The phase formation process of Bi₂Cr_1/6Mn_1/6Fe_1/6Co_1/6Ni_1/6Cu_1/6Nb₂O_9+Δ containing 3d-ions of transition elements in equimolar quantities was studied in a wide temperature range (400–1050 °C). The complex oxide crystallizes in the structural type of pyrochlore (sp. gr. Fd-3m:2, a = 10.4937(2) Å). The investigation of the multi-element pyrochlore phase formation process showed that the synthesis goes through a series of successive stages, during which the transition from Bi-rich to Bi-depleted compounds takes place. The predecessor of the pyrochlore phase is bismuth orthorhombic modification orthoniobate (α-BiNbO₄) with an equimolar ratio of Bi(III)/Nb(V) ions. The pyrochlore phase is formed as a result of bismuth orthoniobate doping with transition element ions. The complex oxides Bi₁₄CrO₂₄, Bi₂₅FeO₄₀, BiNbO₄, and Bi₅Nb₃O₁₅ appeared as intermediate phases during the synthesis. The interaction between the initial oxide precursors is fixed at temperatures above 500 °C. The phase transition of α-Bi₂O₃ into β-Bi₂O₃ near 500 °C is observed. Varying the heat treatment duration at each synthesis step did not qualitatively change the phase composition of the sample but had an effect on the quantitative phase ratio. Phase-pure pyrochlore of the given composition by solid-phase synthesis method can be obtained at a temperature no lower than 1050 °C. Ceramics are characterized by low-porous dense microstructure with blurred outlines of grain boundaries.

A comparative study of the electronic structure of the salen ligand in the H₂(Salen) molecule and the [Ni(Salen)] complex was performed using the experimental methods of XPS, UV PES, and NEXAFS spectroscopy along with DFT calculations. Significant chemical shifts of +1.0 eV (carbon), +1.9 eV (nitrogen), and −0.4 eV (oxygen) were observed in the 1s PE spectra of the salen ligand atoms when passing from a molecule to a complex, unambiguously indicating a substantial redistribution of the valence electron density between these atoms. It is proposed that the electron density transfer to the O atoms in [Ni(Salen)] occurred not only from the Ni atom, but also from the N and C atoms. This process seemed to be realized through the delocalized conjugated π-system of the phenol C 2p electronic states of the ligand molecule. The DFT calculations (total and partial DOS) for the valence band H₂(Salen) and [Ni(Salen)] described well the spectral shape of the UV PE spectra of both compounds and confirmed their experimental identification. An analysis of the N and O 1s NEXAFS spectra clearly indicated that the atomic structure of the ethylenediamine and phenol fragments was retained upon passing from the free salen ligand to the nickel complex.

The effect of Fe and Mg-codoping on the crystal structure, optical and dielectric properties of bismuth tantalate-based pyrochlores has been studied. Samples of Bi₂Mg_xFe_1−xTa₂O_9.5−Δ (x ≤ 0.7) are characterized by a porous dendrite-like microstructure. Fe,Mg-codoped bismuth tantalate pyrochlores are thermally stable up to a temperature of 1140 °C (x = 1). The Bi₂Mg_0.5Fe_0.5Ta₂O_9.5−Δ thermal expansion coefficient increases uniformly and weakly from 3.6 to 9.3 × 10⁻⁶ °C⁻¹ (30–1050 °C). The unit cell parameter of solid solutions increases uniformly from 10.5009(1) Å (x = 0.3) up to 10.5225(7) Å (x = 0.7). The structural parameters of disordered pyrochlore are determined by the Rietveld method (sp. gr. Fd$\overline{3}$m:2 (227), Z = 8). According to near edge X-ray absorption fine structure and X-ray photoelectron spectroscopy data, ions in solid solutions are in the charge states Bi (+3), Mg (+2), Fe (+3), Ta (+5-δ). The Mössbauer spectrum is represented by a symmetric doublet with parameters IS = 0.365 ± 0.0020 mm/s, QS = 0.604 ± 0.034 mm/s, related to Fe³⁺ ions in regular axial octahedral positions. The samples exhibit the properties of dielectrics. The permittivity and the tangent of dielectric losses at 20 °C increases with the growth of iron content in the samples in the range of 28.5–30.5 and 0.001 (1 MHz). The width of the band gap of the obtained materials for direct allowed electronic transitions is in the range of 2.16(5)–2.41(5) eV. The studied samples satisfy the condition of efficient conversion of solar energy into an electrical one and are promising as catalysts and light-absorbing elements for solar panels.

