Mössbauer spectroscopy studies of unsupported FeMo sulfide hydrodesulfurization catalysts

Three iron species were detected in FeMo sulfide hydrodesulfurization catalysts:FeS₂(pyrite),Fe_1–xS and the mixed Fe-Mo-S structure.High temperature reduction in hydrogen and resulfidation cause a partial transformation of the above phases into FeS (troilite) and Fe₇S₈(pyrrhotite), respectively.     

Effect of phase transitions on the exciton absorption spectrum of Rb<Subscript>x</Subscript>K<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ag<Subscript>4</Subscript>I<Subscript>5</Subscript> superionic conductors

The absorption spectrum of thin films of solid solutions of Rb_xK_1?xAg₄I₅ superionic conductors is investigated in the energy range 3–6 eV at temperatures from 90 to 290 K upon heating and cooling. It is established that the temperature dependences of the spectral position E _m and the half-width Γ of the long-wavelength exciton band are determined by the exciton-phonon interaction and the generation of Frenkel defects at phase transitions to the superionic state. Fluctuations of the composition of solid solutions do not affect the behavior of the dependences E _m (x) and Γ(x) at 90 K, which is indicative of the localization of excitons in the AgI sublattice of these compounds. A difference in the dependences T _c 1(x) and T _c 2(x) (the γ → β and β → α phase transitions, respectively) is revealed: the curve T _c 1(x) has a minimum at x ≈ 0.5, whereas the curve T _c 2(x) shows a weak maximum.     

The influence of phase transitions in the Rb<Subscript>2</Subscript>CdI<Subscript>4</Subscript> ferroelastic on the exciton absorption spectrum

The parameters of the long-wavelength exciton band for Rb₂CdI₄ films are investigated in the temperature range 90–410 K. It is found that the Rb₂CdI₄ films undergo a sequence of phase transitions at temperatures T_c1=380 K (paraphase → incommensurate phase), T_c2=290 K (incommensurate phase → ferroelastic phase I), and T_c3 = 210 K (ferroelastic phase I → ferroelastic phase II). The parameters of the exciton band (such as the spectral position and the half-width) measured during heating and cooling of the Rb₂CdI₄ film differ significantly. This is especially true for the incommensurate phase. Upon heating of the incommensurate phase, the domain boundaries become frozen, whereas the cooling of this phase is accompanied by the generation of solitons and their pinning, which, in turn, results in a first-order phase transition at the temperature T_c2. It is revealed that the oscillator strength of the exciton band anomalously increases in the range of existence of commensurate phase I (T_c3<-T<-T_c2) due to ordering of the Rb₂CdI₄ crystal lattice.     

High-temperature redistribution of cation vacancies and irreversible magnetic transitions in the Fe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>S nanodisks observed by the Mössbauer spectroscopy and magnetic measurements

The hexagonal pyrrhotite Fe_1?x S nanodisks with the NiAs-type structure were synthesized by thermal decomposition of ferrous chloride and thiourea in oleylamine. The Mössbauer spectroscopy and magnetic measurements data indicate that a mixture of antiferromagnetic (AFM) and ferrimagnetic (FRM) phases with the NC (N ≥ 3) and 2C-type superstructures is present in the Fe_1?x S compound at temperatures between 80 K and Néel temperature T _N. At T < 370 K, the AFM phase prevails over the FRM phase. At T > 370 K, a redistribution of iron vacancies takes place, and the vacancy ordering transforms from the NC (N ≥ 3) to 2C-type which essentially increases the magnetization with maximum value at 470 K. Heating the sample above the Néel temperature 565 K leads to a random distribution of vacancies, and this state is quenched upon subsequent cooling of the sample to 300 K. This gives rise to a pure AFM structure with a zero magnetic moment due to a total compensation of the moments in neighboring iron layers. Thus, the high-temperature redistribution of cation vacancies leads to irreversible magnetic transformations in the Fe_1?x S nanoparticles.     

<Emphasis Type="Italic">N</Emphasis>-shaped voltage-current characteristic and current oscillations in Sm<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> Sr<Subscript>x</Subscript>MnO<Subscript>3</Subscript> manganite

The voltage-current characteristics (VCC) of Sm_1?xSr_x MnO₃ samples with x=0.425 and x=0.450 were experimentally studied at a temperature of 77 K in pulsed and constant electric (E) and magnetic (H) fields up to 10 kOe for the H‖E and H⊥E orientations. N-shaped VCCs and high-frequency (up to 3 MHz) current oscillations were observed. It was found that the effect of colossal magnetoresistance had a threshold character and was smoothly reduced to zero with E→0.     

