Low frequency Raman spectra of barium borate glasses in the system (BaCl2)y[(BaO)x(B2O3)1-y-x]1-y for various x and y

Low frequency Raman spectra of glasses of the types (BaO)_x·(B₂O₃)_1−x and (BaCl₂)_y·[(BaO)_x·(B₂O₃)₁-_y-_x]₁-_y have been reported. The temperature reduced Raman spectra show peaks at 67, 116 and 140 cm⁻¹ for the binary glass. The bands at 116 and 140 cm⁻¹ are ascribed to the librational motions of the borate groups and the 67 cm⁻¹ band arises because of the limited structural correlation range (SCR) of the glass network, causing a maximum of the frequency dependent Raman coupling coefficient. Due to addition of BaO in v-B₂O₃, the oxygen are mostly incorporated in the formation of BO₄ units; however large Ba²⁺ ions also enhance the number of non-bridging oxygen at higher concentrations of dopant. These barium ions as well as chlorine ions are accomodated in the interstitial vacancies of the glass network which leads to an expansion of the network structure.     

Local structure of actinide dioxide solid solutions Th(1-x)U(x)O2 and Th(1-x)Pu(x)O2

Extended X-ray absorption fine structure (EXAFS) has been utilized to investigate the local atomic structure around Th, U, and Pu atoms in polycrystalline mixed dioxides Th(1-x)M(x)O2 (with M = U, Pu) for x ranging from 0 to 1. The composition dependence of the two first-coordination-shell distances was measured throughout the entire composition range for both solid solutions. The first-shell distances vary slightly across the solid-solution composition with values close to those of the pure dioxide parents, indicating a bimodal cation-oxygen distribution. In contrast, the second-shell distance varies strongly with composition, with values close to the weighted amount average distances. Nevertheless, in both systems, the lattice cell parameters, deduced from the first- and second-shell bond determined by EXAFS, are very close to those measured from X-ray diffraction (XRD). They vary linearly with composition, accurately following Vegard's law.     

Indium induced band gap tailoring in AgGa(1-x)In(x)S(2) chalcopyrite structure for visible light photocatalysis

Indium was substituted at gallium site in chalcopyrite AgGaS(2) structure by using a simple solid solution method. The spectroscopic analysis using extended x-ray absorption fine structure and x-ray photoelectron spectroscopy confirmed the indium substitution in AgGaS(2) lattice. The band gap energy of AgGa(1-x)In(x)S(2) (x=0-1) estimated from the onset of absorption edge was found to be reduced from 2.67 eV (x=0) to 1.9 eV (x=1) by indium substitution. The theoretical and experimental studies showed that the indium s orbitals in AgGa(1-x)In(x)S(2) tailored the band gap energy, thereby modified the photocatalytic activity of the AgGa(1-x)In(x)S(2).     

Nanostructured Bi(2-x)Cu(x)S3 bulk materials with enhanced thermoelectric performance

Nanostructured Bi(2-x)Cu(x)S(3) (x = 0, 0.002, 0.005, 0.007, 0.01, 0.03) thermoelectric polycrystals were fabricated by combining mechanical alloying (MA) and spark plasma sintering (SPS) methods. The effect of Cu content on the microstructure and thermoelectric property of Bi(2-x)Cu(x)S(3) bulk samples was investigated. It was found that the subtle tailoring of Cu content could reduce both the electrical resistivity and the thermal conductivity at the same time, and consequently enhancing the thermoelectric property. A low electrical resistivity of 1.34 × 10(-4)Ω m(-1) and a low thermal conductivity of 0.52 W m(-1) K(-1) were obtained for the Bi(1.995)Cu(0.005)S(3) sample at 573 K. The low thermal conductivity is supposed to be due to the nanoscopic Cu-rich regions embedded in the host matrix. A peak ZT value of 0.34 at 573 K was achieved for the Bi(1.995)Cu(0.005)S(3) composition, which is the highest value in the Bi(2)S(3) system reported so far.     

Bandgap engineering of monodispersed Cu(2-x)S(y)Se(1-y) nanocrystals through chalcogen ratio and crystal structure

Bandgap engineering is important in light-absorption optimization of nanocrystals (NCs) for applications such as highly efficient solar cells. Herein, a facile one-pot method is developed to synthesize monodispersed ternary alloyed copper sulfide selenide (Cu(2-x)S(y)Se(1-y)) NCs with tunable composition, structure, and morphology. The energy bandgaps can be tuned with the chalcogen ratio, and the crystal structure of the NCs is found to produce an effect on their bandgap and light absorption. The results are significant in bandgap engineering of semiconductor NCs.     

