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1.
利用密度泛函理论第一性原理,计算了本征单层MoS2以及O、Se和Te掺杂单层MoS2的结构参数、能带结构、氧化还原电势、态密度、光吸收特性和光催化潜力.结果表明,本征和掺杂单层MoS2的晶胞参数、键长随原子半径的增大而增大,键角随原子半径的增大而减小.掺杂后禁带宽度变小,导电性增强.本征和掺杂的单层MoS2的导带底电位负于水解制氢反应的还原势,其价带顶电位正于水解制氢反应的氧化势,均具有光催化水解制氢的潜力.但是,本征和O掺杂,由于价带顶与导带底电位相应于水的氧化还原势和电子空穴需求量均存在不平衡,使其光解水性能不理想.然而,Se和Te掺杂可以平衡其还原与氧化能力,改善单层MoS2的光催化的性能,其中Se掺杂改善效果最为明显.同时,掺杂后的单层MoS2对可见光吸收效率增强.此研究有助于筛选合适的单层MoS2掺杂元素,提高单层MoS2材料的光催化水解制氢性能. 相似文献
2.
X-ray absorption spectroscopy (XAS) was used to characterize vanadium (V) and chromium (Cr) environments in low activity nuclear waste (LAW) glasses synthesized under a variety of redox conditions. V 2O 5 was added to the melt to improve sulfur incorporation from the waste; however, at sufficiently high concentrations, V increased melt foaming, which lowered melt processing rates. Foaming may be reduced by varying the redox conditions of the melt, while small amounts of Cr are added to reduce melter refractory corrosion. Three parent glasses were studied, where CO-CO 2 mixtures were bubbled through the corresponding melt for increasing time intervals so that a series of redox-adjusted-glasses was synthesized from each parent glass. XAS data indicated that V and Cr behaviors are significantly different in these glasses with respect to the cumulative gas bubbling times: V 4+/V total ranges from 8 to 35%, while Cr 3+/Cr total can range from 15 to 100% and even to population distributions including Cr 2+. As Na-content decreased, V, and especially, Cr became more reduced, when comparing equivalent glasses within a series. The Na-poor glass series show possible redox coupling between V and Cr, where V 4+ populations increase after initial bubbling, but as bubbling time increases, V 4+ populations drop to near the level of the parent glass, while Cr becomes more reduced to the point of having increasing Cr 2+ populations. 相似文献
3.
The studies of the media with an open surface of wave vectors (SWV) undertaken by the author in the 1970s are continued. A number of new specific features of these media are revealed. It is shown, in particular, that the focusing upon refraction at a plane boundary (a phenomenon that has recently attracted much attention and is related to the media whose permittivity and permeability are simultaneously negative) can also be realized in a nonmagnetic medium with an open SWV. The boundary problem for a plate and a semi-infinite crystal with an open SWV is solved, and the qualitative differences from the media with a closed SWV are revealed. Biaxial nonmagnetic media and nonmagnetic media in the presence of negative components of the dielectric and magnetic tensors are briefly considered. 相似文献
4.
The thermodynamics of the redox equilibrium of Cu +/Cu 2+ were determined by square-wave voltammetry in glass melts with the base mol% compositions x Na 2O · (100 − x) SiO 2 ( x = 15, 20, 26 and 33) and (26 − x) Na 2O · x CaO · 74 SiO 2 ( x = 0, 5, 10 and 15) doped with 1 mol% CuO in the temperature range from 850 to 1150 °C. All recorded voltammograms showed two maxima attributed to the reductions of Cu 2+ to Cu + and Cu + to metallic copper. Both peaks are shifted to smaller potentials with decreasing temperature. With increasing melt basicity, the [Cu +]/[Cu 2+]-ratio first increases, and remains constant for optical basicities >0.56. The effect of composition on the redox equilibrium is explained by the incorporation of both Cu + and Cu 2+ in octahedral coordination into the melt structure. 相似文献
5.
The redox behavior of various elements (Fe, Sb, Ce, Ti, Zn) was investigated in alkali–alkaline earth-silica CRT (Cathode ray tube: TV panel) model glass melts using the square-wave voltammetry (SWV). The current–potential curve, so called voltammogram, was produced at temperature range of 1000–1400 °C under the scanned potential between 0 and –800 mV at 100 Hz. The Fe, Ti and Zn doped melts exhibited one peak due to reduction reaction. In the case of the Sb doped melts, two traces doubted as peak were found in the voltammogram at low temperature while only one peak existed at high temperature. The peak potential was shifted to the negative direction with decrease of temperature, however, its temperature dependence showed linearity. On the other hand, no peak was found in voltammogram of the melts doped with Ce. Based on the temperature dependence of the peak potential, standard enthalpy (Δ H0) and standard entropy (Δ S0) for the reduction of Fe 3+ to Fe 2+, Sb 3+ to Sb 0 and Zn 2+ to Zn 0 in CRT model glass melts were calculated. 相似文献
6.