Metal-insulator transition in Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>S crystals

Results of an experimental study of MnS, FeS, and Fe _x Mn_1?x S single crystals are presented. The phase composition, the lattice parameters, and the state of paramagnetic ions in Fe _x Mn_1?x S have been determined by x-ray diffraction analysis and Mössbauer spectroscopy. A sequence of transitions have been found in iron manganese sulfide with x = 0.29 at temperatures T ₁ ≈ 25–50 K, T ₂ ≈ 125 K, and T ₃ ≈ 190 K with a change in kinetic properties and the formation of a metallic state at low temperatures T ≈ 2 K. The possibility of a Mott-Hubbard transition in Fe _x Mn_1?x S sulfides with variation of the composition and the temperature is discussed.     

Mössbauer spectroscopic study on chemical changes of iron compounds with the aid of sulfate-reducing bacteria

⁵⁷Fe Mössbauer spectra were measured of reaction products formed during an incubation experiment with sulfate-reducing bacteria, which were isolated from estuarine sediments of the Tama River in Tokyo. The spectrum of the product incubated for several days showed some overlapping sextets. This product had a different chemical form from amorphous iron monosulfide produced by inorganic reaction between ferrous and sulfide ions. It was estimated that the structure of nearest neighbor of iron in this product was similar to that of pyrrhotite (Fe_1?x S). After several months of incubation, other singlet and doublet appeared successively on the spectrum, corresponding to mackinawite (FeS_1?x ) and new sulfide, respectively. Both values of isomer shift and quadrupole splitting of new sulfide increased with increasing incubation time and approached those of pyrite (FeS₂). Extended X-ray absorption fine structure (EXAFS) showed that iron atoms were coordinated by sulfur in the incubation product.     

Existence of two types of perfect Bi<Subscript>2</Subscript>Sr<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>La<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>CuO<Subscript>6+δ</Subscript> single crystals

It is found that perfect Bi₂Sr_2?x La _x CuO_6+δ single crystals with the same concentrations of lanthanum x = 0.64 and excess oxygen δ = 0.237 exist in two types. Single crystals of the first type are obtained by slow cooling (the synthesis time is 90–105 h). They have a monoclinic superlattice and exhibit no superconducting transition down to 2 K. Crystals of the second type are obtained by rapid cooling (the synthesis time is 30–40 h) and are characterized by a orthorhombic superlattice and T _c = 18 K. Thus, the superconducting transition temperature is determined not only by the concentration of carriers but also by the configuration of defects. A rhombic superlattice prevails in single crystals obtained by slow cooling in the lanthanum concentration range x = 0.3–0.5, while a monoclinic superlattice dominates in the range x = 0.75–0.85. This fact explains the high values of T _c at optimal doping (x = 0.4) and the absence of high-T _c superconductivity at p < 0.10.     

Mössbauer study of products of the thermocatalytic treatment of kerogen-containing rocks

To understand the mechanism of highly efficient catalyst formation from precursors, the active form of an iron-containing catalyst and kerogen samples from the Bazhen formation are studied by Mössbauer spectroscopy and X-ray diffraction analysis. It is established that as a result of phase changes, the multicomponent precursors are transformed into mixed transition metal oxides. It is found that the thermocatalytic effect on pyrite-containing kerogen leads to the formation of pyrrhotite FeS_{1 ? x} and mixed oxides of iron.     

Mössbauer study of copper ferrite diluted by Ga<Superscript>3+</Superscript> and Al<Superscript>3+</Superscript> ions

Mössbauer spectra of the CuGa _x Al_2x Fe_{2 ? 3x} O₄ system (x = 0.1, 0.2, 0.3, 0.4, 0.5) have been studied at a temperature of 295 K. The results obtained are compared with Mössbauer data for the CuGa _x Al _x Fe_2?2x O₄ system. It is established that the hyperfine magnetic fields H _B (for octahedral sites) and H _A (for tetrahedral sites) for ferrites in both systems with ferrimagnetic ordering decrease linearly depending on the total number of nonmagnetic ions in octahedral and tetrahedral sites of the two systems.     

