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54 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Modulating Mid-Gap Electronic States Through Site-Selective Modification in B-Pbx/B'-CuyV2O5/CdS Heterostructures for Photocatalytic Hydrogen Evolution

We interfaced ..beta..-Pbx/..beta..'-CuyV2O5 compounds, with varying stoichiometries of precisely positioned Pb-ions (x) and Cu-ions (y) in interstitial sites along a tunnel-structured ?-V2O5 framework, with cysteine-capped CdS (cysCdS) quantum dots (QDs) to yield heterostructured photocatalysts. ..beta..-Pbx/..beta..'-CuyV2O5 compounds exhibit midgap electronic states with orbital contributions from both Cu 3d and stereochemically active Pb 6s states that show distinctive light-initiated reactivity with photoexcited QDs. ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures were prepared by linker-assisted assembly (LAA). Scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, and Raman spectroscopy revealed that cysCdS QDs were deposited onto surfaces of ..beta..-Pbx/..beta..'-CuyV2O5 via LAA. HAXPES revealed that the site-selective positioning of Pb-ions and Cu-ions promoted close energetic alignment of the midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds with the valence-band maximum of cysCdS QDs. Transient absorption spectroscopy revealed that photogenerated holes were transferred from CdS QDs to midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds on time scales <50 ps. Finally, photoelectrochemical and photochemical experiments revealed that ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures promoted the photocatalytic reduction of H+ to H2. In photoelectrochemical experiments, under oxidative conditions, for all ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, H2 was evolved at a Pt counter electrode while a sacrificial donor was oxidized at the heterostructure-functionalized working electrode. In contrast, under reductive conditions, for ..beta..-Pb0.152V2O5/CdS and ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, H2 was evolved at the working electrode. In photochemical experiments, dispersed ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures promoted the reduction of H+ to H2 under white-light illumination; ..beta..'-Cu0.55V2O5/CdS and ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, for which midgap states have Cu 3d orbital character, generated 2-fold more H2 than ..beta..-Pb0.152V2O5/CdS heterostructures. Cu-ion insertion thus appends additional acceptor surface states that improve ligand-mediated hole transfer from photoexcited QDs, but such states are intrinsically limited in mediating hole transport to the substrate as a result of the low mobility of holes in narrow Cu 3d-states. Our results reveal that the density and orbital character of midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds, tunable through recently developed site-selective ion insertion strategies, determine efficiencies of charge-transfer and charge-transport mechanisms that underpin photocatalysis.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Electrochemical Phase Engineering of γ′-V 2 O 5 Thin Films for Sodium-Ion Storage Electrodes

V 2 O 5 is a promising sodium-ion cathode material due to its high theoretical capacity (147 mAh/g) and working voltage (3.3 V vs Na/Na + ). Among its various crystal phases, γ′-V 2 O 5 has a large interlayer spacing, ensuring the reversible insertion–extraction of sodium ions. However, current synthesis methods for γ′-V2O5 require high temperatures (>600 °C) and toxic chemicals (NO 2 BF 4 ), which make the preparation demanding. Herein, we put forward an electrochemical phase engineering method combining thermal annealing and electrochemistry to easily prepare thin-film γ′-V 2 O 5 . Electrochemical characterization shows near-ideal performance as a thin-film cathode material for sodium-ion batteries. It shows a measured initial capacity of 152 mAh/g, a high working voltage (3.3 V vs Na + /Na), and an exceptional Coulombic efficiency of 98%, significantly surpassing previously reported values (∼50% CE). Cyclic voltammogram and galvanostatic capacity curves confirm the sodium insertion–deinsertion, which remains stable at 2 C. The γ′-V 2 O 5 thin film has electrochemical performance similar to γ′-V 2 O 5 powder, indicating another workable morphology of γ′-V 2 O 5 for sodium-ion batteries.

batteries↗
NASA NTRS1978

Reactions of yttria-stabilized zirconia with oxides and sulfates of various elements