Glasses with the base mol% composition xNa 2O · 10CaO · (90 ? x)SiO 2 with x = 10, 16, 20 and 26 were investigated at high temperatures using square-wave voltammetry. The recorded voltammograms exhibit two peaks. That at less negative or (depending on temperature and glass composition) even positive potential is attributed to the reduction of Cu 2+ to Cu +, while that observed at more negative potential is caused by the reduction of Cu + to metallic copper. For both redox steps, the peak potentials decrease linearly with temperature. Those of the composition with 10 mol% Na 2O show the most negative values. The diffusion coefficients can be fitted to Arrhenius equation. If referenced to the same viscosity, the diffusion coefficients decrease with increasing Na 2O-concentration. The effect of composition on the thermodynamics as well as on diffusivities is explained by the incorporation of the copper ions into the melt structure. 相似文献
7.
This study highlights the role of two platinum-group metals, ruthenium and palladium, in the redox equilibria of nuclear waste containment glass. Electrochemical measurements in simplified R7/T7 glass melts were used to develop a thermodynamic model of ruthenium redox equilibrium. The oxygen fugacity at equilibrium, corresponding to the coexistence of ruthenium oxide and ruthenium metal dispersed in the molten glass, was measured at different ratios at temperatures ranging from 1000 °C to 1200 °C. Experiments were carried out on glass with and without Pd, revealing the combined role of palladium and tellurium on redox equilibria in the glass. The formation of palladium-tellurium alloys in nuclear glass was observed to result in oxidation of the elements dissolved in the melt. 相似文献
8.
Poly(p-phenylene sulfide), PPS, a melt and solution processible polymer, can be made highly conducting by doping with strong electron acceptors such as ASF5. Virgin PPS is an insulator with a relatively high ionization potential compared to polyacetylene. This, coupled with its high melting and solubilization points, restricts possible dopants to those which are particularly aggressive and capable of reacting with PPS in the solid state. These aggressive dopants induce a variety of chemical changes in the polymer backbone upon doping. While fluorination and crosslinking occur to some extent, infrared spectra and independent chemical synthesis suggest that the predominant chemical change is via intrachain bridging (cyclization) of adjacent phenyl rings. In an attempt to find processible systems with lower ionization potentials and which are less prone to chemical modification, a variety of polyaromatic sulfides were prepared. The influence of polymer structure, morphology, and dopant-induced chemical modifications upon conductivity is discussed. 相似文献
9.
The factors responsible for the formation of different configurations of boundaries between adjacent crystallites during their growth from melt by Bridgman and Czochralski methods have been considered by an of example Fe–20 wt % Ga alloy and Ni bicrystals. It is found that the configuration of intercrystallite boundary is related to the features of crystallite growth, caused by the strained state of intercrystallite and interphase (crystal–melt) boundaries, the difference in the linear thermal expansion coefficients of the crystallite boundaries and bulk, and the shape (geometry) of the bicrystal cross section. It is suggested that the strained state of boundaries and the formation of substructure in crystallites during directional crystallization from metal melt are significantly affected by their deformation under the melt weight. 相似文献
10.
In this study, a numerical simulation is performed to investigate the effect of the shape of the heat shield on the oxygen concentration in the melt. The results show that the oxygen concentration in the melt can be significantly decreased by increasing the speed of the argon gas near the crucible wall. This can be achieved by enlarging the horizontal length of the heat shield. The oxygen concentration at the melt–crystal interface varies with the length of the crystal growth. In the initial stage, there is a significant decrease in the oxygen concentration as the growth length increases. There is also a significant reduction in the emission of oxygen from the crucible wall due to the lower melt depth and crucible temperature. The transportation of oxygen impurity towards the melt–crystal interface is suppressed by the vortex motion in the melt. When the crystal exceeds a certain length, the oxygen concentration in the melt–crystal interface starts to increase with increasing crystal length, due to the drop in vortex motion in the melt. 相似文献
11.
It is shown that the melt growth of low-temperature phase aluminum beryllate crystals, Al 2BeO 4 (ABO), requires specific metastable conditions. These are, first of all, the melt pretreatment and insertion of a “cold” seed preserving the stability of its structure and providing a local decrease in melt temperature in the seeding zone. Contact of thermally treated melt with the high-temperature phase must be avoided as the melt loses its metastable state. The role of d-element dope in polymorphous transformations of ABO and narrowing of crystallization field of its high-temperature phase from melt is demonstrated. Some features of polymorphism and crystallization of ABO melt are interpreted in terms of associative complexing as the basis of mechanism of structure formation in condensed media. 相似文献
12.
