Photon Synthesis of Nanometric Films Based on Transitional Metal oxides for Multi-Parameter Sensors

The reactive pulsed laser deposition (RPLD) based on a KrF laser was used for photon synthesis of nanometric iron and chromium oxides films. RPLD allows controlling the thickness and stoichiometry of deposits with definite band gap. So RPLD was used for synthesizing nanometric iron and chromium oxides films for thermo-photo-chemical sensors. We compared sensing properties of iron and chromium oxides nanometric films deposited on <100>Si substrate by RPLD. These iron and chromium oxides films have semiconductor properties with the band gaps less than 1.0 eV. The largest photosensitivity of iron and chromium oxides films was about 44 Vc/W and 2.5 Vc/W, accordingly, for white light at power density ~ 6x10-3 W/cm2. Vc is “chemical” photo e.m.f.. Maximum value of thermo electromotive force (e.m.f.) coefficient of iron and chromium oxides films was about 1.65 mV/K and 3.5-4.5mV/K, accordingly. Iron oxides films were tested as chemical sensors: the largest sensitivity of NO molecules was at the level of 7x1012 cm-3. Our results showed that nanometric iron and chromium oxides films synthesized by UV photons can be used as up-to-date materials for multi-parameter sensors operating at moderate temperature

Anaerobic Contributions Are Influenced by Active Muscle Mass and The Applied Methodology in Well-Controlled Muscle Group

International Journal of Exercise Science 15(7): 599-615, 2022. The anaerobic metabolism determination is complex and the applied methodologies present limitations. Thus, the purpose of this study was to investigate the effects of different calculations (MAOD vs. AOD) on the anaerobic contribution using the dynamic knee extension. Twenty-four male were recruited [Mean (SD); age 27 (1) years, body mass 90 (3) kg, height 181 (2) cm]. This study was divided into two independent experiments (EXP1: ­one-legged; EXP2: two-legged). In both experiments, it was performed a graded exercise test to determine maximal power (MP-GXT); 2-4 submaximal efforts (VO2-intensity relationship); and an exhaustive effort. The theoretical energy demand for the exhaustive effort (TEDex) was constructed from the submaximal efforts. Therefore, MAOD was assumed as the difference between the TEDex and the accumulated VO2 (AVO2). In contrast, the energy demand for AOD was calculated as the product between VO2 at the end of exercise and time to exhaustion (TEDaod). Thus, AOD was assumed as the difference between TEDaod and AVO2. Bayesian paired t-test was used to compare the differences between the applied methods. Also, correlations between the anaerobic indices and performance were verified. In EXP1, AOD was higher than MAOD [1855 (741) vs. 434 (245); BF10 = 2925; ES = 2.5]. In contrast, in EXP2, MAOD was higher than AOD [2832 (959) vs. 1636 (549); BF10 = 3.33; ES = 1.4]. Also, AOD was correlated to performance (r = .59; BF10 = 4.38). We concluded that MAOD and AOD are a distinct phenomenon and must be utilized according to the exercise model

Surface Reactivity of Ag-Modified Ceria to Hydrogen: A Combined Experimental and Theoretical Investigation

We investigate the mechanism of H2 activation on Ag-modified cerium oxide surfaces, of interest for different catalytic applications. The study is performed on thin epitaxial cerium oxide films, investigated by X-ray photoemission spectroscopy to assess the changes of both the Ag oxidation state and the concentration of Ce3+ ions, O vacancies, and hydroxyl groups on the surface during thermal reduction cycles in vacuum and under hydrogen exposure. The results are interpreted using density functional theory calculations to model pristine and Ag-modified ceria surfaces. Although the reactivity of ceria toward H2 oxidation improves when a fraction of Ce cations is substituted with Ag, the concentration of reduced Ce3+ ions in Ag-modified ceria is found to be lower than in pure ceria under the same conditions. This behavior is observed even though the number of surface oxygen vacancies caused by the thermal treatment under hydrogen exposure is larger for the Ag-modified surface. These results are explained in terms of a change of the oxidation state of the surface Ag, which is able to acquire some of the extra surface electrons created by the oxygen vacancies and the adsorbed hydrogen atoms. Our findings provide new insights into the reactivity of Ag-modified ceria, which has been proposed as a promising alternative to platinum electrodes in electrochemical devices

