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Nuclear Data Sheets for A = 65

The evaluators present in this publication spectroscopic data and level schemes from radioactive decay and nuclear reactions studies for all isobars with mass number A=65. Not much is known experimentally about {sup 65}V and {sup 65}Cr, although they are expected to decay by {beta}-emission. Spin/parity assignments for {sup 65}Mn, {sup 65}Fe, {sup 65}As, and {sup 65}Se are not firmly established.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

MoS{sub 2}@ZnO nano-heterojunctions with enhanced photocatalysis and field emission properties

The molybdenum disulfide (MoS{sub 2})@ZnO nano-heterojunctions were successfully fabricated through a facile three-step synthetic process: prefabrication of the ZnO nanoparticles, the synthesis of MoS{sub 2} nanoflowers, and the fabrication of MoS{sub 2}@ZnO heterojunctions, in which ZnO nanoparticles were uniformly self-assembled on the MoS{sub 2} nanoflowers by utilizing polyethyleneimine as a binding agent. The photocatalytic activities of the composite samples were evaluated by monitoring the photodegradation of methylene blue (MB). Compared with pure MoS{sub 2} nanoflowers, the composites show higher adsorption capability in dark and better photocatalytic efficiency due to the increased specific surface area and improved electron-hole pair separation. After irradiation for 100 min, the remaining MB in solution is about 7.3%. Moreover, the MoS{sub 2}@ZnO heterojunctions possess enhanced field emission properties with lower turn-on field of 3.08 V μm{sup −1}and lower threshold field of 6.9 V μm{sup −1} relative to pure MoS{sub 2} with turn-on field of 3.65 V μm{sup −1} and threshold field of 9.03 V μm{sup −1}.

36 MATERIALS SCIENCE↗

Tuning Optical and Electrical Properties of Vanadium Oxide with Topochemical Reduction and Substitutional Tin

Vanadium oxides are widely tunable materials, with many thermodynamically stable phases suitable for applications spanning catalysis to neuromorphic computing. The stability of vanadium in a range of oxidation states enables mixed-valence polymorphs of kinetically accessible metastable materials. Low-temperature synthetic routes to, and the properties of, these metastable materials are poorly understood and may unlock new optoelectronic and magnetic functionalities for expanded applications. In this work, we demonstrate topochemical reduction of α-V 2 O 5 to produce metastable vanadium oxide phases with tunable oxygen vacancies (>6%) and simultaneous substitutional tin incorporation (>3.5%). The chemistry is carried out at low temperature (65 °C) with solution-phase SnCl 2 , where Sn 2+ is oxidized to Sn 4+ as V 5+ sites are reduced to V 4+ during oxygen vacancy formation. Despite high oxygen vacancy and tin concentrations, the transformations are topochemical in that the symmetry of the parent crystal remains intact, although the unit cell expands. Band structure calculations show that these vacancies contribute electrons to the lattice, whereas substitutional tin contributes holes, yielding a compensation doping effect and control over the electronic properties. The SnCl 2 redox chemistry is effective on both solution-processed V 2 O 5 nanoparticle inks and mesoporous films cast from untreated inks, enabling versatile routes toward functional films with tunable optical and electronic properties. The electrical conductance rises concomitantly with the SnCl 2 concentration and treatment time, indicating a net increase in density of free electrons in the host lattice. This work provides a valuable demonstration of kinetic tailoring of electronic properties of vanadium–oxygen systems through top-down chemical manipulation from known thermodynamic phases.

36 MATERIALS SCIENCE↗

Syntheses, crystal structures and characterizations of new vanadium arsenites and arsenates