Melts with the basic compositions 10Na 2O · 10MgO · xAl 2O 3 · (80− x)SiO 2 ( x=0, 5, 10, 15 and 20), 10Na 2O · xMgO · 10Al 2O 3 · (80− x)SiO 2 ( x=5, 10, 15 and 20) and xNa 2O · 10MgO · 10Al 2O 3 · (80− x)SiO 2 ( x=5, 10 and 15) all doped with 0.25 mol% Fe 2O 3 were studied using square-wave voltammetry. The temperatures applied were in the range of 1000–1600 °C. The square-wave voltammograms recorded show peaks caused by the reduction of Fe 3+ to Fe 2+. The attributed peak potentials measured decreased linearly with decreasing temperatures. Increasing the MgO-concentration led to more negative peak potentials. Introducing alumina in the melt first resulted in less negative peak potentials. If the molar Al 2O 3-concentration is equal to that of Na 2O (=10 mol%) the peak potentials are least negative. Further increase of the Al 2O 3-concentration led to more negative peak potentials. The variation of the Na 2O-concentration led to a maximum in the peak potentials at an Na 2O-concentration of 10 mol%. An empirical formula which allows the calculation of standard potentials from the chemical composition is proposed. Furthermore, a structural explanation for the effect of the chemical composition is given. Especially, the incorporation of Al 2O 3 as AlO 4−-tetrahedra at [Al 2O 3] < [Na 2O] and as network modifier at larger concentrations was structurally explained by the similarities of Fe 2+ and Mg 2+, with respect to cation radii and metal–oxygen bond lengths. 相似文献
13.
X-ray (XS) and X-ray photoelectron (XPS) spectra are reported for vanadium oxides. Because of the multivalent character of vanadium in the oxide system high quality measurements can be used for chemical shift investigation. Both inner level and valence band spectroscopy give information on the electronic structure and their systematic change with increasing oxidation state. The experimental results are discussed favourable in terms of molecular orbital theory (MO-theory). The complete set of XS and XPS data reported here for V-oxides allows the identification of unknown vanadium oxidation states too. 相似文献
14.
In a melt with the base mol% composition 25Na 2O-15B 2O 3-60SiO 2, doped with chromium and manganese, a redox reaction takes place during cooling the melt. This reaction was studied using high temperature UV-vis spectroscopy. Above 600 °C, the reaction is in equilibrium and shifted during cooling to the Cr 3+ and Mn 3+ species. At temperatures between 500 and 600 °C, the kinetics of the redox reaction is decisive and the cooling rate plays an important part. At temperatures < 500 °C, the reaction is frozen in. The smaller the cooling rate, the smaller is the Cr 6+ concentration and the lower is the fictive redox temperature.The kinetics of the reaction was described by a differential equation assuming Arrhenian behaviour. The equation was numerically solved and fictive temperatures were calculated. These temperatures depended on cooling rate similar to Bartenev equation. Activation energies calculated hereof were around 38 kJ?mol −1 larger than those inserted into the kinetic equation. The experimentally determined activation energy is 565 kJ?mol −1, a value much larger than the activation energies of diffusion of the polyvalent elements. The rate determining step in the case of the Cr 3+/Cr 6+/Mn 2+/Mn 3+ system is the electron transfer reaction, because a notable structural rearrangement is necessary during the course of the electron transfer reaction (Cr 3+ and Cr 6+ occur in octahedral and tetrahedral coordination, respectively). The latter leads to a large inner reorganisation energy and to an activation energy similar to that of the viscous flow. In the case of the redox reaction between copper and arsenic, the activation energy is much smaller (210 kJ?mol −1), because here the coordination numbers do not change during the course of the redox reaction. 相似文献
15.
In this paper, the role of seed rotation on the characteristics of the two‐dimensional temperature and flow field in the oxide Czochralski crystal growth system has been studied numerically for the seeding process. Based on the finite element method, a set of two‐dimensional quasi‐steady state numerical simulations were carried out to analyze the seed‐melt interface shape and heat transfer mechanism in a Czochralski furnace with different seed rotation rates: ωseed = 5‐30 rpm. The results presented here demonstrate the important role played by the seed rotation for influencing the shape of the seed‐melt interface during the seeding process. The seed‐melt interface shape is quite sensitive to the convective heat transfer in the melt and gaseous domain. When the local flow close to the seed‐melt interface is formed mainly due to the natural convection and the Marangoni effect, the interface becomes convex towards the melt. When the local flow under the seed‐melt interface is of forced convection flow type (seed rotation), the interface becomes more concave towards the melt as the seed rotation rate ( ωseed) is increased. A linear variation of the interface deflection with respect to the seed rotation rate has been found, too. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
16.
