Structural and thermoelectric power properties of Na-doped V2O5·nH2O nanocrystalline thin films

X-ray diffraction (XRD), thermoelectric power (S) and at room temperature electrical conductivity (σ) of Na⁺¹-doped V₂O₅·nH₂O nanocrystalline thin films fabricated by sol gel technique (colloid route) were studied. XRD showed that the Na₂O–V₂O₅·nH₂O thin films are highly oriented nanocrystals. The average value of particle size was found to be about 7.5 nm. The thermoelectric power showed that the thermoelectric power for all present nanocrystalline thin films samples decreased with increasing Na⁺¹ content. However, the electrical conductivity increased with increasing Na⁺¹ content. There is evidence that small polarons are responsible for determining the transport properties of the Na⁺¹ doped V₂O₅·nH₂O nanocrystalline thin films samples. The high value of electrical conductivity and small value of thermoelectric power is ideal for device applications, where device to device variation of the thermoelectric power must be small. This preparation technique was demonstrated to fabricate high quality Na₂O–V₂O₅·nH₂O nanocrystalline thin films for thermoelectric device applications. However, this may be further used for deposition with an ink-jet printer.     

H-center interactions during thermal annealing in KBr

Formation of the V₄-center and the H_A-center during thermal annealing in pure and Na⁺- and Li⁺-doped KBr, X-irradiated at low temperatures, is studied. It is found that these centers are produced accompanied with the annealing of the H-center at the second stage, of which the reaction order is two. The dependence of the concentration of Na⁺ impurity on the formation yield of the V₄-center by thermal annealing is studied and it is shown that the yield of the V₄-center formation is proportional to the square of the concentration of the H-center annealed at the second stage. This result confirms the former di-H-center model of the V₄-center.     

Enhanced luminescence of Ca3B2O6:Dy phosphors by Na-codoping for LED applications

The Ca_2.95−yDy_0.05B₂O₆:yNa⁺ (0≤y≤0.20) phosphors were synthesized at 1100 °C in air by the solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), photoluminescence excitation (PLE), photoluminescence (PL) spectra and thermoluminescence (TL) spectra. The PLE spectra show the excitation peaks from 300 to 400 nm due to the 4f-4f transitions of Dy³⁺. This mercury-free excitation is useful for solid-state lighting and light-emitting diodes (LEDs). The emission of Dy³⁺ ions on 350 nm excitation was observed at 480 nm (blue) due to the ⁴F_9/2→⁶H_15/2 transitions, 575 nm (yellow) due to ⁴F_9/2→⁶H_13/2 transitions and 660 nm (red) due to weak ⁴F_9/2→⁶H_11/2 emissions. The PL results from the investigated Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors show that Dy³⁺ emissions increase with the increase of the Na⁺ codoping ions. The integral intensity of yellow to blue (Y/B) can be tuned by controlling Na⁺ content. By the simulation of white light, the optimal CIE value (0.328, 0.334) can be achieved when the content of Na⁺-codoping ions is y=0.2. The results imply that the Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors could be potentially used as white LEDs.     

Kinetics of ion-exchange in sodium rare-earth silicates

The mobile Na⁺-ions (42/90 of the total) in Na₅GdSi₄O₁₂ have been replaced by K⁺ ions in K-NaCl melts at 800°C. K_xNa_3?xGdSi₃O₉ (Na₃GdSi₃O₉-type structure) was formed on the surface during immersion, and its quantity was found to be dependent on the (K⁺)/(Na⁺) ratio in the melt. Hydronium rare earth silicate was subsequently obtained by means of field-assisted ion exchange in acid. Dc resistivities for the hydronium rare earth silicates ((H₃ONa)₅GdSi₄O₁₂ and (H₃ONa)₅YSi₄O₁₂) were estimated as 1.8×10⁷ and $\text{7.3×10}{}^7\text{Ω}\text{cm}$, respectively, at room temperature with activation energies of 0.49 eV and 0.77 eV between room temperature to 90°C.     

