characterizing the fundamental nature of the f orbitals and their modes of bonding as well as their potential in catalysis. Uranium(III/IV) arene complexes dominate much of uranium organometallic chemistry, with bonding interactions stabilized by δ-back-bonding. Recent additions to this area of chemistry include the first UI and new additions of U II organouranium compounds. Uranium–transition metal complexes are still rare and maintain U IV oxidation states, with variable bond lengths determining the transition-metal oxidation state. Resultant reactivities are discussed as synthetic complexes, and unique bonding and coordination motifs are highlighted. In conclusion, this Viewpoint will focus on significant developments in uranium chemistry from the last 15 years while considering key areas for future research.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2020

Co(salen)-Catalyzed Oxidation of Lignin Models to Form Benzoquinones and Benzaldehydes: A Computational and Experimental Study

Lignin is a highly abundant polyphenolic polymer that imparts mechanical strength to plant biomass. Transition-metal complexes can catalyze lignin oxidation to produce value-added products, but low catalytic efficiency has hampered their use in industry. Identifying the chemical and structural factors that govern catalytic activity is a prerequisite to rational design of catalysts with improved activity. In this study, we combine computational and experimental approaches to investigate the mechanism of Co(salen)-catalyzed oxidation of the monomeric lignin models syringyl (S), vanillyl (G), and 4-hydroxybenzyl alcohol (H) to produce benzoquinone and benzaldehyde products. Experimentally, S oxidation to form dimethoxybenzoquinone proceeded efficiently with a Co(salen) catalyst coordinated by a pyridine ligand, but G and H did not undergo oxidation. Density functional theory calculations reveal that catalyst regeneration is energetically unfavorable in the presence of H, which prevents oxidation. In contrast, S readily facilitates catalyst regeneration. Formation of methoxybenzoquinone from G was achieved experimentally by adding bulky, noncoordinating bases. These findings provide a fundamental baseline for enhancing the activity of Co-Schiff base catalysts toward lignin-like molecules by adding sterically hindered nitrogenous bases or potentially by including a cocatalyst that promotes catalyst regeneration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