Luminescence study of pure and Fe- or Mo-doped ZnWO4 crystals

ZnWO₄, ZnWO₄:Fe and ZnWO₄:Mo crystals were investigated by the methods of time-resolved spectroscopy in the temperature range of 4.2–300 K. It is shown that the Mo and Fe impurities significantly reduce the light yield of ZnWO₄. The main 2.5 eV emission of ZnWO₄ and the 1.77 eV emission band of ZnWO₄:Mo are shown to originate from the triplet excited state of the WO₆ and MoO₆ complex, respectively. In ZnWO₄:Fe,Mo the MoO₆ emission band is shifted to lower energies due to the perturbing influence of the iron impurity. No perturbing effect of Fe or Mo ions was observed for the main emission of ZnWO₄:Fe and ZnWO₄:Mo. The creation spectrum of self-trapped holes was measured for ZnWO₄, ZnWO₄:Fe and ZnWO₄:Mo crystals in the energy region of 4–30 eV.     

Impact of Mo and Ce on growth of single-walled carbon nanotubes by chemical vapour deposition using MgO-supported Fe catalysts

A series of nine catalysts containing Ce/Fe and Mo/Fe at various loadings on MgO supports have been studied as catalysts for chemical vapour deposition (CVD) of single-walled carbon nanotubes (SWCNTs) using a methane carbon source. Our results show that the Ce/Fe system is very suitable as a catalyst that favours SWCNT growth, and we question the special importance that has been attributed to Mo as an additive to Fe-based catalysts for SWCNT growth, as it appears that Ce is equally effective. Our results indicate that dehydroaromatization (DHA) is not a defining step for the growth mechanism, as has been suggested for Mo/Fe systems previously, and show that Ce and Mo do not seriously perturb the well-known Fe/MgO system for growth of high quality SWCNT. Using Raman spectroscopy, we have shown that the Ce/Fe/MgO catalyst system favours growth of SWCNTs with a different distribution of chiralities compared to the analogous Mo/Fe/MgO system.     

Mössbauer and TDPAC Studies on Fe/Mo Multilayers

Hyperfine fields at Fe and Mo layers in polyimide/Fe(10 nm)/[Mo(1.1 nm)/Fe(2.0 nm)]₁₂₀ and [Mo(1.3 nm) /Fe(2.0 nm)]₁₂₀ multilayers prepared by the electron-beam evaporation technique were measured at room-temperature by Mössbauer spectroscopy and perturbed-angular-correlation spectroscopy. The hyperfine fields in the Fe layers do not show a clear dependence on the Mo layer thickness. On the other hand, the hyperfine fields in the Mo layers show different magnetic structures in these samples. The difference suggests a variation of electron spin polarization in the Mo layers.     

Ab initio calculations of interfacial magnetism in Fe/Mo superlattices

Ab initio calculations have been performed on Fe/Mo(1 0 0) superlattices in order to study the interfacial magnetic properties and layer thickness effect on the magnetic moments. In most cases, the magnetic moments of interfacial Fe monolayers are always smaller than those of the inner layers, and the induced magnetic moments of interfacial Mo monolayers oriented in the opposite direction. Calculation results show that the Fe layers are ferromagnetic when n = 3. As the thickness of the Mo layers increases, the influence of the Mo layer increases and the magnetic state of the Fe layer gradually changes into an antiferromagnetic or non-magnetic state. The change of magnetic moments of Fe/Mo superlattices is in agreement with the experimentally observed oscillation periods.     

过渡元素掺杂对Mo力学性能的第一性原理研究

基于密度泛函理论,采用第一性原理方法计算了在Mo中掺杂摩尔百分比分别为2.08%和4.17%的过渡金属元素W,Ti,Cu和Fe后,体系在[111](110)滑移系统上的广义层错能以及解理能,并研究了掺杂元素对Mo的剪切形变以及脆性一韧性的影响,研究发现,掺杂W和Ti原子会使体系剪切形变的发生变得困难,并使Mo材料变脆;而掺杂Cu和Fe原子则会使体系剪切形变的发生变得相对容易,并使Mo材料的韧性增强,此外,随着掺杂浓度的增加,掺杂W会使体系剪切形变的发生变得更为困难,并使Mo材料脆性更强;而掺杂Fe则会使体系剪切形变的发生变得更为容易,并使Mo材料的韧性更强。     

