X-ray photoelectron spectroscopy of FeP phosphide

The structure of the outer and inner electron spectra of iron (2p, 3p, 3s, and 3d) and phosphorus (3s and 3p) atoms in FeP monophosphide is studied in detail by the X-ray photoelectron spectroscopy (XPS) method. On the basis of the analysis of the binding energy of electrons, as well as the parameters characterizing the structure of experimental spectra, a conclusion is made that Fe³⁺ (d ⁵) cations in FeP are stabilized in a state with intermediate value of the total spin (IS, S = 3/2). The range of values of intra-atomic parameters (10Dq, J _H ) is established in which the consideration of the high degree of covalence of Fe–P bonds may lead to the stabilization of (FeP₆)^15– clusters in the IS state.     

Mn3<Emphasis Type="Italic">s</Emphasis> X-ray photoelectron spectra of polynuclear trimethylacetate complexes of manganese

The Mn3s X-ray photoelectron spectra of manganese at oms in mono-, bi-, tri-, and hexanuclear trimethylacetate Mn complexes and Mn^IICl₂, Mn^IIIOOH, Mn^IVO₂. ionic compounds were measured. The 3s spectra of the manganese atoms in Mn^II, Mn^III, and Mn^IV valent states were calculated within the isolatedion approximation. The relationship between the characteristics of the Mn3s spectra and the magnetic moments of the manganese ions in the complexes is discussed.     

Mössbauer study of iron uptake in cucumber root

⁵⁷Fe Mössbauer spectroscopy was used to study the uptake and distribution of iron in the root of cucumber plants grown in iron-deficient modified Hoagland nutrient solution and put into iron-containing solution with 10 μM Fe citrate enriched with ⁵⁷Fe (90%) only before harvesting. The Mössbauer spectra of the frozen roots exhibited two Fe³⁺ components with typical average Mössbauer parameters of δ?=?0.5 mm s^?1, Δ?=?0.46 mm s^?1 and δ?=?0.5 mm s^?1, Δ?=?1.2 mm s^?1 at 78 K and the presence of an Fe²⁺ doublet, assigned to the ferrous hexaaqua complex. This finding gives a direct evidence for the existence of Fe²⁺ ions produced via root-associated reduction according to the mechanism proposed for iron uptake for dicotyledonous plants. Monotonous changes in the relative content of the components were found with the time period of iron supply. The Mössbauer results are interpreted in terms of iron uptake and transport through the cell wall and membranes.     

Valence states of iron ions in nanostructured yttrium iron garnet Y3Fe5O12 studied by means of soft X-ray absorption spectroscopy

Nanostructured samples of yttrium iron garnet Y₃Fe₅O₁₂ obtained by plastic deformation method (high-pressure torsion) were studied with help of soft X-ray absorption spectroscopy using Fe 2p and O 1s spectra. Experimental spectra were compared with crystal field multiplet calculations for Fe ions. Some amount of Fe²⁺ ions in nanostructured Y₃Fe₅O₁₂ was found. The concentration of Fe²⁺ ions was found to be increased with the increase of the degree of plastic deformation.     

Analysis of XPS spectra of Fe and Fe ions in oxide materials

Samples of the iron oxides Fe_0.94O, Fe₃O₄, Fe₂O₃, and Fe₂SiO₄ were prepared by high temperature equilibration in controlled gas atmospheres. The samples were fractured in vacuum and high resolution XPS spectra of the fractured surfaces were measured. The peak positions and peak shape parameters of Fe 3p for Fe²⁺ and Fe³⁺ were derived from the Fe 3p XPS spectra of the standard samples of 2FeO·SiO₂ and Fe₂O₃, respectively. Using these parameters, the Fe 3p peaks of Fe₃O₄ and Fe_1−yO are analysed. The results indicate that high resolution XPS techniques can be used to determine the Fe²⁺/Fe³⁺ ratios in metal oxides. The technique has the potential for application to other transition metal oxide systems.     