Systematic study of compositional and synthetic control of vacancy and magnetic ordering in oxygen-deficient perovskites Ca2Fe(2-x)Mn(x)O(5+y)and CaSrFe(2-x)Mn(x)O(5+y) (x = 1/2, 2/3, and 1; y = 0-1/2)

Ten compounds belonging to the series of oxygen-deficient perovskite oxides Ca(2)Fe(2-x)Mn(x)O(5) and CaSrFe(2-x)Mn(x)O(5+y), where x = 1/2, 2/3, and 1 and y ≈ 0-0.5, were synthesized and investigated with respect to the ordering of oxygen vacancies on both local and long-range length scales and the effect on crystal structure and magnetic properties. For the set with y ≈ 0 the oxygen vacancies always order in the long-range sense to form the brownmillerite structure containing alternating layers of octahedrally and tetrahedrally coordinated cations. However, there is a change in symmetry from Pnma to Icmm upon substitution of Sr for one Ca for all x, indicating local T(d) chain (vacancy) disorder. In the special case of CaSrFeMnO(5) the neutron diffraction peaks broaden, indicating only short-range structural order on a length scale of ~160 ?. This reveals a systematic progression from Ca(2)FeMnO(5) (Pnma, well-ordered tetrahedral chains) to CaSrFeMnO(5) (Icmm, disordered tetrahedral chains, overall short-range order) to Sr(2)FeMnO(5) (Pm3m, destruction of tetrahedral chains in a long-range sense). Systematic changes occur in the magnetic properties as well. While long-range antiferromagnetic order is preserved, the magnetic transition temperature, T(c), decreases for the same x when Sr substitutes for one Ca. A review of the changes in T(c) for the series Ca(2)Fe(2-x)M(x)O(5), taking into account the tetrahedral/octahedral site preferences for the various M(3+) ions, leads to a partial understanding of the origin of magnetic order in these materials in terms of a layered antiferromagnetic model. While in all cases the preferred magnetic moment direction is (010) at low temperatures, there is a cross over for x = 0.5 to (100) with increasing temperature for both the Ca(2)Fe(2-x)Mn(x)O(5) and the CaSrFe(2-x)Mn(x)O(5) series. For the y > 0 phases, while a brownmillerite ordering of oxygen vacancies is preserved for the Ca(2) phases, a disordered Pm3m cubic perovskite structure is always found when Sr is substituted for one Ca. Long-range magnetic order is also lost, giving way to spin glass or cluster-glass-like behavior below ~50 K. For the x = 0.5 phase, neutron pair distribution function (NPDF) studies show a local structure related to brownmillerite ordering of oxygen vacancies. Neutron diffraction data at 3.8 K show a broad magnetic feature, incommensurate with any multiple of the chemical lattice, and with a correlation length (magnetic domain) of 6.7(4) ?.     

Core-shell microspherical Ti(1-x)Zr(x)O2 solid solution photocatalysts directly from ultrasonic spray pyrolysis

A series of Ti(1-x)Zr(x)O(2) solid solutions photocatalysts (x = 0.000, 0.045, 0.090, 0.135, and 0.180) was directly obtained by an ultrasonic spray pyrolysis method. Compared with previous methods for solid solutions, our preparation was very fast. The resulting samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, nitrogen adsorption, and UV-vis diffuse reflectance spectroscopy. The characterizations revealed core-shell spherical structures of the resulting solid solutions. We evaluated photocatalytic activities of the solid solutions on degradation of rhodamine B in aqueous solution under simulated solar light. It was found that Ti(0.91)Zr(0.09)O(2) solid solution exhibited the highest photocatalytic activity among all the as-prepared samples. Its activity was much higher than that of P25. The formation mechanism of core-shell spherical structures was proposed. Moreover, we successfully extended this method to prepare microspheres of ceria and ceria-zirconia solid solutions. We think this general method may be easily scaled up for industrial production of microspherical solid solutions photocatalysts and catalysts.     