Systematic explorations in vanadium arsenites and arsenates led to the isolation four new compounds, namely, {alpha}-(V{sup IV}O){sub 3}(As{sup III}O{sub 3}){sub 2} (1), {beta}-(V{sup IV}O){sub 3}(As{sup III}O{sub 3}){sub 2} (2), (V{sup IV}O)[V{sup IV}O(H{sub 2}O)]{sub 2}(As{sup V}O{sub 4}){sub 2} (3), V{sup III}V{sup IV}O{sub 2}(As{sup V}O{sub 4}) (4). Compounds 1, 2 and 4 were synthesized by standard solid-state reactions, and compound 3 is a vanadium arsenate dihydrate synthesized through hydrothermal reactions. Compounds 1 and 2 are isomers, and they represent the first examples of ternary inorganic vanadium(IV) arsenites. Single crystal X-ray diffraction analysis indicated that the four compounds display four different structural types. Magnetic property measurements for compound 1 indicated that it exhibits ferromagnetism with the Curie temperature T{sub c}=65 K. Thermal stability and optical properties for compounds 1 and 3 were also investigated. - Graphical abstract: Hydrothermal or solid state reactions of V{sub 2}O{sub 5} (or VO{sub 2}) and As{sub 2}O{sub 3} yielded four new ternary compounds with four different types of structures, namely, {alpha}-(VO){sub 3}(AsO{sub 3}){sub 2} (1), {beta}-(VO){sub 3}(AsO{sub 3}){sub 2} (2), (VO)[VO(H{sub 2}O)]{sub 2}(AsO{sub 4}){sub 2} (3), (VO){sub 2}(AsO{sub 4}) (4). {alpha}-(VO){sub 3}(AsO{sub 3}){sub 2} (1), {beta}-(VO){sub 3}(AsO{sub 3}){sub 2} (2) represent the first examples of ternary inorganic vanadium(IV) arsenites. Highlights: Black-Right-Pointing-Pointer Hydrothermal or solid state reactions of V{sub 2}O{sub 5} (or VO{sub 2}) and As{sub 2}O{sub 3} yielded two new arsenites. Black-Right-Pointing-Pointer They represent the first examples of ternary vanadium arsenites. Black-Right-Pointing-Pointer Two new ternary vanadium arsenates were also obtained. Black-Right-Pointing-Pointer They exhibit four different structural types.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Continuous tuning of W-doped VO{sub 2} optical properties for terahertz analog applications

Vanadium dioxide (VO{sub 2}), with its characteristic metal-insulator phase transition, is a prospective active candidate to realize tunable optical devices operating at terahertz (THz) frequencies. However, the abrupt phase transition restricts its practical use in analog-like continuous applications. Incorporation of tungsten is a feasible approach to alter the phase transition properties of thin VO{sub 2} films. We show that amplitude THz modulation depth of ∼65%, characteristic phase transition temperature of ∼40 °C, and tuning range larger than 35 °C can be achieved with W-doped VO{sub 2} films grown on sapphire substrates. W-doped VO{sub 2} films can also be used to suppress Fabry-Perot resonances at THz frequencies but at temperatures much lower than that observed for undoped VO{sub 2} films. The gradual phase transition temperature window allows for precise control of the W-doped VO{sub 2} optical properties for future analog based THz devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Cyclohexene epoxidation with H 2 O 2 in the vapor and liquid phases over a vanadium-based metal–organic framework

A metal–organic framework, MIL-47(V) containing coordinatively saturated V +IV sites linked together by terephthalic linkers, was prepared by a solvothermal method and evaluated as a catalyst in the epoxidation of cyclohexene. We have compared the catalytic activity in the condensed and gas phase oxidation of cyclohexene to discuss the effect of temperature and reaction phase in cyclohexene epoxidation over MIL-47(V). The catalysts were examined for the epoxidation of cyclohexene with H 2 O 2 at 50, 65, 120, and 150 °C. Finally, we observed significant differences in product selectivity between liquid-phase and gas-phase operations and confirmed that the active sites are tightly incorporated into the MOF as node channels and thus resistant to leaching.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A hybrid analytical and numerical model for cross-over and performance decay in a unit cell vanadium redox flow battery

Developing an accurate and efficient model for cross-over is critical for improving the long-term performance of redox flow batteries (RFBs). Here, this work presents a hybrid analytical and numerical model that combines a two-dimensional analytical solution to the active species, a one-dimensional analytical model for cross-over mechanisms, and a zero-dimensional numerical model for outlet concentrations of reactants. By comparing with experiment over 41 cycles (ca. 144 h), the model reported a mean voltage difference of 0.0089 V, mean time difference of 14 s per cycle (of 3.5 h), maximum relative difference for capacity and energy of 1.34% and 1.63%, respectively. The predicted mean concentrations for V 2+ , V 3+ , and VO$_{2}^{+}$ in membrane are 65%~77% of measured values from the literature. Upon validation, the model reproduced behaviors in electrolyte imbalance similar to those observed in experiments and numerical models, and revealed the control of cross-over, self-discharge, stoichiometry of side reactions, and Coulombic efficiency on electrolyte imbalance. The model also demonstrates excellent computational efficiency for simulating 41 cycles (around 37,000 points) within 3~4 s. The demonstrated efficiency and accuracy for predicting cross-over and its impacts on voltage, capacity&energy decay, membrane concentrations, and electrolyte imbalance makes it a reliable tool for optimizing RFBs’ long-term performance.