Structural analysis of Fe/Ni(001) films by photoelectron diffraction

The structure of Fe films, epitaxially grown on Ni(001), has been studied in the 0-14 ML coverage range by means of photoelectron diffraction (PD) in the forward scattering regime. Quantitative analysis by a multiple scattering approach has been performed on Fe films at a coverage of 3 and 7 ML. Analysis of the 3-ML data showed that growth was not layer-by-layer but rather occurred through islands nucleation and that transition from the pseudomorphic fee to the bcc phase was located in this early stage of growth. In fact, best fit was obtained by calculations on a 2 ML bcc(110)/3 ML fcc(001) Fe film with the bcc[111]parallel to fcc[110] in-plane orientation. Interlayer spacings of 2.05 +/- 0.068 Angstrom, 2.01 +/- 0.03 Angstrom, and 1.85 +/- 0.03 Angstrom were found in the bcc region, between bcc and fee layers and in the fee region, respectively. Best-fit in-plane nearest-neighbors (n-n) distance was 2.49 +/- 0.02 Angstrom, in registry with that of the Ni substrate. To analyze the 7-ML data a 4 ML bcc(110)/3 ML fcc(001) film was employed, varying the fitting parameters in the bcc region only. Best fit was obtained for an interlayer spacing of 2.04 +/- 0.04 Angstrom and in plane n-n distance of 2.47 +/- 0.01 Angstrom. At 14 ML the PD pattern collected over a 94 degrees azimuthal range displayed symmetry around the [110] substrate direction, which was explained by the equipopulation of the 4 bcc(110) domains satisfying the bcc[111]parallel to fcc[110] alignment

Backward extrapolation technique: analysis of different criteria after supramaximal exercise in cycling

Background: Backward extrapolation technique (BE) was used to estimate V̇O2 from postexercise measuring, eliminating oronasal mask (OM) during the efforts. Despite its advantage, literature presents discrepancy in applied methods. Thus, the first aim of this study was to compare different mathematical criteria to estimate values of V̇O2 during a supramaximal effort (V̇O2PEAK), while the second aim was to verify the effects of OM on cycling performance. Methods: Twenty-four male cyclists (35±6 years, 81.3±8.9 kg, 180±6 cm) performed three days of tests, with at least 24 h of interval between each test. Firstly, a graded exercise test was applied to determine V̇O2max and your correspondent intensity (MAP). The second and the third day were destined to supramaximal efforts at 120% of MAP, performed with (Supramask) and without (Suprabe) oronasal mask (OM) in a randomized order. After Suprabe, OM was coupled, and BE was applied. Sixty-six values of V̇O2 were obtained based on a linear regression fitting. Results: V̇O2peak can be estimated using different curve lengths. However, only curves between 20 and 60 s with extrapolation to 3 s or lesser shows at least one consistent criterion. The 60 s curve extrapoled to -3 s was the most accurate criteria (P=0.723; ES=-0.055; r=0.824; Bias=-0.36 and LoA=7.72 mL.kg.min-1). Performance was not impaired with OM and was similar in both condition (P=0.84, ES=0.04). Conclusions: We conclude that it was possible to accurately estimate V̇O2 values of a supramaximal effort without any respiratory apparatus with a time-efficient analysis. Therefore, we recommended the use of a 60 seconds V̇O2 curve analysis with a negative extrapolation for 3 seconds

Investigation of Ni@CoO core-shell nanoparticle films synthesized by sequential layer deposition

Films of Ni@CoO core-shell nanoparticles (NP Ni core size d ≈ 11 nm) have been grown on Si/SiOx and lacey carbon supports, by a sequential layer deposition method: a first layer of CoO was evaporated on the substrate, followed by the deposition of a layer of pre-formed, mass-selected Ni NPs, and finally an overlayer of CoO was added. The Ni NPs were formed by a magnetron gas aggregation source, and mass selected with a quadrupole mass filter. The morphology of the films was investigated with Scanning Electron Microscopy and Scanning Transmission Electron Microscopy. The Ni NP cores have a shape compatible with McKay icosahedron, caused by multitwinning occurring during their growth in the source, and the Ni NP layer shows the typical random paving growth mode. After the deposition of the CoO overlayer, CoO islands are observed, gradually extending and tending to merge with each other, with the formation of shells that enclose the Ni NP cores. In situ X-ray Photoelectron Spectroscopy showed that a few Ni atomic layers localized at the core-shell interface are oxidized, hinting at the possibility of creating an intermediate NiO shell between Ni and CoO, depending on the deposition conditions. Finally, X-ray Magnetic Circular Dichroism at the Ni L2,3 absorption edge showed the presence of magnetization at room temperature even at remanence, revealing the possibility of magnetic stabilization of the NP film