Vertically oriented TiO(x)N(y) nanopillar arrays with embedded Ag nanoparticles for visible-light photocatalysis

We present a straightforward method to produce highly crystalline, vertically oriented TiO(x)N(y) nanopillars (up to 1 μm in length) with a band gap in the visible-light region. This process starts with reactive dc sputtering to produce a TiN porous film, followed by a simple oxidation process at elevated temperatures in oxygen or air. By controlling the oxidation conditions, the band gap of the prepared TiO(x)N(y) can be tuned to different wavelength within the range of visible light. Furthermore, in order to inhibit carrier recombination to enhance the photocatalytic activity, Ag nanoparticles have been embedded into the nanogaps between the TiO(x)N(y) pillars by photoinduced reduction of Ag(+) (aq) irradiated with visible light. Transmission electron microscopy reveals that the Ag nanoparticles with a diameter of about 10 nm are uniformly dispersed along the pillars. The prepared TiO(x)N(y) nanopillar matrix and Ag:TiO(x)N(y) network show strong photocatalytic activity under visible-light irradiation, evaluated via degradation of Rhodamine B.     

Soft X-ray characterization of Zn(1-x)Sn(x)O(y) electronic structure for thin film photovoltaics

Zinc tin oxide (Zn(1-x)Sn(x)O(y)) has been proposed as an alternative buffer layer material to the toxic, and light narrow-bandgap CdS layer in CuIn(1-x),Ga(x)Se(2) thin film solar cell modules. In this present study, synchrotron-based soft X-ray absorption and emission spectroscopies have been employed to probe the densities of states of intrinsic ZnO, Zn(1-x)Sn(x)O(y) and SnO(x) thin films grown by atomic layer deposition. A distinct variation in the bandgap is observed with increasing Sn concentration, which has been confirmed independently by combined ellipsometry-reflectometry measurements. These data correlate directly to the open circuit potentials of corresponding solar cells, indicating that the buffer layer composition is associated with a modification of the band discontinuity at the CIGS interface. Resonantly excited emission spectra, which express the admixture of unoccupied O 2p with Zn 3d, 4s, and 4p states, reveal a strong suppression in the hybridization between the O 2p conduction band and the Zn 3d valence band with increasing Sn concentration.     

Fullerene-like (IF) Nb(x)Mo(1-x)S2 nanoparticles

IF-Mo1-xNbxS2 nanoparticles have been synthesized by a vapor-phase reaction involving the respective metal halides with H2S. The IF-Mo1-xNbxS2 nanoparticles, containing up to 25% Nb, were characterized by a variety of experimental techniques. Analysis of the powder X-ray powder diffraction, X-ray photoelectron spectroscopy, and different electron microscopy techniques shows that the majority of the Nb atoms are organized as nanosheets of NbS2 within the MoS2 host lattice. Most of the remaining Nb atoms (3%) are interspersed individually and randomly in the MoS2 host lattice. Very few Nb atoms, if any, are intercalated between the MoS2 layers. A sub-nanometer film of niobium oxide seems to encoat the majority of the nanoparticles. X-ray photoelectron spectroscopy in the chemically resolved electrical measurement mode (CREM) and scanning probe microscopy measurements of individual nanoparticles show that the mixed IF nanoparticles are metallic independent of the substitution pattern of the Nb atoms in the lattice of MoS2 (whereas unsubstituted IF-MoS2 nanoparticles are semiconducting). Furthermore the IF-Mo1-xNbxS2 nanoparticles are found to exhibit interesting single electron tunneling effects at low temperatures.     

Relaxation dynamics in (HF)x(H2O)1-x solutions

The high-frequency dynamics of (HF)(x)(H(2)O)(1-x) solutions has been investigated by inelastic x-ray scattering. The measurements have been performed as a function of the concentration in the range x = 0.20-0.73 at fixed temperature T = 283 K. The results have been compared with similar data in pure water (x = 0) and pure hydrogen fluoride (x = 1). A viscoelastic analysis of the data highlights the presence of a relaxation process characterized by a relaxation time and a strength directly related to the presence of a hydrogen-bond network in the system. The comparison with the data on water and hydrogen fluoride shows that the structural relaxation time continuously decreases at increasing concentration of hydrogen fluoride passing from the value for water to the one for hydrogen fluoride tau(alphaHF), which is three times smaller. This is the consequence of a gradual decreasing number of constraints of the hydrogen-bond networks in passing from one liquid to the other.     

