Insight into the Phase Transformation Pathways of Copper Oxidation: from Oxygen Chemisorption on the Clean Surface to Multi-Layer Bulk Oxide Growth
Explore the source record for details and available documents.
99 GENERAL AND MISCELLANEOUS↗
SEARCH · Search NASA
Results for “controller tuning”
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Defect Engineering of WO 3 by Rapid Flame Reduction for Efficient Photoelectrochemical Conversion of Methane into Liquid Oxygenates
Photoelectrochemical (PEC) conversion is a promising way to use methane (CH 4 ) as a chemical building block without harsh conditions. However, the PEC conversion of CH 4 to value-added chemicals remains challenging due to the thermodynamically favorable overoxidation of CH 4 . Here, we report WO 3 nanotube (NT) photoelectrocatalysts for PEC CH 4 conversion with high liquid product selectivity through defect engineering. By tuning the flame reduction treatment, we carefully controlled the oxygen vacancies of WO 3 NTs. The optimally reduced WO 3 NTs suppressed overoxidation of CH4 showing a high total C1 liquid selectivity of 69.4% and a production rate of 0.174 μmol cm –2 h –1 . Scanning electrochemical microscopy revealed that oxygen vacancies can restrain the production of hydroxyl radicals, which, in excess, could further oxidize C1 intermediates to CO 2 . Additionally, band diagram analysis and computational studies elucidated that oxygen vacancies thermodynamically suppress overoxidation. In conclusion, this work introduces a strategy for understanding and controlling the selectivity of photoelectrocatalysts for direct conversion of CH 4 to liquids.
36 MATERIALS SCIENCE↗
Kinetic Isotope Effect in the Radical Step-Growth Termination of On-Surface Synthesized Graphene Nanoribbons
Bottom-up on-surface synthesis has emerged as a versatile tool to access and finely tune the electronic structure of nanographenes. The controlled generation of reactive intermediates catalyzed and stabilized by a supporting substrate has enabled the design, assembly, and characterization of a wide range of exotic tailor-made quantum materials. Even under these tightly controlled conditions, the growth of extended structures remains limited by termination processes and undesired side reactions. Here, we identify an H atom transfer as one principal contributor to the radical step growth termination that limits the on-surface growth of N = 7 armchair graphene nanoribbons (7-AGNRs) on Au(111) surfaces. Analysis of 7-AGNR lengths grown from protiated and deuterated molecular precursors reveals a primary kinetic isotope effect of KIE ∼ 1.4. First-principles density functional theory calculations suggest that a concerted H atom transfer mechanism that involves the breaking of a C–H/D bond in the transition state is associated with radical chain termination.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Selective Oxidation and Cr Segregation in High-Entropy Oxide Thin Films
High-entropy oxides (HEOs) offer exceptional compositional flexibility and structural stability, making them promising materials for energy and catalytic applications. Here, in this study, we investigate Sr doping effects on B-site cation oxidation states, local composition, and structure in epitaxial La 1–x Sr x (Cr 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 )O 3 thin films. X-ray spectroscopies reveal that Sr doping preferentially promotes Cr oxidation from Cr 3+ to Cr 6+ , partially oxidizes Co and Ni, while leaving Mn 4+ and Fe 3+ unchanged. Atomic-resolution scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy shows pronounced Cr segregation, with depletion at the interface and enrichment at the surface, along with partial amorphization in heavily Sr-doped samples. This segregation is likely driven by oxidation-induced migration of smaller, high-valence Cr cations during growth. These findings highlight the critical interplay between charge compensation, local strain, and compositional fluctuations in HEOs, indicating that precise control over growth conditions is critical for tuning their surface composition and electronic structure toward more robust electrocatalyst design.