Investigation of structural evolution of hydrogen-bond networks of water clusters at 1 and 300 K

Computer simulation of water clusters (H₂O) _n , Na⁺(H₂O) _n and K⁺(H₂O) _n (n ?? 8) at temperatures of 1 and 300 K was carried out using the Monte Carlo method. All the types of the hydrogen-bond network structures at equilibrium configurations of the water clusters and, among them, the most probable ones at temperatures of 1 and 300 K, were detected. The analysis of the most probable types of hydrogen-bond networks at equilibrium configurations of water clusters revealed that clusters with n water molecules inherit the configuration of clusters with n ? 1 water molecules with an accuracy of one hydrogen bond.     

Thiolated cyclodextrin self-assembled monolayer-like characterized with secondary ion mass spectrometry

In the work the focus is on the preparation of self-assembled monolayer-like films consisting of thiolated cyclodextrin on gold substrate and a characterization by using secondary ion mass spectrometry. The short (1 min) and long (1 h) time preparations of self-assembled monolayer-like films, resulting in submonolayer and monolayer regimes, are investigated, respectively. The observed species of thiolated cyclodextrin (M as molecular ion) self-assembled monolayer-like films are assigned to three groups: Au_xH_yS_z clusters, fragments with origin in cyclodextrin molecule associated with Au, and molecular ions. The group of Au_xH_yS_z (x = 2-17, y = 0-2, z = 1-5) clusters have higher intensities than other species in the positive and even more in negative mass spectra. Interestingly, the dependence between the number of Au and S atoms shows that with the increasing size of Au_xH_yS_z clusters up to 11 Au atoms, the number of associated S atoms is also increasing and then decreasing. Molecular species as (M−S+H)Na⁺, (M+H)Na⁺, AuMNa⁺, (M₂−S)Na⁺, and M₂Na⁺ are determined, and also in cationized forms with K⁺. The intensities of thiolated cyclodextrin fragments at the long time preparation are approximately 10 times higher than the intensities of the same fragments observed at the short time. The largest observed ions in thiolated cyclodextrin self-assembled monolayer-like films are AuM₂ and Au₂M. The thiolated cyclodextrin molecular ions are compared with hexadecanethiol molecular ions in the form of Au_xM_w where the values of x and w are smaller for thiolated cyclodextrin than for hexadecanethiol. This result is supported with larger, more compact, and more stabile thiolated cyclodextrin molecule.     

Proton conducting (Na,H)5GdSi4O12 ceramics and their use in steam electrolytes

A polycrystalline proton conductor has been obtained by field-assisted ion exchange (FAIE) of the mobile Na⁺ in Na₅GdSi₄O₁₂ by H₃O⁺. Polycrystalline Na₅GdSi₄O₁₂ (NGS) and (K_xNa_5−x)GdSi₄O₁₂ (KNGS) were examined as precursor ceramics. By modelling the FAIE process, it appears that KNGS is superior to NGS for ion exchange. The time required to complete the ion exchange process is ≈1.7×;10²h at 338 K, and the activation energy for proton conduction is 10.7±0.3 (kcal/mol). The H₃O-NGS ceramic was successfully incorporated into steam electrolysis cell operating at ≈90°C.     