Experiments on Al–25 at%Ni peritectic alloy consisting of melting followed by thermal stabilization ranging from 0 to 2 h were carried out in a Bridgman-type furnace. Temperature distribution, microstructure evolution and solute concentration in the mushy zone are characterized. An analytical model is proposed to evaluate the Ni concentration of the melt after thermal stabilization. Effect of temperature gradient and volume fraction of liquid phase in the mushy zone on the Ni concentration of the melt is discussed. The steady state Ni concentration of the melt is inappropriately below the initial Ni concentration of the sample. The deviation increases with decreasing temperature gradient. Finally, the influence of thermal stabilization on the solute concentration of the melt is discussed based on a comparison of Al–Ni peritectic alloys with Al–Ni hyper-eutectic alloys and Al–Cu hypo-eutectic alloys. 相似文献
17.
The goal of the research presented here is to apply a global analysis of an inductively heated Czochralski furnace for a real sapphire crystal growth system and predict the characteristics of the temperature and flow fields in the system. To do it, for the beginning stage of a sapphire growth process, influence of melt and gas convection combined with radiative heat transfer on the temperature field of the system and the crystal‐melt interface have been studied numerically using the steady state two‐dimensional finite element method. For radiative heat transfer, internal radiation through the grown crystal and surface to surface radiation for the exposed surfaces have been taken into account. The numerical results demonstrate that there are a powerful vortex which arises from the natural convection in the melt and a strong and large vortex that flows upwards along the afterheater side wall and downwards along the seed and crystal sides in the gas part. In addition, a wavy shape has been observed for the crystal‐melt interface with a deflection towards the melt. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
18.
Bidirectional temperature gradients coexist virtually in surface tension driven flows. However, the simulations have been performed to the flow with only one temperature gradient. A series of 3 D numerical simulations are conducted to investigate the Marangoni‐thermocapillary flow of silicon melt in a thin annular layer with bidirectional temperature gradients. The temperature gradients are produced by the temperature difference Δ T between walls and the constant heat flux q on the bottom, respectively. When changing q, the melt presents different state evolutions at different Δ T. Furthermore, two critical q are found, one makes the minimum melt temperature higher than the crystallization temperature and the other makes the flow unsteady. Both of the critical heat fluxes decrease with increasing Δ T. q contributes more to the elevation of the melt temperature, while Δ T contributes more to the enhancement of the melt instability. In addition, the melt on the free surface flows mainly along the radial direction. 相似文献
19.
In order to understand the effects of the thermophysical properties of the melt on the transport phenomena in the Czochralski (Cz) furnace for the single crystal growth of silicon, a set of global analyses of momentum, heat and mass transfer in small Cz furnace (crucible diameter: 7.2 cm, crystal diameter: 3.5 cm, operated in a 10 Torr argon flow environment) was carried out using the finite‐element method. The global analysis assumed a pseudosteady axisymmetric state with laminar flow. The results show that different thermophysical properties will bring different variations of the heater power, the deflection of the melt/crystal interface, the axial temperature gradient in the crystal on the center of the melt/crystal interface and the average oxygen concentration along the melt/crystal interface. The application of the axial magnetic field is insensitive to this effect. This analysis reveals the importance of the determination of the thermophysical property in numerical simulation. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
20.
The electrochemical behaviour of undercooled melts and glasses is considered in detail. First the thermodynamic properties of the corresponding phases are calculated and then the temperature course of the emf and of other thermodynamic functions of a galvanic cell in which the net reaction is: undercooled melt (glass)→crystal, are determined. Some additional problems concerning the electrochemistry of amorphous electrodes are analyzed, e.g. hydrogen overvoltage upon hydrogen evolution on crystalline or amorphous electrodes of a given metal. Several variants are discussed for the possible experimental realization of a galvanic cell in which the emf is determined by the difference in the chemical potentials of the undercooled melt (or the glass) and the crystal, i.e. of a galvanic cell with a vitreous and a crystalline electrode made of one and the same electronic conductor or of a bipolar cell with an amorphous and a crystalline electrolyte, etc. An attempt is made to estimate the interal electric (Galvani) potential at the melt/crystal interface by using data for the difference of the Peltier coefficient between the respective phases.The analysis of the electrochemical behaviour of vitreous, liquid and crystalline electrodes is performed on the basis of formal thermodynamics and in terms of classical model approaches. It is shown how to determine by electrochemical measurements the main thermodynamic parameters of glasses which are considered as frozen-in non-equilibrium systems. 相似文献
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