36 MATERIALS SCIENCE↗
Fluorescence Enhancement in the Solid State by Isolating Perylene Fluorophores in Metal–Organic Frameworks
Polycyclic aromatic hydrocarbons such as perylene, pyrene, and their derivatives are highly emissive fluorophores in solution. Furthermore, the practical applications of these materials in the field of molecular electronic and light emitting devices are often hindered by self-quenching effects due to the formation of non-fluorescent aggregates in concentrated solutions or in the solid state. Herein, we demonstrate that aggregation caused quenching of perylenes can be minimalized by molecular incorporation into metalorganic frameworks (MOFs). This study utilized a stable Zr 6 cluster-based MOF, UiO-67, as a matrix. Linear linkers containing the photo-responsive moieties were designed and incorporated into the parent UiO-67 scaffold through the partially replacement of the non-fluorescent linkers of a similar length, forming mixed-linker MOFs. Here, the average distance between perylene moieties was tuned by changing the linker ratios, thus controlling the fluorescence intensity, emission wavelength, and quantum yield. Molecular modeling was further adopted to correlate the number of isolated perylene linkers within the framework to the ratio between the two linkers, therefore rationalizing the change in the observed fluorescent properties. Taking advantage of the tunable fluorescence, inherent porosity, and high chemical stability of this MOF platform, it was applied as a fluorescent sensor for oxygen detection in the gas phase, a model reaction, showing fast response and good recyclability.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Strain-Induced Lateral Heterostructures in Patterned Semiconductor Nanomembranes for Micro- and Optoelectronics
The ability to tailor the energy band lineup of semiconductor materials plays a key role in the development of many electronic and optoelectronic devices and normally relies on heteroepitaxy. In this work, we report a different method, based on strain engineering, for the controlled introduction of variations in bandgap energy with lateral position in thin films. External stress is applied on Ge nanomembranes stacked with an array of amorphous-Si pillars in order to create a non-uniform strain (and therefore bandgap energy) distribution commensurate with the sample thickness variations. The resulting strain profiles are mapped using Bragg diffraction with a hard X-ray probe featuring nanoscale spatial resolution. Compared with traditional heterostructures grown by epitaxial techniques, these strain-engineered samples involve a single chemical composition and are not limited in the choice of compatible materials by any restriction imposed by lattice-matching requirements. Furthermore, their energy band lineups can be patterned in nearly arbitrary shapes using nanolithography to control the thickness profile and can be tuned actively by varying the applied stress. As a result, these structures are attractive for a wide range of device applications (including lasers, LEDs, solar cells, and thermoelectrics) that require complex heterostructure lineups with multiple bandgap energies.
36 MATERIALS SCIENCE↗
Inducing Kondo screening of vacancy magnetic moments in graphene with gating and local curvature
In normal metals the magnetic moment of impurity-spins disappears below a characteristic Kondo temperature which marks the formation of a cloud of conduction-band electrons that screen the local-moment. In contrast, moments embedded in insulators remain unscreened at all temperatures. What then is the fate of magnetic-moments in intermediate, pseudogap systems, such as graphene? Theory predicts that coupling to the conduction-band electrons will drive a quantum phase transition between a local-moment phase and a Kondo-screened phase. However, attempts to experimentally confirm this prediction and its intriguing consequences, such as electrostatically tunable magnetic-moments, have been elusive. Here we report the observation of Kondo-screening and the quantum phase-transition between screened and unscreened phases of vacancy magnetic moments in graphene. Using scanning tunneling spectroscopy and numerical renormalization-group calculations we show that this transition enables to control the screening of local moments by tuning the gate voltage and the local curvature of the graphene membrane.
36 MATERIALS SCIENCE↗
Weyl nodal ring states and Landau quantization with very large magnetoresistance in square-net magnet EuGa 4
Magnetic topological semimetals allow for an effective control of the topological electronic states by tuning the spin configuration. Among them, Weyl nodal line semimetals are thought to have the greatest tunability, yet they are the least studied experimentally due to the scarcity of material candidates. Here, using a combination of angle-resolved photoemission spectroscopy and quantum oscillation measurements, together with density functional theory calculations, we identify the square-net compound EuGa 4 as a magnetic Weyl nodal ring semimetal, in which the line nodes form closed rings near the Fermi level. The Weyl nodal ring states show distinct Landau quantization with clear spin splitting upon application of a magnetic field. At 2 K in a field of 14 T, the transverse magnetoresistance of EuGa 4 exceeds 200,000%, which is more than two orders of magnitude larger than that of other known magnetic topological semimetals. Our theoretical model suggests that the non-saturating magnetoresistance up to 40 T arises as a consequence of the nodal ring state.
36 MATERIALS SCIENCE↗
Compositional and temporal division of labor modulates mixed sugar fermentation by an engineered yeast consortium
Abstract Synthetic microbial communities have emerged as an attractive route for chemical bioprocessing. They are argued to be superior to single strains through microbial division of labor (DOL), but the exact mechanism by which DOL confers advantages remains unclear. Here, we utilize a synthetic Saccharomyces cerevisiae consortium along with mathematical modeling to achieve tunable mixed sugar fermentation to overcome the limitations of single-strain fermentation. The consortium involves two strains with each specializing in glucose or xylose utilization for ethanol production. By controlling initial community composition, DOL allows fine tuning of fermentation dynamics and product generation. By altering inoculation delay, DOL provides additional programmability to parallelly regulate fermentation characteristics and product yield. Mathematical models capture observed experimental findings and further offer guidance for subsequent fermentation optimization. This study demonstrates the functional potential of DOL in bioprocessing and provides insight into the rational design of engineered ecosystems for various applications.
