Phosphorous-doped graphene nanoflakes (GNFs) were first synthesized by several methods, including pyrolysis of PPh3 solution in toluene, post-treatment of GNFs with H3PO4 and hydrothermal post-treatment of GNFs or oxidized GNFs with PPh3 solution in DMF. The products were characterized by scanning and transmission electron microscopy, low-temperature nitrogen physisorption and X-ray photoelectron spectroscopy. Correlations between composition and structural features were revealed.

Synthesis of polymorphic modifications of samarium tungstate from a mechanically activated oxide mixture.

Heterosubstitution is widely used to control the surface properties of graphene materials. The knowledge of the mechanism of organic solvent vapour sorption on doped graphene materials is necessary for development of air purification technologies, volatile organic compounds sensors, metal-free catalysis and for many other applications. The effect of N, S and Si doping and oxidative functionalization of few-layer graphene nanoflakes on the adsorption of organic solvent vapours was measured. The nanoflakes were also analyzed by TEM, XPS, Raman spectroscopy and low-temperature nitrogen physisorption. Special attention was paid to the dependence of the isosteric heat of adsorption on the surface coverage for various adsorbate-adsorbent pairs, which carry information about the energy inhomogeneity of the surface, the hierarchy of adsorbate-adsorbate, adsorbate-basal plane and adsorbate-functional groups interactions, and the mechanism of adsorption. This dependence for the hexane sorption can be used to detect hydrophilic groups on the surface, and to compare the degree of curvature of graphene layers in different heterosubstituted graphene materials.

The phase formation of samarium tungstate (Sm2WO6) from a mechanically activated oxide mixture of Sm2O3 : WO3 = 1 : 1 was studied using thermal analysis methods. The microstructure of the powder samples and high-temperature ceramics was examined by SEM. The influence of activation in mills with different specific power intensities was considered: a high-energy mill designed by Aronov and a SPEX 8000M mill. The conditions for obtaining polycrystalline samples of new modifications, beta-Sm2WO6, alpha-Sm2WO6 and delta-Sm2WO6, whose existence is reported here for the first time, have been determined. The structures of the new polymorphs were characterized by XRD with Rietveld refinement and Raman spectroscopy.

In the present work, extensive studies of ionic conductors with pyrochlore and fluorite structures in the Gd2O3-HfO2 system are carried out. Gd2Hf2O7 and Gd2.1Hf1.9O6.95, Gd2.16Hf1.84O6.92, and Gd2HfO5 solid solutions known as "stuffed" pyrochlores were synthesized by mechanical activation of oxides followed by high temperature annealing at 1500-1600 degrees C. The main investigation methods were X-ray diffraction with Rietveld refinement, SEM microscopy and impedance spectroscopy in dry and wet air and N2. Proton conductivity was first found in Gd2HfO5 (1 x 10-6 at 600 degrees C), and solid solutions based on it, doped with lanthanum and calcium with pure fluorite structure. Proton conduction of the best proton-conducting ceramics Gd1.9La0.1HfO5 (3 x 10-6 at 600 degrees C) was confirmed by measurements in O2/D2O, Ar/D2O atmospheres. At all temperatures, the conductivity sigma D2O was lower than that of sigma H2O. Gd1.9Ca0.1HfO4.95 has a higher oxygen ion component of conductivity in dry air than Gd2HfO5, but the proton conductivity is the same. An attempt was made to synthesize the HEO composition (Lu0.2Y0.2Ho0.2Nd0.2La0.2)2HfO5, which turned out to be two-phase, containing similar to 70% fluorite and similar to 30% pyrochlore. The two-phase HEO (Lu0.2Y0.2Ho0.2Nd0.2La0.2)2HfO5 shows a total conductivity of similar to 3 x 10-6 at 600 degrees C and similar to 3 x 10-5 at 750 degrees C, respectively.

Solid solutions of rare earth titanates with high contents of rare earth oxides of up to 50-62% have been synthesized by the co-precipitation method and their structure, microstructure and conductivity in dry and wet air have been studied. Proton conductors have been found for the first time in solid solutions of rare earth titanates with a high content of Ln2O3 (>50%) with a nominal formula composition of (LnxTi1-x)4O8-2x (Ln = Yb, Er, Ho, 0.667 ≤ x ≤ 0.765). Among (LnxTi1-x)4O8-2x (Ln = Yb, Er, Ho, x = 0.684), (HoxTi1-x)4O8-2x (x = 0.684) showed the maximum conductivity in wet air. In this context, four additional compositions (HoxTi1-x)4O8-2x (x = 0.718, 0.734, 0.75, and 0.765) were synthesized in the holmium series. An increase in the holmium content leads to an increase in the proton transfer coefficients; at the same time, a more complex nature of the dependence of the conductivity under dry and wet atmospheres is observed. For the fluorite-like solid solution (HoxTi1-x)4O8-2x (0.701 ≤ x ≤ 0.765), the proton transfer coefficients were found to be ∼0.9 in the range of 200-450 °C. As the temperature continues to rise, the proton conductivity decreases quite sharply and the transfer coefficient becomes as low as 0.3 at 700 °C. The increase in proton conductivity in the Yb-Er-Ho series is associated with an increase in the hydrophilic properties of rare earth cations. In the (HoxTi1-x)4O8-2x (x = 0.667 ≤ x ≤ 0.765) series, the conductivity in wet air was ∼1 × 10-6 S cm-1 at 450 °C for most compositions. The conductivity of ceramics with x = 0.701 and 0.75 is about 2 times higher, which may be due to the optimal size of pyrochlore nanodomains in the fluorite matrix for x = 0.701 and the formation of pure fluorite for x = 0.75, respectively.