Local magnetic fields in the Mo layer of Mo/Fe multilayer

Using time-differential perturbed-angular-correlation technique, hyperfine fields at ⁹⁹Tc (←⁹⁹Mo) in the Mo layers in polyimide/Fe (10 nm)/[Mo (t _Mo)/Fe (2.0 nm)]₁₂₀, where t _Mo is in the range between 0.4 and 1.5 nm, were measured at room temperature. The values of the magnetic hyperfine field at the Mo/Fe interface were extracted. Its dependence on the Mo layer thickness suggests that the oscillatory interlayer exchange coupling is due to conduction electron spin polarization in the Mo layer, which in turn is produced via an RKKY-type mechanism.     

EPR studies of weakly coupled oxomolybdenum (V) and low-spin iron (III) porphyrin centers

Novel compounds containing twoS=1/2 coupled spin centers (Mo(V) and low spin Fe(III) have been investigated in detail by X- and Q-band EPR spectroscopy, spectral simulation and molecular modelling calculations. For one system with a Mo?Fe distance of ≈9.4 Å the dominant dipolar coupling allows distinction among structures that are consistent with molecular modelling calculations. For the second system with a Mo?Fe of ≈ 7.9 Å the exchange interaction is dominant (0.5 <J < 3.0 GHz). These coupled systems are preliminary benchmarks for using EPR to investigate the Mo?Fe interaction in sulfite oxidase.     

Sonolysis induced decomposition of metal carbonyls: kinetics and product characterization

The decomposition kinetics of Fe(CO)₅ and Mo(CO)₆ induced by sonolysis in hexadecane solvent was studied as a function of temperature (303–343 K) under an inert atmosphere. The decomposition data, obtained over at least two half lives in most of the runs, yielded first-order rate constant (k) values with correlation co-efficient (R²)>0.95. The products were characterized by various spectroscopic techniques. The transmission electron microscopy (TEM) yielded images from which the mean particle diameter (MPD) of 10 nm for Fe and <3 nm for Mo were estimated. The generation of amorphous Fe and semi-crystalline Mo particles was determined from line broadening and corresponding d-spacing values in the X-ray diffraction (XRD) spectra. The XAFS/XANES data were consistent with the production of Fe(0) metal but carbided Mo (Mo₂C). The one-step production of high-yield pyrophoric products demonstrated the applicability of sonolysis to effectively produce gram-quantity of zero-valent metals.     

Specific features of magnetic properties of three-component magnetic superlattices based on Fe/Co/Mo

Synthesis of three-component magnetic superlattices based on the Fe/Co/Mo system by cathode sputtering in an electron-oscillating discharge and their complex investigations have been performed for the first time. The fields have been investigated by X-ray diffraction, vibrational magnetometry, and Mössbauer spectroscopy with the use of completely computerized systems. Oscillations of the main magnetic parameters with a change in the Mo thickness and giant spontaneous magnetization have been found. The properties of three-component superlattices are compared with those of the analogous system based on Fe/Mo.     

发射光谱法同时测定钛基复合材料中的镍铁钼锰和硼的研究

研究了用碳粉、碳酸钙、氧化铜和氧化铍作缓冲剂同时测定钛基复合材料中的镍、铁、钼、锰和硼的发射光谱法,选择铍作内标线,不需分离、不需化学处理,直接压样于杯形的石墨电极中,具有简便、快速、准确。对测定条件、干扰因素进行了研究,从而建立测定镍、铁、钼、锰和硼的新方法。镍、铁、钼、锰和硼的分析线分别为300.36,248.33,315.82,260.57和249.68 nm,内标线选择为铍的298.61 nm,镍、铁、钼、锰和硼的线性范围分别为0.003%～0.30%;0.001%～0.20%;0.003%～0.30%;0.001%～0.20%;0.001%～0.20%。镍、铁、钼、锰和硼的检测限分别0.003%,0.001%,0.003%,0.001%,0.001%,其回收率在95.80%～104.8%范围内,当n=9时,相对标准偏差RSD均小于5%。用于样品的测定取得了满意的结果。     

A study of in-situ Mössbauer spectroscopy on Fe−Mo oxides for selective oxidation of toluene

In-situ Mössbauer spectroscopy, as well as x-ray diffraction and x-ray photoelectron spectroscopy has been used to study the Fe?Mo oxide catalysts with the ratio of Fe/Mo=0.29 and 0.67. The results showed that Fe₂(MoO₄)₃ in the catalysts was reduced to β-FeMoO₄ during the oxidation of toluene, and the β-FeMoO₄ was reoxidized to Fe₂(MoO₄)₃ by the air. The catalyst with the ratio of Fe/Mo=0.29, which was easier to be reduced to β-FeMoO₄, showed higher catalytic activity. The different effects of Fe and Mo in the catalysts are discussed.     