25 ENERGY STORAGE↗

Accurate electronic and chemical properties of 3d transition metal oxides using a calculated linear response U and a DFT + U(V) method

We validate the usage of the calculated, linear response Hubbard U for evaluating accurate electronic and chemical properties of bulk 3d transition metal oxides. We find calculated values of U lead to improved band gaps. For the evaluation of accurate reaction energies, we first identify and eliminate contributions to the reaction energies of bulk systems due only to changes in U and construct a thermodynamic cycle that references the total energies of unique U systems to a common point using a DFT + U(V ) method, which we recast from a recently introduced DFT + U(R) method for molecular systems. We then introduce a semi-empirical method based on weighted DFT/DFT + U cohesive energies to calculate bulk oxidation energies of transition metal oxides using density functional theory and linear response calculated U values. We validate this method by calculating 14 reactions energies involving V, Cr, Mn, Fe, and Co oxides. We find up to an 85% reduction of the mean average error (MAE) compared to energies calculated with the Perdew-Burke-Ernzerhof functional. When our method is compared with DFT + U with empirically derived U values and the HSE06 hybrid functional, we find up to 65% and 39% reductions in the MAE, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Complex additive systems for Mn-Zn ferrites with low power loss

Mn-Zn ferrites were prepared via an oxalate-based wet-chemical synthesis process. Nanocrystalline ferrite powders with particle size of 50 nm were sintered at 1150 °C with 500 ppm CaO and 100 ppm SiO{sub 2} as standard additives. A fine-grained, dense microstructure with grain size of 4–5 μm was obtained. Simultaneous addition of Nb{sub 2}O{sub 5}, ZrO{sub 2}, V{sub 2}O{sub 5}, and SnO{sub 2} results low power losses, e.g., 65 mW/cm{sup 3} (500 kHz, 50 mT, 80 °C) and 55 mW/cm{sup 3} (1 MHz, 25 mT, 80 °C). Loss analysis shows that eddy current and residual losses were minimized through formation of insulating grain boundary phases, which is confirmed by transmission electron microscopy. Addition of SnO{sub 2} increases the ferrous ion concentration and affects anisotropy as reflected in permeability measurements μ(T)

36 MATERIALS SCIENCE↗

Control of Carbon Content in Ultrafine Cemented Carbide by Heat Treatment in Reducing Atmospheres Containing Carbon Oxides

In this work, the method of control of carbon content in the ultrafine-grained cemented carbide alloy was proposed. The treating of the WC-8Co-0.4VC-0.4Cr{sub 3}C{sub 2} compacts was made in a CO + CO{sub 2} gas mixture at CO concentrations from 0 to 80 vol.% during 50 min at the initial stage of the conventional sintering at a temperature of 700 °C. Conditions for increasing and decreasing the carbon content are CO concentrations of CO in gas mix more than 65 vol.% and less than 35 vol.%, respectively. It is shown that even a small deviation from the stoichiometric carbon content (0.3 wt.%) leads to an increase in porosity and a multiple decrease in the strength of the ultrafine-grained cemented carbide. A comparative analysis with literature data showed that the obtained ultrafine-grained solid alloy WC-8Co-0.4VC-0.4Cr{sub 3}C{sub 2} with stoichiometric composition is not inferior in hardness and toughness to the analogs obtained by hot pressing and electrospark sintering.

36 MATERIALS SCIENCE↗

Transport properties of lithium ions doped vanado-bismuth-tellurite glasses

The glasses of composition (65-x)V{sub 2}O{sub 5}-xLi{sub 2}O-20TeO{sub 2}-15Bi{sub 2}O{sub 3} (x = 15 and 25 mol%) were prepared by conventional melt quenching method and their electrical conductivity and dielectric measurements have been carried out in the frequency range 40 Hz to 6 MHz over a temperature 373 to 473 K. The conductivity values increased with both Li{sub 2}O concentration and temperature. Interestingly, the dielectric response showed the existence of a negative capacitance effect in the present glass system and concluded that this effect arose from the presence of external inductive reactance.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