Relation between 2p X-ray photoelectron and Kα X-ray emission spectra of manganese and iron oxides

The high resolution Mn and Fe Kα X-ray emission spectra (XES), and Mn and Fe 2p X-ray photoelectron spectra (XPS) for manganese and iron oxides were measured. The spectra were compared with those of [MnO₄]⁻, [Fe(CN)₆]⁴⁻ and [Fe(CN)₆]³⁻ ions. As the electronic structure of the latter compounds do not change with electron hole creation in the core levels, satellite peaks due to charge transfer are not observed in the 2p XPS spectra, and the peak profiles of metal 2p XPS and Kα XES are governed by the exchange splitting between 2p and valence electrons. The metal 2p XPS spectra of the oxides had satellite peaks, but the XES spectra had no satellites. FWHMs of the metal 2p_3/2 main peaks of the compounds being low spin states are smaller than those of metal Kα₁ XES spectra. However, FWHMs of Mn 2p_3/2 of the manganese oxide were nearly equal to those of Mn Kα₁ XES spectra, and those of Fe 2p_3/2 XPS spectra of the iron oxides are greater than those of Fe Kα₁ XES spectra.     

Nitrogen 1s electron binding energy assignment in carbon nitride thin films with different structures

Carbon nitride thin films deposited by dc unbalanced magnetron sputtering have been analyzed by high-resolution X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The XPS data show that N 1s binding states depend on substrate temperature (T_s). By comparison with the Raman spectra, N 1s binding states are assigned in which nitrogen atoms are mainly bound to sp² and sp³ carbon atoms at T_s = 100°C, whereas at T_s = 500°C nitrogen atoms are mainly bonded to sp², sp³ and sp¹ carbon atoms.     

An AES analysis of oxide films on iron

The Auger spectra of the iron oxides have been investigated. The relative amplitudes of the Auger lines from oxygen and iron have been determined for FeO, Fe₃O₄, α-Fe₂O₃, γ-Fe₂O₃, and FeOOH. It was found that the amplitude ratio s of the O (510 eV)/Fe (703 eV) lines was, to a first approximation, directly proportional to the ratio of oxygen and iron in the chemical formula. Structure was observed in the spectra resulting from the Fe M_2,3 VV transition. Different spectra were observed for Fe, FeO, Fe₃O₄, Fe₃O₃, and FeOOH; however, the same spectra were obtained for α- and γ-Fe₂O₃.     

Application of X-ray absorption spectroscopy to the investigation of charge states of iron ions in iron borate nanoceramics

The method of X-ray absorption spectroscopy has been used for the investigation of charge states of iron ions in iron borate nanoceramics prepared by shear deformation under pressure. The experimental Fe 2p X-ray absorption spectra have been presented in comparison with the calculation of atomic multiplets of iron ions taking into account the charge transfer from the 2p orbitals of oxygen to the 3d orbitals of iron and the crystal-field splitting of the 3d orbitals of iron. Our results indicate that, in addition to iron ions in the ground charge state Fe³⁺, nanostructured FeBO₃ contains a few percent of Fe²⁺ ions. It has been found that an increase in the degree of plastic deformation (the rotation angle of the anvils) leads to a decrease in the size of crystallites and to an increase in the concentration of Fe²⁺ ions without the formation of new phases. The results of this work agree with the magnetic and optical measurements and confirm high defectness of FeBO₃ nanoceramics.     

The iron oxidation state in Mg-Al-Fe mixed oxides derived from layered double hydroxides: An XPS study

Mixed oxides with large surface area and high thermal stability can be obtained by thermal treatment of the layered double hydroxides (LDH). Mg-Al-Fe mixed oxide samples with varying Mg/Al ratio and 5 mol.% of Fe were prepared in this way and the iron oxidation state (Fe_ox) in these compounds was studied by X-ray photoelectron spectroscopy (XPS), using a calibration based on the relation of Fe_ox to the splitting between the O 1s and Fe 2p_3/2 centroids. The XPS results confirm Fe³⁺ as a dominant oxidation state in the studied mixed oxides. A vacuum-induced reduction of iron in the Fe₂O₃ and Mg-Al-Fe oxide samples has been observed and an influence of the Mg:Al ratio on this effect in mixed oxides has been detected. The role of the local variations of the electron density distribution in the close neighbourhood of the surface oxygen atoms in the mixed oxides in the reduction processes is discussed.     

The interaction of oxygen molecules with iron films studied with MIES,UPS and XPS

X-ray Photoelectron Spectroscopy (XPS), Metastable Induced Electron Spectroscopy (MIES) and Ultraviolet Photoelectron Spectroscopy (UPS) were applied to study the interaction of oxygen molecules with iron films. Supplementarily, iron oxide was investigated for comparison.With XPS from the Fe 2p_3/2 range contributions of metallic Fe as well as Fe²⁺ and Fe³⁺ can be distinguished. During the interaction with oxygen an oxide film is formed on the iron surface. Nevertheless, XPS still shows metallic contributions even for a surface which is saturated with more than 10⁴ L. The oxide film hinders the dissociation of further impinging oxygen molecules.The interaction of He* atoms with iron oxide surfaces during MIES is dominated by Auger Neutralization. This surprising result follows from the high work function and the fact that intrinsic defects result in a Fermi level pinning to the conduction band.     