Magnetic and Mössbauer studies of Fe/Mo multilayered thin films

Fe(x)/Mo(y), multilayered thin films (MLF) with y=7.0 nm and x=0.7, 1.3, 2.6, 3.6, 13.0 nm were fabricated by radio frequency (RF) sputtering. X-ray diffraction evidences that these films have a good periodicity and bcc structure for both Fe and Mo layers. Mössbauer spectra at room temperature (RT) are used to investigate the structure and the local magnetic properties of the interfaces between Fe and Mo layers. It is found that the interfaces present alloying features, i.e. the Fe atoms are randomly substituted by Mo atoms. Magnetic anisotropy which forces magnetic moments to lie in the film plane and reduced magnetic moments in interface region were observed. The specific magnetization of the films exhibits a BT^3/2 dependence with very large values of B which can be attributed to the distribution of exchange interaction in the interfaces.     

X-ray absorption and magnetic circular dichroism characterization of Mo1–xFexO2 (x = 0–0.05) thin films grown by pulsed laser ablation

The electronic and magnetic properties of well characterized Mo_1???xFe_xO₂ (x = 0–0.5) thin films that show ferromagnetism at room temperature (RT) have been investigated by the means of near edge x-ray absorption fine structure (NEXAFS) and x-ray magnetic circular dichroism (XMCD) experiments at the O K-, Fe L-, and Mo M-edges. The NEXAFS spectra at O K- and Mo M_3,2 -edges show a strong hybridization of O 2p-4d Mo orbitals, and Mo ions change their symmetry with the substitution of Fe ions into MoO₂ matrix. The Fe 2p NEXAFS/XMCD spectra exhibit multiple absorption peaks and an appreciable XMCD signal that persists even at RT. These results demonstrate that Fe is in a mixed valence state of Fe^2?+?–Fe^3?+?, substituting at the Mo site and that the Fe^2?+?/3?+? ions are ferromagnetically polarized.     

ATOMIC FORCE MICROSCOPY STUDIES AND MODELING OF SURFACE STRUCTURES PATTERNED DURING OSTWALD RIPENING AT Fe/Mo MULTILAYER SYSTEMS

Fe/Mo multilayers which were grown by sputtering, annealed in high vacuum and analyzed by means of Atomic Force Microscopy and Scanning Electron Microscopy. Concentric circle-1ike patterns were observed after annealing. Two-dimensional Ostwald ripening mechanisms in immiscible systems of Fe/Mo may explain the formation of these structures. We simulated pattern formation in a late stage of the phase separation by applying the Thomas-Freundlich thermodynamic relation. Based on a two-dimensional mode1 in the framework of the Lifshitz-Slyozov theory, our modeling has been extended to include the diffusion limitation in a multi-cluster system.     

Electrical and nonlinear optical studies of flux grown Mo and Fe doped KTP crystals

The molybdenum (Mo) and ferric (Fe) doped potassium titanyl phosphate (KTP) crystals were grown by high temperature solution growth (HTSG) technique. The concentration of Mo and Fe in grown crystals was measured by EDX analysis. The SHG efficiencies of the Mo and Fe doped KTP crystals were measured and it was found to be 1.77 and 1.38 times respectively higher than that of pure KTP crystal. The frequency dependence of dielectric constant, loss and ac conductivity was studied at room temperature. The phase matching measurements were made using a Q-switched Nd:YAG laser operating at 1064 nm and the measured phase matching angles are 44.2° and 87.88° for Mo and Fe doped KTP crystals respectively.     