The reactions between partially stabilized zirconia, containing 8 weight-percent yttria, and oxides and sulfates of various elements were studied at 1200, 1300, and 1400 C for times to 800, 400, and 200 hours, respectively. These oxides and sulfates represent impurities and additives potentially present in gas turbine fuels or impurities in the turbine combustion air as well as the elements of the substrate alloys in contact with zirconia. Based on the results, these compounds can be classified in four groups: (1) compounds which did not react with zirconia (Na2SO4, K2SO4, Cr2O3, Al2O3 and NiO); (2) compounds that reached completely with both zirconia phases (CaO, BaO, and BaSO4); (3) compounds that reacted preferentially with monoclinic zirconia (Na2O, K2O, CoO, Fe2O3, MgO, SiO2, and ZnO); and (4) compounds that reacted preferentially with cubic zirconia (V2O5, P2O5).

Zaplatynsky, I.↗
NASA NTRS1979

Reactions of calcium orthosilicate and barium zirconate with oxides and sulfates of various elements

Calcium orthosilicate and barium zirconate were evaluated as the insulation layer of thermal barrier coatings for air cooled gas turbine components. Their reactions with various oxides and sulfates were studied at 1100 C and 1300 C for times ranging up to 400 and 200 hours, respectively. These oxides and sulfates represent potential impurities or additives in gas turbine fuels and in turbine combustion air, as well as elements of potential bond coat alloys. The phase compositions of the reaction products were determined by X-ray diffraction analysis. BaZrO3 and 2CaO-SiO2 both reacted with P2O5, V2O5, Cr2O3, Al2O3, and SiO2. In addition, 2CaO-SiO2 reacted with Na2O, BaO, MgO, and CoO and BaZrO3 reacted with Fe2O3.

Zaplatynsky, I.↗
NASA NTRS1983

Interatomic Auger transitions in maximal valent V and Cr compounds

The sensitivity of the intensities of the L(3)M(23)M(45) and L(3)M(45)M(45) Auger transitions toward the 3d character in the valence band has been demonstrated by using argon ion bombardment as a means of in situ reduction for the valence state of V and Cr in their maximal valent compounds. The selected V(5+) and Cr(6+) compounds were V2O5, NH4VO3, K2Cr2O7, K2CrO4, and CrO3. Auger and X-ray photoelectron spectra of fresh samples were obtained, and the samples were then subjected to ion bombardment of various durations. The subsequent spectra were recorded to monitor possible alterations due to the reduction of the cation valence state. The interatomic to intraatomic transitions of the Auger spectra transitions of the Auger spectra were observed dynamically and in situ. In particular, the intensity of the cation L(3)M(23)N(45) transitions was observed to increase dramatically with ion bombardment. The correlation between the interatomic Auger transition and covalency as well as the movements of the 3d electrons are discussed.

Yin, L. I.↗
NASA NTRS1986

Hydrazine reduction of transition metal oxides - In situ characterization using X-ray photoelectron spectroscopy

The transition metal oxides (TMOs) V2O5, FeO3, Co3O4, NiO, CuO, and ZnO were exposed to hydrazine at various pressures. The metallic surfaces were surveyed by in situ X-ray photoelectron spectroscopy to determine the irrelative rate of reduction by hydrazine. The most easily reducible oxide, CuO, could be reduced to the metallic state at room temperature and 10 to the -6th torr. The reaction is first order with respect to CuO, with an activation energy of about 35 kJ/mol. Two types of adsorption were seen to occur at 295 K: (1) a reversible component in which the measured N:Cu ratio increased to 0.60 at hydrazine pressures up to 0.5 torr, and (2) an irreversible component, with a N:Cu ratio of 0.28, which could not be removed by extended vacuum pumping. The results of this study are useful for the identification of TMO's that can be used as solid neatallizers of hydrazine spills, and for the preparation of metal surfaces for electroplating and evaporative thin-film coating.