The effect of Zn-doping on the phase composition and optical properties of the Bi₂Zn_xFe_1-xTa₂O_9.5-Δ (x = 0.3, 0.5, 0.7) was studied. XRD data showed that the samples crystallize in the structural type of pyrochlore (sp. gr.Fd-3m). For all the samples, an admixture of bismuth orthotantalate β-BiTaO₄ triclinic modification up to 22.5 wt.% is observed. The content of β-BiTaO₄ increases with zinc doping. The unit cell parameter of the pyrochlore phase rises from 10.4878 (x = 0.3) to 10.5154 Å (x = 0.7). The samples are characterized by a porous microstructure with indistinct grain boundaries. Zinc oxide has a sintering effect on ceramics. The charge state of the ions in Bi₂Zn_xFe_1-xTa₂O_9.5-Δ was investigated by X-ray spectroscopy. NEXAFS and XPS data show that zinc doping does not change the oxidation degree of iron and bismuth ions in pyrochlore. The ions are in the charge states Bi(+3), Fe(+3), Zn(+2). In the Ta4fspectrum, an energy shift of the absorption band towards lower energies by ΔE = 0.5 eV is observed, which is typical for tantalum ions with an effective charge of (+5-δ). With the increase of x(Zn), the Bi 4f_7/2 and Bi 4f_5/2 bands are observed to shift to lower energies due to the distribution of some Zn(II) ions in the bismuth position.

The results of studies of marine sponge carbonization processes during thermal treatment in an argon atmosphere in the temperature range from room temperature to 1200 °C are presented. The spatial structure, atomic composition of native and carbonized sponges, and their changes during pyrolysis were characterized using a set of methods that are informative at the macro- (thermogravimetric analysis, derivative thermogravimetric analysis, differential scanning calorimetry), micro- (Raman spectroscopy, scanning electron microscopy, energy dispersive spectroscopy), and nanoscales (X-ray absorption and photoelectron spectroscopy using synchrotron radiation and a sample charge compensation system). Preservation of the 3D architecture at the macro- and microlevels and graphitization of the interfibril medium with the formation of turbostratic graphite at the nanolevel were demonstrated. It was shown that the atomic contents of nitrogen, carbon, and oxygen in the spongin were ~2–3 at.%, ~5 at.%, and ~4 at.%, respectively. The matter concentrated in the space between the spongin fibrils included ~70 at.% carbon and ~11 at.% oxygen, with a large proportion of carbon (~63 at.%) involved in the formation of aromatic and C–C bonds and the remainder in carbon monoxide compounds. After the decomposition of spongin at 400 °C, this substance transformed into turbostratic graphite, preserving the 3D architecture of the original marine sponge as the temperature rose.

The possibility of high-temperature solid-phase synthesis of Ni-doped bismuth tantalate pyrochlore, not only from the oxide compounds BiTaO₄ and NiO but also using nickel chloride NiCl₂ as a precursor, was shown for the first time. The concentration range of the formation of nickel pyrochlore Bi₂Ni_xTa₂O_9−δ (0.85 ≤ x ≤ 1.0) at an equal molar ratio of bismuth(III)/tantalum(V) ions was determined. This indicates that the pyrochlore structure may be stable at 20–33% vacant bismuth sublattice. The influence of non-stoichiometric composition relative to bismuth and tantalum, by the example of Bi_2±xNiTa₂O_9−δ and Bi₂NiTa_2−xO_9−δ (x ≤ 0.5) compositions, on the phase composition of ceramics was studied. X-ray powder diffraction phase analysis of Bi₂Ni_1+yTa_1.75−yO_9−δ samples made it possible to determine the solubility limit of nickel ions in the tantalum sublattice. It was shown that the molar ratio of metal atoms (Ta, Ni) in the B₂O₆ (B-Ni(II), Ta(V)) octahedral sublattice of mixed pyrochlores is also limited.