57Fe Mössbauer study of Li x Fe1-y Co y PO4 (y = 0, 0.1, 0.2) as cathode material for Li-ion batteries

Lithium iron phosphates LiFe_1-y Co _y PO₄ (y = 0, 0.1, 0.2) exposed to a charging process were studied by ⁵⁷Fe Mössbauer spectroscopy taking into account XRD and SEM data. Hyperfine parameters of the spectra were determined above and below the magnetic ordering temperature for all the samples. It was shown that the presence of Co impurity atoms in lithium phosphates gives no effect on the hyperfine interaction of ⁵⁷Fe²⁺ cations. However, Co atoms in the nearest cation environment of Fe atoms lead to a significant change of the hyperfine interactions of ⁵⁷Fe³⁺ cations. The Co impurity atoms distribution over the positions of the iron atoms in the structure is found not to be statistical,but correlated.     

Hyperfine magnetic interactions of 57Fe nuclei in NaFeAs arsenide

The results of the Mössbauer effect studies of layered NaFeAs arsenide in a wide temperature range are presented. The measurements at T > T _N demonstrate that the main part (～90%) of iron atoms are in the low-spin state Fe²⁺. The other atoms can be attributed to the impurity NaFe₂As₂ phase or to the extended defects in NaFeAs. The structural phase transition (at T _S ≈ 55 K) does not produce any effect on hyperfine parameters (δ, Δ) of iron atoms. At T < T _N, the spectra exhibit the existence of a certain distribution of the hyperfine magnetic field (H _Fe) at ⁵⁷Fe nuclei, indicating the inhomogeneity of the magnetic environment around iron cations. The analysis of the temperature behavior of the distribution function p(H _Fe) allows us to determine the temperature of the magnetic phase transition (T _N = 46 ± 2 K). It has been found that the magnetic ordering in the iron sublattice has a two-dimensional type. The analysis of the H _Fe(T) dependence in the framework of the Bean-Rodbell model reveals a first-order magnetic phase transition accompanied by a drastic change in the electron contributions to the main component (V _ZZ ) and the asymmetry parameter (η) of the tensor describing the electric field gradient at ⁵⁷Fe nuclei.     

57Fe Mössbauer Spectroscopic Investigation of Low-Iron Coals and Their Flyash

Trends in the speciation of iron and sulfur in high iron/sulfur coals are well-established. Less is known concerning iron and sulfur speciation in low sulfur coals such as those investigated in this study. Low sulfur coals and their flyash from Thunder Bay, Ontario, Canada and Atikokan, West Virginia, U.S.A. have been investigated by means of ⁵⁷Fe Mössbauer spectroscopy, X-ray diffraction and X-ray fluorescence. Virgin coals, containing approximately 0.1% Fe, exhibited Mössbauer spectra too low in intensity to characterize the phases present. The flyash exhibited well-resolved, simple doublets with ΔE_Q=1.16 mm s^?1 (Canada) and 1.26 mm s^?1 (U.S.A.) and isomer shift values (w.r.t. Fe) of 0.22 mm s^?1 and 0.23 mm s^?1, respectively, characteristic of Fe³⁺. The linewidths of ～0.80 mm s^?1 are unusually large. Treatment of the flyash with cold, hydrofluoric acid resulted in a sample that exhibited very little absorption in its ⁵⁷Fe Mössbauer spectrum. This result, in conjunction with the linewidths, indicates that the Fe is present in the flyash mainly as a silicate glass.     

Magnetic,electronic and structural properties of ZnxFe3−xO4

A series of samples Zn_xFe_3−xO₄ have been prepared by the chemical coprecipitation technique and characterized by X-ray diffraction (XRD), vibrating sample magnetometry (VSM) and X-ray photoelectron spectroscopy (XPS). XRD demonstrates all the samples of Zn_xFe_3−xO₄ have a spinel structure same as Fe₃O₄. The magnetic hysteresis loops of Zn_xFe_3−xO₄ obtained from VSM indicate that the saturation magnetization has a maximum when x is ∼1/3. The chemical states of Fe atoms and Zn atoms in zinc ferrites have been measured using XPS and Auger electron spectroscopy (AES). The Fe 2p core-level XPS spectra and Zn L₃M₄₅M₄₅ Auger peaks have been analyzed and the results have been discussed in correlation with the samples’ magnetic properties. These results suggest most of Zn atoms occupy the tetrahedral sites and a small amount of them occupy the octahedral sites.     