Preparation and Characterization of High Purity Al（2-x）Mg（x＋y）Ti（1-y）O（5-0.5x-y） Solid Solution

A small amount of mineralizer MgO was added into Al2TiO5 synthesized from the sludge of aluminum factory to form Al（2-x）Mg（x＋y）Ti（1-y）O（5-0.5x-y） solid solution and inhibit the decomposition of Al2TiO5 solid solution. It increased the content of Al2TiO5 solid solution and improved the thermal stability of materials. In this work,XRD and SEM methods were adopted to characterize the crystalline structure and microstructure of each kind of sample. Rietveld Quantification method was used to determine the content of crystalline phases in each sample. Results show as follows： the optimal addition concentration of MgO was 2.0%,and the corresponding content of Al2TiO5 solid solution which displayed irregular bulk shape was 100%; the addition of mineralizer MgO could enhance the flexural strength and thermal stability of Al2TiO5 solid solution materials. The optimal addition concentration of MgO determined by performance analysis was 2.0%,and its corresponding retention rate of thermal-shock flexural strength was 86.4%. Structure analysis and performance analysis resulted in good accordance.     

Nanostructured Cu(x)Ce1-xO2-y mixed oxide catalysts: characterization and WGS activity tests

Cu(x)Ce(1-x)O(2-y) mixed oxide catalysts were prepared by different preparation procedures: co-precipitation, the sol-gel peroxide route, and the sol-gel citric acid-assisted route. The resulting solids were investigated by means of XRD, BET, H(2) and CO temperature-programmed reduction (TPR), oxidation (TPO) and desorption (TPD) analyses, and N(2)O pulse selective reaction. It was confirmed that H(2) (CO) consumed for complete reduction of well-dispersed and bulk-like CuO phases to Cu(0), reduction of surface ceria and H(2) (CO) adsorption on the catalyst surface contribute to the total H(2) (CO) consumption. Among catalysts examined, the Cu(0.15)Ce(0.85)O(2-y) mixed oxide sample prepared by means of co-precipitation method exhibits the highest activity and stability for water-gas shift (WGS) pulse reaction in the range of employed operating conditions. WGS activity of copper-ceria mixed oxide catalysts is determined by the extent of surface ceria reduction and dispersion of copper species.     

Local structural distortion of BaZr(x)Ti(1-x)O3 nanocrystals synthesized at room temperature

Single crystalline, sub-15 nm BaZr(x)Ti(1-x)O(3) (0 ≤x≤ 1) nanocrystals were synthesized at room temperature via the vapor diffusion sol-gel method. As-prepared nanocrystals exhibit noncentrosymmetric regions whose volume fraction increases significantly upon substitution of small amounts of Zr(4+) for Ti(4+) and reaches a maximum for substitution levels ranging from 10 to 20 mol%.     

红色荧光粉KYyEu1-y(WO4)x(MoO4)2-x的制备及其发光性能研究

采用高温固相法结合超声波技术合成了红色荧光粉KYyEu1-y(WO4)x(MoO4)2-x系列,探讨了其合成工艺条件,确定了最佳烧结温度为750℃,烧结时间为5 h;并确定了当x=0.5,y=0.1时样品的相对发光亮度达到最大值为118.2,发射峰的位置处在615nm附近(Eu3+离子的5Do→7F2跃迁),色纯度高,显色性能好.经过研究发现,随着钨酸盐的浓度增加,以466 nm波长激发时,Eu3+的5Do→7F2跃迁发射强度也相应增加,当Mo/W=3时亮度达到最大值.     

Ce-doped ZnO (Ce(x)Zn(1-x)O) becomes an efficient visible-light-sensitive photocatalyst by co-catalyst (Cu2+) grafting

We have fabricated an efficient visible-light-sensitive Cu(2+)-grafted Ce-doped ZnO photocatalyst (Cu(2+)-Ce(x)Zn(1-x)O) by adopting a metal ion doping and co-catalyst modification. Impurity states were formed below the conduction band (CB) edge in Ce(x)Zn(1-x)O, and these impurity states induce the visible-light absorption. Ce(x)Zn(1-x)O without a Cu(2+)-co-catalyst showed negligible visible-light activity due to the low reduction power of electrons in impurity levels. Surprisingly, Cu(2+)-modification over Ce(x)Zn(1-x)O drastically increased its visible-light activity. Excited electrons in impurity states can transfer to the Cu(2+)-ions on the surface and form Cu(2+)/Cu(+) redox couples, which cause the efficient oxygen reduction through a multi-electron reduction process. One of the striking features of the present study is that the metal doped semiconductors which were inactive due to their impurity states become efficient visible-light photocatalysts upon co-catalyst modification. The successful strategy used here for designing a highly active visible-light photocatalyst would provide numerous opportunities to develop an efficient metal-ion based visible-light photocatalyst.     