Synthesis, characterization and spectroscopic investigation of new tetrakis(acetylacetonato)thulate(III) complexes containing alkaline metals as countercations

In this work a series of tetrakis complexes C[Tm(acac)₄], where C⁺=Li⁺, Na⁺ and K⁺ countercations and acac=acetylacetonate ligand, were synthesized and characterized for photoluminescence investigation. The relevant aspect is that these complexes are water-free in the first coordination sphere. The emission spectra of the tetrakis Tm³⁺-complexes present narrow bands characteristic of the ¹G₄→³H₆ (479 nm), ¹G₄→³F₄ (650 nm) and ¹G₄→³H₅ (779 nm) transitions of the Tm³⁺ ion, with the blue emission color at 479 nm as the most prominent one. The lifetime values (τ) of the emitting ¹G₄ level of the C[Tm(acac)₄] complexes were 344, 360 and 400 ns for the Li⁺, Na⁺ and K⁺ countercations, respectively, showing an increasing linear behavior versus the ionic radius of the alkaline ion. An efficient intramolecular energy transfer process from the triplet state (T) of the ligands to the emitting ¹G₄ state of the Tm³⁺ ion is observed. This fact, together with the absence of water molecules in first coordination sphere, allows these tetrakis Tm³⁺-complexes to act as efficient blue light conversion molecular devices.     

Characterization of polycrystalline (Na,K)β/β′- alumina ceramics

K β′-alumina is unstable at >1300°C. Mixed alkali β′-alumina has a variable stability depending on the alkali ratio, [K⁺]/([Na⁺]+[K⁺]). For f(β)<[K⁺]/([Na⁺]+[K⁺]), the β′-Al₂O₃ phase decomposes to Kβ-Al₂O₃ 0997 0815 V 3 and a solid solution of Na β′-Al₂O₃ and K β′-Al₂O₃. For f(β)=[K⁺]/([Na⁺]+[K⁺], the ceramic consists of K β-Al₂O₃ and Naβ′-Al₂O₃ and for f(β)>[K⁺]/([Na⁺]+[K⁺]), the excess Na⁺ after Na β′-Al₂O₃ dissolves in the β phase, giving Na β-Al₂O₃/K β-Al₂O₃ solid solution and Na β′-Al₂O₃. These sequences were confirmed by measuring the dependence of the c-axis lattice parameters of β- and β′-Al₂O₃ phases on the f(β), and the change of these parameters during the ion-exchange of Na⁺ and K⁺ ions.     

硫酸(氢)根吸附层对Pd(111)电极上甲酸氧化反应的影响研究

本文使用循环伏安法和电势阶跃法分别研究了添加和不添加Na₂SO₄的0.1 mol/LH₂SO₄+0.1 mol/LHCOOH溶液中Pd(111)电极上甲酸氧化反应(FAO)的动力学行为,并与同样条件下0.1 mol/LHClO₄中的动力学行为进行比较. 加入0.05 mol/L或者0.1 mol/LNa₂O₄后,在相同的电位下负向扫描的FAO电流比正向扫描的显著减小. 本文推测在(SO₄^*_ad)_m+[(H₂O)_n-H₃O⁺]或(SO₄^*_ad)_m+[Na⁺(H₂O)_n-H₃O⁺]吸附层相转变电势以正的电位, 这个吸附层的结构可能随着电位的增加或Na₂SO₄的加入变得更加致密和稳定. 因此,破坏或者脱附致密的硫酸(氢)根吸附层变得更加困难,使得FAO 动力学在较高电位和随后的负扫电位受到明显的抑制.     

Effect of H2O on Na+ diffusivity in beta alumina

The effect of H₂O on Na⁺ diffusivity in polycrystalline, and single crystal, beta-alumina was investigated. We found no evidence that water affects the diffusion kinetics and conclude that H₂O is not as easily introduced as a blocking impurity into either the grain boundaries or fast conducting planes, nor is Na⁺ easily removed from the structure by leaching.     

Vibrational studies of two phosphotellurates: Te(OH)62(NH4)2HPO4 and Te(OH)6Na2HPO4· H2O

IR and Raman spectra of the two phospsotellurates Te(OH)₆2(NH₄)₂HPO₄ and Te(OH)₆Na₂HPO₄· H₂O have been analysed on the basis of vibrations of HPO₄²⁻, TeO₆, NH₄⁺ and H₂O groups. It has been found that the NH₄⁺ ion rotates freely in the crystalline lattice. The splitting of the non-degenerate v_sPO₃, mode into two components suggests the possibility of resonance interaction between the HPO²⁻₄ ions in Te(OH)₆Na₂HPO₄· H₂O. The non-existence of H₃O⁺ ion in this crystal was also noticed.     