59 BASIC BIOLOGICAL SCIENCES↗
Chirality manipulation of ultrafast phase switches in a correlated CDW-Weyl semimetal
Light engineering of correlated states in topological materials provides a new avenue of achieving exotic topological phases inaccessible by conventional tuning methods. Here we demonstrate a light control of correlation gaps in a model charge-density-wave (CDW) and polaron insulator (TaSe 4 ) 2 I recently predicted to be an axion insulator. Our ultrafast terahertz photocurrent spectroscopy reveals a two-step, non-thermal melting of polarons and electronic CDW gap via the fluence dependence of a longitudinal circular photogalvanic current. This helicity-dependent photocurrent reveals continuous ultrafast phase switches from the polaronic state to the CDW (axion) phase, and finally to a hidden Weyl phase as the pump fluence increases. Additional distinctive attributes aligning with the light-induced switches include: the mode-selective coupling of coherent phonons to the polaron and CDW modulation, and the emergence of a non-thermal chiral photocurrent above the pump threshold of CDW-related phonons. The demonstrated ultrafast chirality control of correlated topological states here holds large potentials for realizing axion electrodynamics and advancing quantum-computing applications.
36 MATERIALS SCIENCE↗
Deep eutectic solvent route synthesis of zinc and copper vanadate n-type semiconductors – mapping oxygen vacancies and their effect on photovoltage
Ternary metal oxides M 2 V 2 O 7–δ (M = Zn and Cu) were synthesized by dissolving binary metal oxide precursors in an environmentally benign deep eutectic solvent (DES), which is a eutectic mixture of a hydrogen bond donor and acceptor, followed by annealing in an open crucible. The unique reaction environment provided by the evolved ammonia allows for stabilization of oxygen vacancies and reduced oxidation states of metal ions within an oxide matrix without the need for any post-treatment with flammable reducing agents. According to comprehensive characterization, including X-ray photoelectron spectroscopy (XPS), neutron powder diffraction, and UV-vis spectroscopy, oxygen deficiency is accompanied by reduced oxidation states of metal centers (Cu + or V 4+ ), resulting in oxides with mixed-valence metal oxidation states. The amount of oxygen vacancies can be tuned by changing the annealing temperature providing control over band gaps of ternary metal oxides and mid-gap states from reduced metal centers. All synthesized vanadates are n-type semiconductors based on negative photovoltages obtained from surface photovoltage spectroscopy (SPS). A decay of the photovoltage with increasing annealing temperatures is attributed to electron trapping and electron/hole recombination at V 4+ and Cu + mid-gap states. This work shows for the first time the impact of oxygen vacancies on the electronic structure of DES synthesized oxides for solar energy conversion applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Lanthanum-based double perovskite nanoscale motifs as support media for the methanol oxidation reaction
In this report we have not only analyzed the performance of perovskite oxides as support media for the methanol oxidation reaction (MOR) but also examined the impact and significance of various reaction parameters on their synthesis. Specifically, we have generated (a) La 2 NiMnO 6 , LaMnO 3 , and LaNiO 3 nanocubes with average sizes of ~200 nm, in addition to a series of La 2 NiMnO 6 (b) nanocubes possessing average sizes of ~70 and 400 nm and (c) anisotropic nanorods characterized by average diameters of 40-50 nm. All of these samples, when used as supports for Pt nanoparticles, exhibited activities which were at least twice that measured for Pt/C. We have investigated and correlated the effect of varying perovskite (i) composition, (ii) size, and (iii) morphology upon the measured MOR activity. (i) The Ni-containing perovskites yielded generally higher performance metrics than LaMnO 3 alone, suggesting that the presence of Ni is favorable for MOR, a finding supported by a shift in the Pt d-band in XPS. (ii) MOR activity is enhanced as the perovskite size increases in magnitude, suggesting that a growth in the perovskite particle size enables favorable, synergistic metal–support interactions. (iii) A comparison of the nanorods and nanocubes of a similar diameter implied that the one-dimensional morphology achieved a greater activity, a finding which can be attributed not only to the anisotropic structure but also to a desirable surface structure. Overall, these data yield key insights into the tuning of metal–support interactions via rational control over the composition, size, and morphology of the underlying catalyst support.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The electric field manipulation of magnetization in La{sub 1−x}Sr{sub x}CoO{sub 3}/Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}-PbTiO{sub 3} heterostructures
La{sub 1−x}Sr{sub x}CoO{sub 3} (x = 0.18, 0.33, and 0.5) films were grown epitaxially on piezoelectric Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}-PbTiO{sub 3} substrates by pulsed laser deposition. The magnetization of these films varies with the external electric field, showing the magnetoelectric effect. With different doping content of Sr{sup 2+} ions, the change of magnetization for these films show different behaviors with increasing temperature, which can be attributed to the competition between electric-field-induced changes of spin state and double exchange interaction. This work presents an alternative mechanism to investigate the electric field control of magnetism in magnetoelectric heterostructure by tuning the spin state.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Ferromagnetism and the electronic band structure in (Ga,Mn)(Bi,As) epitaxial layers