Mössbauer spectroscopy studies of the preparation steps of unsupported Fe- and FeMo-sulfide hydrotreating catalysts

Both the gas atmosphere (Ar, 15% H₂S−H₂, H₂) and the temperature of treatment strongly affect the distribution of iron atoms among different phases (FeS₂-pyrite, Fe_1−x S-pyrrhotite, FeS-troilite, mixed Fe−Mo−S structure) in Fe- and FeMo sulfide catalysts. In FeMo sulfide catalysts FeS₂ (pyrite) and the Fe−Mo−S structure are stabilized by MoS₂.     

Heat capacity of PMN near an electric-field-induced phase transition

The heat capacity of a single crystal of Pb(Mg_1/3Nb_2/3)O₃ (PMN) in an electric filed with E = 3 kV/cm applied along the [111] direction has been measured using adiabatic calorimetry over the temperature range 170–250 K. Anomalies in C _p have been found, which correspond to a field-induced phase transition from a relaxor to a ferroelectric state at 225 K under field cooling conditions or at 235–240 K on the subsequent field heating. The field-induced ferroelectric phase persists in a metastable state at low temperatures and is destroyed on zero-field heating at 210 K. The small entropy change ΔS = 0.028R in the field-induced phase transition suggests an insignificant change in the volume fraction of existing polar nanoregions.     

Multicomponent <Emphasis Type="Italic">n</Emphasis>-(Bi,Sb)<Subscript>2</Subscript>(Te,Se,S)<Subscript>3</Subscript> solid solutions with different atomic substitutions in the Bi and Te sublattices

The thermoelectric properties of n-Bi_{2 ? x} Sb _x Te_{3 ? y ? z} Se _y S _z solid solutions are studied in the temperature range 300–550 K. It is shown that an increase in the parameter β determining the figure-of-merit Z of the material is observed in compositions with the optimally related effective mass of the density of states m/m ₀, the carrier mobility μ₀, and the lattice thermal conductivity κ _L . Within the temperature range 300–350 K, the parameter β and the figure-of-merit Z are found to increase in solid solutions with substitutions in both bismuth telluride sublattices Bi → Sb and Te → Se, S (x = 0.16, y = z = 0.12) for optimum electron concentrations. An increase in the electron concentration and substitutions of atoms only in the tellurium sublattice bring about an increase in the β parameter and the value of Z at higher temperatures. Within the range 350–450 K, the parameters β and Z are observed to increase in a solid solution with a low content of substituted atoms in the tellurium sublattice Te → Se, S for y = z = 0.09 and, at higher temperatures up to 550 K, in compositions with tellurium substituted by selenium only, with increasing content of substituted atoms.     

Thermodynamic study of compounds of the Nd-Ba-Cu-O system

Standard enthalpies of formation for solid solutions of composition Nd_{1 + x} Ba_{2 ? x} Cu₃O _y (x = 0–0.8, y = 6.65–7.24) from oxides were determined by solution calorimetry. The heat capacity of NdBa₂Cu₃O_6.87 phase was measured in the range 5–320 K by low-temperature adiabatic calorimetry. The absolute entropy S ^o(T), the difference of enthalpies H ^o(T)-H ^o(0 K), and the reduced Gibbs energy Φ^o(T) = S ^o(T)–[H ^o(T)–H ^o(0)]/T were calculated on the basis of smoothed dependence C _p (T) in the 0–320 K range. An assessment was made for the heat capacities and the absolute entropies of solid solutions Nd_1+x Ba_2?x Cu₃O _y . The obtained set of thermodynamic parameters can be used for the calculation of phase equilibria in the Nd-Ba-Cu-O system.     

Colossal room-temperature magnetoresistance in thin La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ag<Subscript>y</Subscript>MnO<Subscript>3</Subscript> epitaxial films

The first thin La_1?xAg_yMnO₃ epitaxial films (_y ≤ x) were grown on SrTiO₃ (110) substrates with silver present in the ionized state (Ag⁺) only. The Curie temperatures T_C of the compositions with x = y = 0.05, x = y = 0.1, and x = 0.3 and y = 0.27 crystallizing in the hexagonal structure \(R\bar 3c\) above or close to room temperature. The temperature dependences of electrical resistivity ρ and of magnetoresistance ¦Δρ/ρ/¦ = ¦(ρ_H ? ρ _H = 0)/ρ_H=0¦ pass through maxima near T_C, with the magnetoresistance being negative and reaching colossal values of ～7–20% in a magnetic field H = 8.2 kOe not only at T_C but also at room temperature. The magnetic moment per formula unit as derived from the saturation magnetization at T = 5 K is substantially smaller than expected for complete ferromagnetic ordering. The magnetization in fields of up to 6 kOe depends on the actual sample cooling conditions, and the hysteresis loop of a field-cooled sample is displaced along the H axis by ΔH. The above properties can be accounted for by the fact that the films are in a two-phase magnetic (ferromagnetic-antiferromagnetic) state induced by strong s-d exchange. The maximum value of Δ H was used to calculate the energy of exchange coupling between the ferromagnetic and antiferromagnetic parts of a sample.     