Mobile-ion concentrations and mixed-alkali effects in β-alumina solid electrolytes

A theory of the mixed-alkali effect based on the weak electrolyte model is used in the analysis of conductivity isotherms in the Na/K β-alumina system. This gives mobile interstitialcy concentrations, [Na²⁺₂] or [Na⁺_i], which agree remarkably well with those obtained by Wolf from calculations based on changes in the Haven ratio, H_R. The high conductivity of β-alumina arises apparently from a high “defect mobility” rather than from the existence of quasi-liquid motions. Other consequences of the weak electrolyte theory are discussed.     

Assessment of the nature of interactions of cations with cycloheptatriene derivatives using change in the aromaticity: Comparison with electron density and NBO results

ABSTRACT

Interactions of cycloheptatriene derivatives, C₇H₆X, (X?=?NH, PH, AsH, O, S, Se) with the cations H⁺, CH₃⁺, Cu⁺, Al⁺, Li⁺, Na⁺, and K⁺ are studied using B3LYP functional and 6-311++G(d,p) basis set. The calculated gas-phase cation affinities (CA) and cation basicities (CB) for all molecules decrease as H⁺ > CH₃⁺ > Cu⁺ > Al⁺ > Li⁺ > Na⁺ > K⁺. We used the induced aromaticity in the 7-membered ring of C₇H₆X upon interaction with the cations, M⁺, as a measure of C₇H₆X/M⁺ interaction. Nucleus-independent chemical shift (NICS) and harmonic oscillator model of aromaticity (HOMA) were used as two indices of aromaticity. The highest and lowest induced aromaticities were observed for interactions of H⁺ and K⁺, respectively. Also, the aromaticity induced by interaction with a cation in C₇H₆AsH and C₇H₆PH was larger than that in C₇H₆NH and C₇H₆O. Hence, the aromaticity was considered as a measure of covalency for the C₇H₆X/M⁺ interactions showing a rational dependence on both the molecule and cation. The nature of the interactions was also assessed using electron density, charge distribution analysis and NBO calculations. The results of the aromaticity indices, NICS and HOMA, were compared with the electron density and NBO results.     

A computational study of interplay between hydride bonding and cation–π interactions: H-Mg-H···X···Y triads (X = Li+, Na+, Y = C2H2, C2H4, C6H6) as model systems

In the present study, H-Mg-H···X···Y (X = Li⁺, Na⁺ and Y = C₂H₂, C₂H₄, C₆H₆) triads have been investigated at MP2/6-311++G(2d,2p) computational level to characterise cooperative effects between hydride bonding and cation–π interactions. Molecular geometries, binding energies, cooperative energies and many-body interaction energies were evaluated. The diminutive energy values in triads with Li⁺ are larger than respective values in triads with Na⁺. The electronic properties of the complexes are analysed using parameters derived from the quantum theory of atoms in molecules methodology.     

Ion-electron coincidence study of the thermal He(23S) + H2 Penning reaction

A new Penning-electron-Penning-ion coincidence method is described. It is applied to the study of the thermal reaction of He(2³S) with H₂. The main results reported are separate electron energy spectra that are coincident with the three different ions formed: HeH₂⁺, HeH⁺ and H₂⁺. Based on these results it is shown that the Penning reaction of the He(2³S)/H ₂ system proceeds in two well-separated steps: (i) ionization at distances R (HeH₂) ? 6a₀ in which H₂⁺ (v) is formed in different vibrational states; and (ii) reactive collision of H₂⁺ (v) with He. For the second step the variation of the branching ratios with vibrational quantum numbers v = 0 to v = 10 is derived, and it is shown that these branching ratios may be regarded as relative vibrational-energy-dependent cross-sections for the collision of H₂⁺ (v) with He at an average relative kinetic energy of ～20 meV.     