含MoFe3S4单元的μ2—OR或μ2—SR桥联双类立方烷簇合物的红？…

对下列含ＭｏＦｅ３Ｓ４单元的μ２－ＯＲ或μ２－ＳＲ桥联双类立方烷簇合物的红外光谱进行了研究：（Ｅｔ４Ｎ）３「Ｍｏ２Ｆｅ６Ｓ８Ｃｌ６（ＯＭｅ）３」（１）,（Ｅｔ４Ｎ）３「Ｍｏ２Ｆｅ６Ｓ８（ＳＰｈ）６（ＯＭｅ）３」（２）,（Ｂｕ４Ｎ）３「Ｍｏ２Ｆｅ６Ｓ８（ＳＰｈ）６（ＯＭｅ）３」（３）（Ｅｔ４Ｎ）３「Ｍｏ２Ｆｅ６Ｓ８（ＳＢｕ＾ｔ）６（ＯＭｅ０３」（４）ｍ,（Ｅｔ４Ｎ）３「Ｍｏ２Ｆｅ６Ｓ８（ＳＰｈ）９」     

Mn掺杂Mo2 FeB2的电子结构，磁性和弹性的第一性原理研究

用第一性原理计算（ Mo,Fe,Mn）3 B2的结构稳定性、磁性、电子结构和弹性。过程中采用了密度泛函理论和超软赝势。研究表明反铁磁性具有最低的能量,为基态。计算所得的（ Mo,Mn,Fe） B2电子态密度和布局数与Mo2 FeB2的类似。从电子态密度和重叠布局数发现,B?B和B?Mo为共价键,对剪切模量起促进作用。通过磁性分析,发现Fe和Mn原子起主要作用。然而,Mn的掺杂对硬质相Mo2 FeB2的成键和弹性的影响微小。     

First principles study on electronic properties and occupancy sites of molybdenum doped into LiFePO4

The electronic properties of Mo-doped LiFePO₄ and occupancy sites of Mo are investigated by employing the density functional theory plane-wave pseudopotential method. The calculated results show that Mo doping at Fe site has lower formation energy, which implies that Mo dopants prefer to occupy Fe sites within the LiFePO₄ lattice. Furthermore, the LiFe_1?3/12Mo_1/12PO₄ has wider lithium ion migration channels than Li_1?6/12Mo_1/12FePO₄. For the case of LiFe_1?3/12Mo_1/12PO₄, the calculated narrow band gap (0.18 eV) indicates that the electronic conductivity of LiFePO₄ could be enhanced by doping Mo at the Fe sites. The density of states and charge densities of LiFe_1?3/12Mo_1/12PO₄ demonstrate that the Mo-4d states and MoO bonding play important roles in band gap reduction of LiFe_1?3/12Mo_1/12PO₄.     

Determination of trace iron (II) and molybdenum (VI) in ground water by pyrocatechol resin-phase spectrophotometry]

In weak acid medium (pH 6.20), Fe(III) and Mo(VI) can form colored complexes with pyrocatechol and quantitatively adsorbed on 717 strong base anion exchange resin. The apparent molar absorption coefficients of resin phase are epsilon = 4.1 x 10(4) L/(mol x cm) at 520 nm for Fe(III) and epsilon = 9.0 x 10(4) L/(mol x cm) at 400 nm for Mo(VI). Beer's law is obeyed for Fe (III) and Mo(VI) in the range of 0-2.2 mg x L(-1) and 0-1.6 mg x L(-1). The method has been applied to the determination of trace Fe(III) and Mo(VI) in ground water. The relative standard deviations are 3.3% and 3.2%, respectively.     

Atomic displacements in dilute alloys of Cr, Nb and Mo

Kanzaki lattice static method is used to calculate the atomic displacements due to substitutional impurities in 3d (Cr) and 4d (Nb, Mo) metals. Wills and Harrison interatomic potential is used to calculate dynamical matrix and the impurity-induced forces up to second nearest neighbors. The calculated atomic displacements for 3d, 4d and 5d impurities in Cr (V, Mn, Fe, Ni, Nb, Mo, Ta and W), Nb (V, Cr, Mn, Fe, Zr, Mo, Ta and W) and Mo (V, Cr, Mn, Fe, Zr, Nb, Ta and W) are tabulated up to 10 NN’s. The strain field due to 3d impurities is least in Cr metal while it is larger in Nb and Mo metals. For 4d and 5d impurities the strain is larger in Cr metal than in Nb and Mo hosts. Similar trend is found for relaxation energies also.