Photoluminescence of Ca(Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>S<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript> compounds

Photoluminescence (PL) observed in solid solutions of Ca(Al _x Ga_1–x )₂S₄:Eu²⁺ (x = 0.1–0.3) is studied. It is shown that the increase in emission intensity by 18% is caused by changes in the x values and electronic 5d → 4 f transitions in Eu²⁺ ions. A change in the position of the emission spectrum or its partial shift toward shorter wavelengths is due to an increase in the aluminum concentration and a decrease in the crystal field energy. The energy of the zero phonon line E ₀, redshift D, and the Stokes shift ΔS are determined. A decrease in the photoluminescence intensity maximum and an increase in the half-width of the spectrum are found in the temperature range of 10–300 K. The efficiency of emission at temperatures of 20 and 300 K is almost independent of the excitation power density of up to ~10⁴ W/cm². The luminescence lifetime of Eu²⁺ ions was 383, 357, 346, and 333 ns for x = 0, 0.1, 0.2, and 0.3, respectively.     

Optical activity of γ<Subscript>1</Subscript>-(Ga<Subscript>x</Subscript>In<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>Se<Subscript>3</Subscript> crystals

The optical activity of uniaxial γ₁-(Ga_xIn_1?x )₂Se₃ crystals (x=0.1, 0.2, 0.3, 0.4) is studied at T=295 and 77 K in the spectral range 0.5–0.8 πm. It is found that the cationic substitution In → Ga leads to a nonlinear increase in the specific rotation of the plane of polarization ρ and the component g ₃₃ of the gyration tensor. It is shown that the gyrotropy of the crystals studied is determined by high-energy transitions whose energy exceeds the energy of the edge transitions and that the gyrotropy observed has a molecular origin.     

Magnetic properties of single crystals of a new cobaltite TbBaCo<Subscript>4</Subscript>O<Subscript>7+<Emphasis Type="Italic">x</Emphasis></Subscript>

The temperature and field dependences of the magnetization of a single crystal of a new class of layered cobaltites, TbBaCo₄O_7+x , with a structure containing a Kagomé lattice and a triangular lattice were measured. The measurements were performed on a SQUID magnetometer at temperatures in the range 2–300 K and in magnetic fields of up to 55 kOe for two field orientations. The anisotropy of the magnetization was studied, and the presence of antiferromagnetic ordering in fields H < H _c and a weak magnetic-field-induced (H > H _c ) ferromagnetic component in the low-temperature range was demonstrated. The magnetic characteristics of the initial TbBaCo₄O_7+x single crystal and the single crystal annealed in an O₂ atmosphere were compared.     

Hall effect in the Ce(Al<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript> heavy-fermion system

The influence of substitution on the binding energy of many-body states and the formation of the magnetically ordered state in a heavy-fermion compound (CeAl₂) have been studied by measuring the transport characteristics (Hall effect, resistivity) in intermetallic compounds of the Ce(Al_1?x M _x )₂ system (M = Ni, Co; x ≤ 0.08). It is established that the Hall coefficient R _H in Ce(Al_1?x Co _x )₂ intermetallides with x = 0.05 and 0.08 grows by more than an order of magnitude as the temperature decreases from 1.8 to 300 K. The experimental data are used to estimate the effective mass of charge carriers, the relaxation time, and the localization radius of many-body states.     

Determination of the region of existence of ferromagnetic nanostructures in the paraphase of La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ba<Subscript>x</Subscript>MnO<Subscript>3</Subscript> by the EPR method

In the paraphase of a number of La_1?x Ba_xMnO₃ single crystals with 0.1 ≤ x ≤ 0.2 below 340 K, signals of the ferromagnetic resonance are observed, which indicates the presence of magnetically ordered nanoscopic objects (ferrons). The region of the existence of ferrons on the Ba density-temperature phase diagram has an approximate triangular shape, which is characteristic of the Griffiths phase. Investigations of the angular and frequency dependences of the position of the ferromagnetic resonance line indicate that the nanostructures have a spherical shape. The parameters of their magnetic anisotropy are found to be H _a1 = 2500 Oe and H _a2 = ?700 Oe.