The sodium conductivity paths in the superionic conductors Na5RESi4O12

From an extended single crystal analysis on the Y variant of a recently discovered new class of extraordinary ionic conductors, the crystallographic sites available to the Na⁺-ions were located. Part of the Na⁺-ions ($\text{7}\text{3}$ of a Na⁺-ion per formula unit) appear to be mobile and are located in the space between stacks of Si₁₂O₃₆ rings. The size of the channels containing the partly occupied Na⁺-sites was changed by substitution of the RE-ion. The highest conductivities and smallest activation energies were found for RE-ions having radii comparable to that of a Na⁺-ion.     

Infrared,Raman and neutron scattering studies of β- and β″-alumina: a static and dynamical structure analysis

Infrared and Raman data on β-aluminates with different compositions (x)=0.0, 0.25, 0.66) containing Na⁺, Ag⁺, K⁺, Tl⁺, H₃O⁺, NH⁺₄ ions are reviewed. β-gallates and β″-aluminates are also considered. Assignments of the cation modes are discussed in terms of oscillations of single cations and of normal modes of clusters (pairs and triangles formed by the conducting cations). The assignment of the spinel block spectra is proposed in the light of recent normal mode calculation and comparison of different experimental results in the literature. Potential barriers and activation energies obtained from these techniques are compared with calculation results and with data obtained from different sources. Inelastic and recent quasi elastic neutron scattering results are reviewed and compared with those deduced from the vibrational study.     

Competitive solvation of K+ by C6H6 and H2O in the K+-(C6H6)n-(H2O)m (n = 1–4; m = 1–6) aggregates

The competitive solvation of the potassium ion by benzene and water is investigated at molecular level by means of Molecular Dynamics simulations on the K⁺-(C₆H₆) _n -(H₂O) _m (n = 1–4; m = 1–6) ionic aggregates. The preference of K⁺ to bind C₆H₆ or H₂O is investigated in the range of temperatures in which isomerisation processes are likely by adding water and benzene to the K⁺-(C₆H₆) _n and K⁺-(H₂O) _m aggregates, respectively. Hydrogen bonds and the π-hydrogen bond, in spite of their weakness with respect to the K⁺-π and K⁺-H₂O interactions, play an important role in stabilising different isomers, thus favouring isomerisation processes. Accordingly with experimental information it has been found that K⁺ bind preferably C₆H₆ rather than H₂O and that the fragmentation of C₆H₆ is only observed for aggregates containing four molecules of benzene.     

Influence of Na-related defects on ArF laser absorption in CaF2

ArF laser pulse transmission through commercial high purity CaF₂ is determined by measuring the energy of each pulse before and behind the sample up to an incident fluence H of 10 mJ/cm². The steady state transmission of ArF laser pulses decreases with increasing fluence. The related absorption coefficients α ^st(H) are proportional to H and rationalized by effective 1- and 2-photon absorption coefficients 2.4×10^?4 cm^?1≤α ^eff≤16.8×10^?4 cm^?1 and 1.7×10^?9 cm?W^?1≤β ^eff≤9.3×10^?9 cm?W^?1, respectively. The α ^eff and β ^eff values increase with the Na content of the CaF₂ samples as identified by the fluorescence of Na-related M _Na centers at 740 nm. This relation is simulated by a rate equation model describing the ArF laser induced M _Na generation in the dark periods between the laser pulses and their annealing during laser irradiation. M _Na generation starts with intrinsic 2-photon absorption in CaF₂, yielding self-trapped excitons (STE). These pairs of F and H centers move upon thermal activation and the F centers combine with F _Na to form M _Na centers. M _Na annealing occurs by its photo dissociation into a pair of F and F _Na centers.