Influence of vacancy ordering on the percolative behavior of (Li(1)(-x)Na(x))(3y)La(2/3-y)TiO(3) perovskites

Influence of the vacancy concentration on the Li conductivity of the (Li(1-x)Na(x))(0.2)La(0.6)TiO(3) and (Li(1-x)Na(x)(0.5)La(0.5)TiO(3) perovskite series, with 0 < or = x < 1, has been investigated by neutron diffraction (ND), impedance spectroscopy (IS), nuclear magnetic resonance (NMR), and Monte Carlo simulations. In both series, Li(+) ions occupy unit cell faces, but Na(+) ions are located at A sites of the perovskite. From this fact, the amount of vacant A sites that participate in Li conductivity is given by the expression n(v) = [Li] + square, where square is the nominal vacancy concentration. Substitution of Li by Na decreases the amount of vacancies, reducing drastically the Li conductivity when n(v) approaches the percolation threshold of the perovskite conduction network. In disordered (Li(1-x)Na(x))(0.5)La(0.5)TiO(3) perovskites, the percolation threshold is 0.31; however, in ordered (Li(1-x)Na(x))(0.2)La(0.6)TiO(3) perovskites, this parameter changes to 0.26. Near the percolation threshold, the amount of mobile Li species deduced by (7)Li NMR spectroscopy is lower than that derived from structural formulas but higher than deduced from dc conductivity measurements. Conductivity values have been explained by Monte Carlo simulations, which assume a random walk for Li ions in the conduction network of the perovskite. In these simulations, distribution of vacancies conforms to structural models deduced from ND experiments.     

Surface S(N)2 reaction by H2O on chlorinated Si(100)-2 x 1 surface

The potential energy surfaces of one, two, and three water molecule sequential adsorptions on the symmetrically chlorinated Si(100)-2 x 1 surface were theoretically explored with SIMOMM:MP2/6-31G(d). The first water molecule adsorption to the surface dimer requires a higher reaction barrier than the subsequent second water molecule adsorption. The lone pair electrons of the incoming water molecule nucleophilically attack the surface Si atom to which the leaving Cl group is bonded, yielding an S(N)2 type transition state. At the same time, the Cl abstracts the H atom of the incoming water molecule, forming a unique four-membered ring conformation. The second water molecule adsorption to the same surface dimer requires a much lower reaction barrier, which is attributed to the surface cooperative effect by the surface hydroxyl group that can form a hydrogen bond with the incoming second water molecule. The third water molecule adsorption exhibits a higher reaction barrier than the first and the second water molecule adsorption channels but yields a thermodynamically more stable product. In general, it is expected that the surface Si-Cl bonds can be subjected to the substitution reactions by water molecules, yielding surface Si-OH bonds, which can be a good initial template for subsequent surface chemical modifications. However, oversaturations can be a competing side reaction under severe conditions, suggesting that the precise control of surface kinetic environments is necessary to tailor the final surface characteristics.     

Metastable 11 K Superconductor Na(1-y)Fe(2-x)As(2)

The topochemical deintercalation of Na(+) ions from solid NaFeAs at room temperature in THF with iodine yields the superconducting phase Na(1-y)Fe(2-x)As(2) (T(c) ≈ 11 K). This metastable iron arsenide decomposes at 120 °C and is not accessible by high-temperature solid-state synthesis. X-ray powder diffraction confirms the ThCr(2)Si(2)-type structure, but reveals very small coherently scattering domains with a mean composition Na(0.9(2))Fe(1.7(1))As(2). HRTEM investigations show crystalline as well as strongly distorted areas with planar defects. The latter are probably due to sodium loss and disorder which is also detected by (23)Na solid state NMR. The (57)Fe-M?ssbauer spectrum of Na(1-y)Fe(2-x)As(2) shows one type of iron atoms in tetrahedral coordination. All results point to one crystallographic phase with very small domains due to fluctuations of the chemical composition. From electronic reasons we suggest the superconducting phase is presumably NaFe(2)As(2) in the ordered fractions of the sample.