Littrell, D. M.↗
NASA NTRS1987

A sputtering derived atomic oxygen source for studying fast atom reactions

A technique for the generation of fast atomic oxygen was developed. These atoms are created by ion beam sputtering from metal oxide surfaces. Mass resolved ion beams at energies up to 60 KeV are produced for this purpose using a 150 cm isotope separator. Studies have shown that particles sputtered with 40 KeV Ar(+) on Ta2O5 were dominantly neutral and exclusively atomic. The atomic oxygen also resided exclusively in its 3P ground state. The translational energy distribution for these atoms peaked at ca 7 eV (the metal-oxygen bond energy). Additional measurements on V2O5 yielded a bimodal distribution with the lower energy peak at ca 5 eV coinciding reasonably well with the metal-oxygen bond energy. The 7 eV source was used to investigate fast oxygen atom reactions with the 2-butene stereoisomers. Relative excitation functions for H-abstraction and pi-bond reaction were measured with trans-2-butene. The abstraction channel, although of minor relative importance at thermal energy, becomes comparable to the addition channel at 0.9 eV and dominates the high-energy regime. Structural effects on the specific channels were also found to be important at high energy.

Ferrieri, Richard A.↗
NASA NTRS1995

Fabrication of advanced electrochemical energy materials using sol-gel processing techniques

Advanced materials play an important role in electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. They are being used as both electrodes and electrolytes. Sol-gel processing is a versatile solution technique used in fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. The application of sol-gel processing in the fabrication of advanced electrochemical energy materials will be presented. The potentials of sol-gel derived materials for electrochemical energy applications will be discussed along with some examples of successful applications. Sol-gel derived metal oxide electrode materials such as V2O5 cathodes have been demonstrated in solid-slate thin film batteries; solid electrolytes materials such as beta-alumina for advanced secondary batteries had been prepared by the sol-gel technique long time ago; and high surface area transition metal compounds for capacitive energy storage applications can also be synthesized with this method.

Chu, C. T.↗
NASA NTRS1996

Sol-gel Technology and Advanced Electrochemical Energy Storage Materials

Advanced materials play an important role in the development of electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. The sol-gel process is a versatile solution for use in the fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. This processing technique is particularly useful in producing porous materials with high surface area and low density, two of the most desirable characteristics for electrode materials. In addition,the porous surface of gels can be modified chemically to create tailored surface properties, and inorganic/organic micro-composites can be prepared for improved material performance device fabrication. Applications of several sol-gel derived electrode materials in different energy storage devices are illustrated in this paper. V2O5 gels are shown to be a promising cathode material for solid state lithium batteries. Carbon aerogels, amorphous RuO2 gels and sol-gel derived hafnium compounds have been studied as electrode materials for high energy density and high power density electrochemical capacitors.

Chung-tse Chu↗
NASA NTRS1998

Thermal Control using Electrochromism

The applicability of a charge balanced electrochromic device to modulate the frequencies in the thermal infrared region is examined in this study. The device consisted of a transparent conductor, WO3 anode, PMMA/LiClO4 electrolyte, V2O5 cathode and transparent conductor. The supporting structure in the device is SnO2 coated glass and the edges are sealed with epoxy to reduce moisture absorption. The performance evaluation comprised of cyclic voltammetric measurements and determination of transmittance at various wavelengths. The device was subjected to anodic and cathodic polarization by sweeping the potential at a rate of 10 mV/sec from -0.8V to 1.8V. The current versus voltage profile indicated no reaction between -0.5 and +0.5 V. The device is colored green at 1.8V with a transmittance of 5% at a wavelength, lambda=900 nm and colorless at -0.8V with a transmittance of 74% at lambda=500 nm. The optical modulation is limited to 400-1500 nm and there is no activity in the thermal infrared. The switching time is 75 seconds for transmittance to decrease from 74% to 50%. The device yielded reproducible values for transmittance when cycled between colored and bleached states by application of 1.8V and -0.8V, respectively.

Vaidyanathan, Hari↗
NASA NTRS1998

Thermal Control Using Electrochromism

The applicability of a charge balanced electrochromic device to modulate the frequencies in the thermal infra red region is examined in this study. The device consisted of a transparent conductor, WO3 anode, PMMA/LiClO4, electrolyte, V2O5, cathode and transparent conductor. The supporting structure in the device is SnO2 coated glass and the edges are sealed with epoxy to reduce moisture absorption. The performance evaluation comprised of cyclic voltammetric measurements and determination of transmittance at various wavelengths. The device was subjected to anodic and cathodic polarization by sweeping the potential at a rate of 10 mV/sec from -0.8 V to 1.8 V. The current versus voltage profile indicated no reaction between -0.5 and +0.5 V. The device is colored green at 1.8 V with a transmittance of 5% at a wavelength, lambda = 900 nm and colorless at -0.8 V with a transmittance of 74% at X = 500 nm. The optical modulation is limited to 400-1500 nm and there is no activity in the thermal infrared. The switching time is 75 seconds for transmittance to decrease from 74% to 50%. The device yielded reproducible values for transmittance when cycled between colored and bleached states by application of 1.8 V and -0.8 V, respectively.