Impact of Bi incorporation into (Ga,Mn)As layers on their electronic- and band-structures as well as their magnetic and structural properties has been studied. Homogenous (Ga,Mn)(Bi,As) layers of high structural perfection have been grown by the low-temperature molecular-beam epitaxy technique. Post-growth annealing treatment of the layers results in an improvement of their structural and magnetic properties and an increase in the hole concentration in the layers. The modulation photoreflectance spectroscopy results are consistent with the valence-band model of hole-mediated ferromagnetism in the layers. This material combines the properties of (Ga,Mn)As and Ga(Bi,As) ternary compounds and offers the possibility of tuning its electrical and magnetic properties by controlling the alloy composition.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Tungsten polyoxometalate molecules as active nodes for dynamic carrier exchange in hybrid molecular/semiconductor capacitors
In this work we study the utilization of molecular transition metal oxides known as polyoxometalates (POMs), in particular the Keggin structure anions of the formula PW₁₂O₄₀³⁻, as active nodes for potential switching and/or fast writing memory applications. The active molecules are being integrated in hybrid Metal-Insulator/POM molecules-Semiconductor capacitors, which serve as prototypes allowing investigation of critical performance characteristics towards the design of more sophisticated devices. The charging ability as well as the electronic structure of the molecular layer is probed by means of electrical characterization, namely, capacitance-voltage and current-voltage measurements, as well as transient capacitance measurements, C (t), under step voltage polarization. It is argued that the transient current peaks observed are manifestations of dynamic carrier exchange between the gate electrode and specific molecular levels, while the transient C (t) curves under conditions of molecular charging can supply information for the rate of change of the charge that is being trapped and de-trapped within the molecular layer. Structural characterization via surface and cross sectional scanning electron microscopy as well as atomic force microscopy, spectroscopic ellipsometry, UV and Fourier-transform IR spectroscopies, UPS, and XPS contribute to the extraction of accurate electronic structure characteristics and open the path for the design of new devices with on-demand tuning of their interfacial properties via the controlled preparation of the POM layer.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Pre-nitridation induced In incorporation in In{sub x}Ga{sub 1−x}N nanorods on Si(111) grown by molecular beam epitaxy
We address the issue of obtaining high quality green emitting InGaN nanorods without any phase separation. Role of pre-nitridation of the Si(111) substrate and growth, temperature on the morphology, structural and optical properties of In{sub x}Ga{sub 1−x}N films grown by plasma assisted molecular beam epitaxy, has been studied. The nitrogen rich growth environment and surface nitridation results in the formation of vertically well-aligned single crystalline nanorods that are coalesced and isolated at 400 °C and 500 °C, respectively. In incorporation is also seen to be enhanced to ≈28% at 400 °C to yield a stable green emission, while the nanorods grown at 500 °C show blue band-edge emission. The orientation, phase separations, and optical properties characterized by Reflection High Energy Electron Diffraction, Field Emission Scanning Electron Microscopy, high resolution x-ray diffraction, x-ray photoelectron spectroscopy, and photoluminescence are corroborated to understand the underlying mechanism. The study optimizes conditions to grow high quality catalyst-free well-aligned InGaN rods on nitrided Si surface, whose band-edge emission can be tuned from blue to green by sheer control of the substrate temperature.
36 MATERIALS SCIENCE↗
Heat flux splitter for near-field thermal radiation
We demonstrate the possibility to efficiently split the near-field heat flux exchanged between graphene nano-disks by tuning their doping. This result paves the way for the development of an active control of propagation directions for heat fluxes exchanged in the near field throughout integrated nanostructured networks.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
New tuning method of the low-mode asymmetry for ignition capsule implosions
In the deuterium-tritium inertial confinement fusion implosion experiments on the National Ignition Facility, the hot spot and the surrounding main fuel layer show obvious P2 asymmetries. This may be caused by the large positive P2 radiation flux asymmetry during the peak pulse resulting form the poor propagation of the inner laser beam in the gas-filled hohlraum. The symmetry evolution of ignition capsule implosions is investigated by applying P2 radiation flux asymmetries during different time intervals. A series of two-dimensional simulation results show that a positive P2 flux asymmetry during the peak pulse results in a positive P2 shell ρR asymmetry; while an early time positive P2 flux asymmetry causes a negative P2 in the fuel ρR shape. The opposite evolution behavior of shell ρR asymmetry is used to develop a new tuning method to correct the radiation flux asymmetry during the peak pulse by adding a compensating same-phased P2 drive asymmetry during the early time. The significant improvements of the shell ρR symmetry, hot spot shape, hot spot internal energy, and neutron yield indicate that the tuning method is quite effective. The similar tuning method can also be used to control the early time drive asymmetries.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