Sorption of copper(II) ions from aqueous solution by activated carbon BAU-A and coal sorbent MIU-S. The relationship between the structure of sorbents and their sorption properties.

The sorption of copper(II) ions in a wide range of pH by two Russian carbon sorbents BAU-A and MIU-S was studied. Sorbents varied in structure, surface area, pH of the point of zero charge (pHZPC), and graphitization degree. The sorption studies were conducted in batch mode. The removal of copper(II) ions from a solution at pH 4, 5, 6, and 6.7 is described by the classical adsorption isotherms of Freundlich, Langmuir, and Dubinin-Radushkevich. With an increase in pH from 4 to 6.7, the sorption capacity of sorbents increases, from 0.910 to 7.163 mg/g for BAU-A, and from 0.265 to 3.307 mg/g for MIU-S. The relationship between the degree of crystallinity and the sorption properties of sorbents has been established.

Dual nature of high-temperature electronic transport in layered perovskite-like cobaltites: exhaustive consideration of experimental features observed.

Complex oxides with the general formula Pr1-xYxBaCo2-yNiyO6-δ (x = 0, 0.1, y = 0, 0.2) were successfully synthesized via combustion of organo-metallic precursors. The high-temperature dc conductivity of the obtained sintered materials was studied in a wide range of oxygen partial pressures and temperatures by means of the 4-probe method. The resulting dependencies were juxtaposed with the previously published data on oxygen non-stoichiometry for the oxides considered. The comprehensive analysis of these datasets in attempts to explain the observed trends has shown the large inadequacy of currently existing conduction models. Consequently, a new model approach was developed to account for the numerous experimental and theoretical peculiarities being characteristic for the cobaltites with a layered double perovskite structure. One of the key propositions made postulates mixed nature of the band structure for materials studied with spin states of Co ions acting as a spatial descriptor of a particular type of conductivity: semiconducting or a metallic one. The abovementioned hypothesis was validated by magnetic, thermodynamic and structural arguments obtained both theoretically and experimentally. The models suggested were shown to be adequate in describing large arrays of data collected. Additionally, the reasons behind doping and temperature/pressure influences on the respective conductivity changes in Pr1-xYxBaCo2-yNiyO6-δ were uncovered. Transport and thermodynamic parameters determined were used to evaluate transference numbers and mobilities of different charge carriers which revealed the dominating role of metallic conductivity under oxidative conditions and the superiority of semiconducting charge transport in reducing environments. The obtained conclusions were further supported by utilizing the derived model equations for successful description of conductivity/non-stoichiometry data for other layered cobaltites. Also, interesting correlations between cation composition, thermodynamic and transport properties were found. Finally, general review of the formulated approach was made and further research directions were proposed.

The formation and migration of non-equivalent oxygen vacancies in PrBaCo2-xMxO6-δ, where M = Fe, Co, Ni and Cu.

The ab initio calculated defect formation energies are used for assessment of high-temperature thermodynamic functions that govern the appearance of oxygen vacancies in PrBaCo2-xMxO6-δ, where M = Fe, Co, Ni and Cu. The free energy of oxygen vacancy formation is shown to depend on the dopant and total oxygen content in the cobaltite. The experimentally observed trend for the oxygen vacancy concentration to increase with the atomic number of 3d dopants from Fe to Cu is explained as a result of the decrease of bond strength. The preferable location of oxygen vacancies near impurity atoms is accompanied by an anisotropic redistribution of electronic charge density. The most pronounced development of this effect in the case of iron doping leads to a low probability of tetrahedrally coordinated iron to exist in the layered cobaltites. It is shown that the calculated enthalpies of defect formation satisfactorily explain the experimentally observed changes of oxygen non-stoichiometry in the doped cobaltite. The energy barriers for oxygen jumps are found to vary only weakly at the doping thus suggesting rather insignificant dependence of the oxygen ion conductivity on 3d dopant nature. The earlier findings and results in the present work are indicative of promising properties combination in PrBaCo2-xNixO6-δ for the application as an electrode material in IT-SOFCs.