Vaidyanathan, Hari↗
NASA NTRS1999

Thermal Control Using Electrochromism

The applicability of a charge balanced electrochromic device to modulate the frequencies in the thermal infrared region is examined in this study. The device consisted of a transparent conductor, WO3, anode, PMMA/LiClO4 electrolyte, V2O5 cathode and transparent conductor. The supporting structure in the device is SnO2 coated glass and the edges are sealed with epoxy to reduce moisture absorption. The performance evaluation comprised of cyclic voltammetric measurements and determination of transmittance at various wavelengths. The device was subjected to anodic and cathodic polarization by sweeping the potential at a rate of 10 mV/sec from -0.8V to 1.8V. The current versus voltage profile indicated no reaction between -0.5 and +0.5 V. The device is colored green at 1.8 V with a transmittance of 5% at a wavelength, lambda = 900 nm and colorless at -0.8 V with a transmittance of 74% at lambda = 500 nm. The optical modulation is limited to 400-1500 nm and there is no activity in the thermal infrared. The switching time is a function of temperature and time for coloring reaction was slower than the bleaching reaction. The device yielded reproducible values for transmittance when cycled between colored and bleached states by application of 1.8V and -0.8V, respectively.

Vaidyanathan, Hari↗
DOE OSTI2023

Vanadium and Niobium MXenes—Bilayered V 2 O 5 Asymmetric Supercapacitors

MXenes offer high metallic conductivity and redox capacitance that are attractive for high-power, high-energy storage devices. However, they operate limitedly under high anodic potentials due to irreversible oxidation. Pairing them with oxides to design asymmetric supercapacitors may expand the voltage window and increase the energy storage capabilities. Hydrated lithium preintercalated bilayered V 2 O 5 ( δ-Li x V 2 O 5 ·nH 2 O) is attractive for aqueous energy storage due to its high Li capacity at high potentials; however, its poor cyclability remains a challenge. To overcome its limitations and achieve a wide voltage window and excellent cyclability, it is combined with V 2 C and Nb 4 C 3 MXenes. Asymmetric supercapacitors employing lithium intercalated V 2 C (Li-V 2 C) or tetramethylammonium intercalated Nb 4 C 3 (TMA-Nb 4 C 3 ) MXenes as the negative electrode, and a δ-Li x V 2 O 5 ·nH 2 O composite with carbon nanotubes as the positive electrode in 5 m LiCl electrolyte operate over wide voltage windows of 2 and 1.6 V, respectively. The latter shows remarkably high cyclability—capacitance retention of ≈95% after 10 000 cycles. Here, this work highlights the importance of selecting appropriate MXenes to achieve a wide voltage window and a long cycle life in combination with oxide anodes to demonstrate the potential of MXenes beyond Ti 3 C 2 in energy storage.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Multinonmetal-Doped V 2 O 5 Nanocomposites for Lithium-Ion Battery Cathodes

Lithium-ion batteries (LIBs) are critical for portable electronics and electric vehicles, demanding higher energy density to meet increasing energy storage needs. Current commercial cathode materials, such as LiFePO 4 and LiCoO 2 , are limited by a single electron transfer, restricting their energy density. Vanadium pentoxide (V 2 O 5 ) emerges as a promising high-capacity cathode due to its high theoretical capacity of 443 mA h g –1 with three Li storage capacities, significantly surpassing conventional materials. However, the practical application of V 2 O 5 is hindered by a large structural evolution and rapid capacity fading during full lithium intercalation. Here, this study introduces a multinonmetal doping (MNM) strategy to enhance V 2 O 5 cathodes by incorporating all-nonmetal dopants (B, P, and Si) and graphene (G). MNM-V 2 O 5 -G exhibits increased surface oxygen defects, improving charge transfer kinetics and thus enhancing the rate performance and cycling stability. Our results provide valuable insights into the role of surface oxygen defects in stabilizing V 2 O 5 with element doping. This research highlights the potential of multinonmetal doping to improve LIB cathode materials, offering a promising pathway for design of high-energy-density V 2 O 5 cathodes and advancing the development of next-generation energy storage solutions.