Ultrafast Formation of Small Polarons and the Optical Gap in CeO2

The ultrafast dynamics of excited states in cerium oxide are investigated to access the early moments of polaron formation, which can influence the photocatalytic functionality of the material. UV transient absorbance spectra of photoexcited CeO2 exhibit a bleaching of the band edge absorbance induced by the pump and a photoinduced absorbance feature assigned to Ce 4f → Ce 5d transitions. A blue shift of the spectral response of the photoinduced absorbance signal in the first picosecond after the pump excitation is attributed to the dynamical formation of small polarons with a characteristic time of 330 fs. A further important result of our work is that the combined use of steady-state and ultrafast transient absorption allows us to propose a revised value for the optical gap for ceria (Eog = 4 eV), significantly larger than usually reported

Structure and Morphology of Silver Nanoparticles on the (111) Surface of Cerium Oxide

The structure of Ag nanoparticles of different size, supported on the cerium oxide (111) surface, was investigated by X-ray absorption fine structure at the Ag K-edge. The results of the data analysis in the near and extended energy range are interpreted with the help of the results obtained by X-ray photoelectron spectroscopy and scanning tunneling microscopy measurements and allow to obtain a detailed atomic scale description of the model system investigated. The Ag nanoparticles have an average size of a few tens of angstroms, which increases with increasing deposited Ag amount. The nanoparticles show a slight tendency to nucleate at the step edges between different cerium oxide layers and they have a face centered cubic structure with an Ag-Ag interatomic distance contracted by 3-4% with respect to the bulk value. The interatomic distance contraction is mainly ascribed to dimensionality induced effects, while epitaxial effects have a minor role. The presence of Ag-O bonds at the interface between the nanoparticles and the supporting oxide is also detected. The Ag-O interatomic distance decreases with decreasing nanoparticle size

Injecting Electrons into CeO2 via Photoexcitation of Embedded Au Nanoparticles

The electron injection efficiency and the steady state absorptance at different photon energies for a composite system made of Au NPs embedded in a cerium oxide matrix are reported. Cerium oxide can be coupled with plasmonic nanoparticles (NPs) to improve its catalytic properties by visible-light absorption. The present work is a study of the ultrafast dynamics of excited states induced by ultraviolet and visible-light excitation in Au NPs combined with cerium oxide, aimed at understanding the excitation pathways. The data, obtained by femtosecond transient absorption spectroscopy, show that the excitation of localized surface plasmon resonances (LSPRs) in the Au NPs leads to an ultrafast injection of electrons into the empty 4f states of the surrounding cerium oxide. Within the first few picoseconds, the injected electrons couple with the lattice distortion forming a polaronic excited state, with similar properties to that formed after direct band gap excitation of the oxide. At sub-picosecond delay times, we observed relevant differences in the energetics and the time dynamics as compared to the case of band gap excitation of the oxide. Using different pump energies across the LSPR-related absorption band, the efficiency of the electron injection from the NPs into the oxide was found to be rather high, with a maximum above 30%. The injection efficiency has a different trend in energy as compared to the LSPR-related static optical absorptance, showing a significant decrease in low energies. This behavior is explained considering different deexcitation pathways with variable weight across the LSPR band. The results are important for the design of materials with high overall solar catalytic efficiency

Exchange-induced frustration in Fe/NiO multilayers

Using spin-polarized low-energy electron microscopy to study magnetization in epitaxial layered systems, we found that the area vs perimeter relationship of magnetic domains in the top Fe layers of Fe/NiO/Fe(100) structures follows a power-law distribution, with very small magnetic domain cutoff radius (about 40 nm) and domain wall thickness. This unusual magnetic microstructure can be understood as resulting from the competition between antiferromagnetic and ferromagnetic exchange interactions at the Fe/NiO interfaces, rather than from mechanisms involving the anisotropy and dipolar forces that govern length scales in conventional magnetic domain structures. Statistical analysis of our measurements validates a micromagnetic model that accounts for this interfacial exchange coupling.Comment: 15 pages, 2 figure