We report a study of nanophases in the La2O3–MO3 (M = Mo, W) systems, which are known to contain a variety of good oxygen-ion and proton conductors. Mechanically activated La2O3 + MO3 (M = Mo, W) mixtures and the final ceramics have been characterized by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) with Rietveld refinement. The microstructure of the materials has been examined by scanning electron microscopy (SEM), and their conductivity in dry and wet air has been determined using impedance spectroscopy. In both systems, the formation of hexagonal La15M8.5O48 (phase II, 5H polytype) (M = Mo, W) nanophases is observed for the composition 1:1, with exothermic peaks in the DSC curve in the range ~480–520 °C for La15Mo8.5O48 and ~685–760 °C for La15W8.5O48, respectively. The crystallite size of the nanocrystalline tungstates is ~40 nm, and that of the nanocrystalline molybdates is ~50 nm. At higher temperatures (~630–690 and ~1000 °C), we observe irreversible reconstructive phase transitions of hexagonal La15Mo8.5O48 to tetragonal γ-La2MoO6 and of hexagonal La15W8.5O48 to orthorhombic β-La2WO6. We compare the temperature dependences of conductivity for nanoparticulate and microcrystalline hexagonal phases and high-temperature phases differing in density. Above 600 °C, oxygen ion conduction prevails in the coarse-grained La18W10O57 (phase I, 6H polytype) ceramic. Low-density La15W8.5O48 and La15Mo8.5O48 (phase II, 5H polytype) nanoceramics exhibit predominantly electron conduction with an activation energy of 1.36 and 1.35 eV, respectively, in dry air.

Tm2(Ti2−xTmx)O7−x/2 (x = 0, 0.1, 0.18, 0.28, 0.74) solid electrolytes have been investigated as potential electrolyte materials for solid oxygen fuel cells (SOFCs), operating in the medium temperature range (600–700 °C). The design of new oxygen-conducting materials is of importance for their possible utilization in the solid oxide fuel cells. The oxygen–ion conductivity of the Tm2(Ti2−xTmx)O7−x/2 (x = 0, 0.1, 0.18, 0.28, 0.74) “stuffed” pyrochlores ceramics was investigated by electrochemical impedance spectroscopy (two-probe AC) in dry and wet air. The synthesis of precursors via co-precipitation and the precipitate decomposition temperature have been shown to be of key importance for obtaining dense and highly conductive ceramics. At ~770 °C, the highest total conductivity, ~3.16 × 10−3 S/cm, is offered by Tm2Ti2O7. The conductivity of the fluorite-like solid solution Tm2(Ti2−xTmx)O7−x/2 (x = 0.74) is an order of magnitude lower. However, for the first time a proton contribution of ~5 × 10−5 S/cm at 600 °C has been found in Tm2(Ti2−xTmx)O7−x/2 (x = 0.74) fluorite. Until now, compositions with proton conductivity were not known for the intermediate and heavy rare earth titanates Ln2(Ti2−xLnx)O7−x/2 (Ln = Ho − Lu) systems. The use of X-ray diffraction (structural analysis with Rietveld refinement), optical spectroscopy and dielectric permittivity data allowed us to follow structural disordering in the solid solution series with increasing thulium oxide content. High and low cooling rates have been shown to have different effects on the properties of the ceramics. Slow cooling initiates’ growth of fluorite nanodomains in a pyrochlore matrix. The fabrication of such nanostructured dense composites is a promising direction in the synthesis of highly conductive solid electrolytes for SOFCs. We assume that high-temperature firing of nanophase precursors helps to obtain lightly doped “stuffed” pyrochlores, which also provide the high oxygen–ion conductivity.

The design of new oxygen- and proton-conducting materials is of paramount importance for their possible utilization in solid oxide fuel cells. In the present work, La2(Hf2–xLax)O7–x/2 (x = 0, 0.1) ceramics were prepared using ball milling of oxide mixtures (La2O3 and HfO2) followed by high-temperature annealing at 1600 °C for 10 h in air. La2Hf2O7 ceramics exhibit an ordered pyrochlore-type structure, whereas La2(Hf1.9La0.1)O6.95 has a defect pyrochlore structure type with oxygen vacancies at the 48f positions. The oxygen ion and proton conductivity of La2(Hf1.9La0.1)O6.95 “stuffed” pyrochlore ceramics was investigated by electrochemical impedance spectroscopy (two-probe AC) and four-probe DC measurements in a dry and a wet atmosphere (air and nitrogen). The use of two distinct conductivity measurement techniques ensured, for the first time, the collection of reliable data on the proton conductivity of the La2(Hf1.9La0.1)O6.95 “stuffed” hafnate pyrochlore. La2Hf2O7 was found to be a dielectric in the range 400–900 °C, whereas the La2(Hf1.9La0.1)O6.95 “stuffed” pyrochlore had both oxygen ion and proton conductivities in this temperature range. The proton conductivity level was found to be equal to ~8 × 10−5 S/cm at 700 °C. Clearly, the proton conductivity of the La2(Hf1.9La0.1)O6.95 “stuffed” hafnate pyrochlore is mainly due to the hydration of oxygen vacancies at 48f positions.

Lithium and complex lithium greases were modified by few-layer graphene nanoflakes. Tribological tests demonstrate improvement of the lubricating characteristics, e.g. increase of the welding load and decrease of the wear scar diameter after the modification. XPS method showed occurrence tribochemical reaction between lithium 12-hydroxystearate molecules and graphene nanoflakes surface during exploitation of the grease. It was shown that graphene nanoflakes are corrosion-inactive in lubricating compositions and compatible with modern additive packages.