25 ENERGY STORAGE↗
DOE OSTI2026

Oxygen Vacancy Evolution at Li x V 2 O 5 /LiPON Solid State Electrochemical Interfaces Using Depth Resolved Cathodoluminescence Spectroscopy

The formation of oxygen vacancies at buried LiPON/ Li x V 2 O 5 interfaces has been observed on a near-nanometer scale and nondestructively using depth-resolved cathodoluminescence spectroscopy (DRCLS) and interfacial markers. Before electrochemical cycling, as-deposited LiPON/Li x V 2 O 5 exhibits a 1.6 eV defect optical emission, which density functional theory calculations identify as originating from oxygen vacancies. This defect appears first within a few nanometers of the buried LiPON/Li x V 2 O 5 interface without cycling, indicating that spontaneous O diffusion from the Li x V 2 O 5 lattice into LiPON may have caused these interface-localized oxygen vacancy defects. DRCLS measured the intensity and spatial distribution of this oxygen vacancy signal as a function of electrochemical cycling in a LiPON/Li x V 2 O 5 half-cell, showing oxygen vacancy signal increasing and moving deeper into the electrode with increased cycle number. Significant electrochemical irreversibility was also observed, with poor Coulombic efficiency and a 15% drop in capacity over 50 cycles. Theoretical simulations predict that the presence of oxygen vacancies increases the energy barrier for lithium diffusion significantly, indicating that this aggregation of oxygen vacancies could be another battery degradation mechanism accompanying lithiation induced phase changes.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Synthesis, structural and electrochemical properties of V4O9 cathode for lithium batteries

Single-phase three-dimensional vanadium oxide (V 4 O 9 ) was synthesized by reduction of V 2 O 5 using a gas stream of ammonia/argon (NH 3 /Ar). The as-synthesized oxide, prepared by this simple gas reduction method was subsequently electrochemically transformed into a disordered rock salt type-“Li3.7V4O9” phase while cycling over the voltage window 3.5 to 1.8 V versus Li. The Li-deficient phase delivers an initial reversible capacity of ∼260 mAhg −1 at an average voltage of 2.5 V vs. Li + /Li 0 . Further cycling to 50 cycles yields a steady 225 mAhg −1 . Ex situ X-ray diffraction studies confirmed that (de) intercalation phenomena follows a solid-solution electrochemical reaction mechanism. As demonstrated, the reversibility and capacity utilization of this V 4 O 9 is found to be superior to battery grade, micron-sized V 2 O 5 cathodes in lithium cells.

25 ENERGY STORAGE↗
DOE OSTI2023

Effect of the Deposition of Vanadium-Oxide on the Photocatalytic Activity of TiO2 Nanotubes and Its Photodiode Performance Interfaced with CH3NH3PbI3 Single Crystal

In this study, we report the influence of vanadium oxide (VO), as a photosensitive component, on the photoactivity of TiO2 nanotubes (TNTs). A series of TNTs of varying tube diameter were synthesized by the anodization of titanium foils at different voltages, while vanadium oxide was deposited on TNTs by wet chemical deposition. An improvement in the optical properties of nanotubes was observed after the deposition of vanadium oxide. An improvement in the optical properties (redshift in UV-Vis spectra) of TNTs and TNT/VO was noted. The photocatalytic activity was improved with increasing tube diameter, while it was weakened after the deposition of VO. Furthermore, photoactivity was investigated in photodiodes based on TNTs or TNT/VO and single crystals of CH3NH3PbI3. The photoelectric measurement revealed that different TNT diameters did not influence the I-V characteristic of the photodiodes, while the deposition of VO improved the photocurrent for smaller TNTs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