Absorption spectroscopic study of the conduction band of titanium dichalcogenides

The L _{2, 3} spectra of titanium in the layered compound TiSe₂ and intercalated compounds Fe_1/2TiSe₂, Cr_1/3TiSe₂, and Fe_1/4TiTe₂ are studied. Theoretical calculations of the electronic structure of these compounds are performed. The experimental data and calculations suggest that the intercalation of the Cr and Fe atoms into the TiSe₂ matrix brings about a partial filling of the Ti 3d states and the spin polarization of the Cr 3d and Fe 3d states. Chemical bonds are formed through the hybridization of the d orbitals of intercalated atoms with the Ti 3d-Se 4p states of the matrix.     

Iron XII to XXII spectra measurements between 250 and 400 Å

This paper reports laboratory measurements of the spectrum of the most abundant transition Fe ions in the universe. Spectrum of iron of low-lying excited states has been observed in the wavelength range 250–400 Å at Chinese Institute of Atomic Energy on the HI-13 tandem accelerator with beams of 130 MeV. A number of spectral lines have been mainly classified as transitions of magnesium-, sodium-, neon-, fluorine-like ions. A total of 54 lines have been measured. Most of them have been mainly ascribed to 3s3p^k–3p^k+1, 3s²3p^k–3s3p^k+1, 2p⁵3s–2p⁵3p, 3s3d–3p3d and 2p⁵3p–2p⁵3d resonance transitions. These spectral lines have been identified, among which 21 are new and accurately measured. The analysis of the spectra was based on a comparison with other experimental results and calculated values.     

Mössbauer investigation of iron uptake in wheat

Iron uptake and distribution in wheat roots were studied with ⁵⁷Fe Mössbauer spectroscopy. Plants were grown both in iron sufficient and in iron deficient nutrient solutions. Mössbauer spectra of the frozen iron sufficient roots exhibited three iron(III) components with the typical average Mössbauer parameters of δ?= 0.50 mm s^???1, Δ?= 0.43 mm s^???1, δ?= 0.50 mm s^???1, Δ?= 0.75 mm s^???1 and δ?= 0.50 mm s^???1, Δ?= 1.20 mm s^???1 at 80 K. These doublets are very similar to those obtained earlier for cucumber [0], which allows us to suppose that iron is stored in a very similar way in different plants. No ferrous iron could be identified in any case, not even in the iron deficient roots, which confirms the mechanism proposed for iron uptake in the graminaceous plants.     

Photooxidation of different organic dyes (RB, MO, TB, and BG) using Fe(III)-doped TiO2 nanophotocatalyst prepared by novel chemical method

The nano-structured Fe(III)-doped TiO₂ photocatalysts with anatase phase have been developed for the oxidation of non-biodegradable different organic dyes like methyl orange (MO), rhodamine B (RB), thymol blue (TB) and bromocresol green (BG) using UV-Hg-lamp. The different compositions of Fe_xTi_1−xO₂ (x = 0.005, 0.01, 0.05, and 0.1) nanocatalysts synthesized by chemical method (CM), have been characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance spectra, specific surface area (BET), transmission electronic microscopy (TEM) analysis, XPS, ESR and zeta potential. From XRD analysis, the results indicate that all the compositions of Fe(III) doped in TiO₂ catalysts gives only anatase phase not rutile phase. For complete degradation of all the solutions of the dyes (MO, RB, TB, and BG), the composition with x = 0.005 is more photoactive compared all other compositions of Fe_xTi_1−xO₂, and degussa P25. The decolorization rate of different dyes decreases as Fe(III) concentration in TiO₂ increases. The energy band gap of Fe(III)-doped TiO₂ is found to be 2.38 eV. The oxidation state of iron has been found to be 3+ from XPS and ESR show that Fe³⁺ is in low spin state.     

XPS study of the valence band spectrum of amorphous Fe-B alloys

XPS spectra of Fe 3s and Fe 3p levels and Fe 3d valence band of amorphous iron-boron alloys were measured as a function of boron concentration over the range from 12 to 25 at% B. It was found that a characteristic hump appeared at lower energy region in Fe 3d band spectrum of every amorphous Fe-B alloy. The origin of the hump was discussed in terms of the formation of a new bonding state between Fe and B atoms in amorphous Fe-B alloys.