Ativação da ligação c-h no metano por espécies MOm n+ (M = Nb, Fe; m = 0, 1; n = 0, 1, 2): estrutura eletrônica, mecanismo de reação e reatividade

The need for renewal and a more efficient use of energy resources has provided an increased interest in studies of methane activation processes in the gas phase by transition metal oxides. In this respect, the present work is an effort to assess , by means of a computational standpoint, the reactivity of NbOm n+ and FeOm n+ (m = 1, 2, n = 0, 1, 2) oxides in the activation process of the methane C-H bond, which corresponds to the first rate limiting step in the process of converting methane to methanol. These oxides are chosen, primarily, because the iron oxides are the most experimentally studied, and iron ions are more abundant in biological mediums. The main motive for choosing niobium oxides is the abundance of natural reserves of this mineral in Brazil (98%), especially in Minas Gerais. Initially, a thorough investigation was conducted, using different theoretical methods, to analyze the structural and electronic properties of the investigated oxides. Based on these results, the most reliable methodology was selected to investigate the activation process of the methane C-H bond by the series of iron and niobium oxides, considering all possible reaction mechanisms known to activate the C-H bond of alkanes. It is worth noting that, up to this moment and to our knowledge, there are no papers, in literature , investigating and comparing all the mechanisms considered in this work. I n general, the main results obtained show different catalytic tendencies and behaviors throughout the series of monoxides and dioxides of iron and niobium. An important and common result found in the two studies is that the increase in the load on the metal center and the addition of oxygen atoms to the metal, clearly favor the initial thermodynamics of the reaction, i.e., favor the approach of the metal center to methane, distorting its electron cloud and, thereby, decreasing its inertia. Comparing the two sets of oxides, we conclude that the iron oxides are the most efficient in activating the methane C-H bond. Among the iron oxides investigated, FeO + showed better kinetic and thermodynamic performance in the reaction with methane, while from the niobium oxides and ions NbO 2+ and NbO2 2+, showed better catalytic efficiency in the activation of the methane C-H bond.

Compartimentos de K, Ca e Mg em solos e sua relação com o crescimento inicial, fisiologia e produtividade do eucalipto

Forestry has grown in a continuous and accelerated manner in Brazil, constituting a strategic activity for the generation of employment, income and tributes, favoring social and economic development of Brazilian agribusiness. The objectives of this study were: (1) evaluate the contents of K, Ca and Mg in the reserve compartments, non-interchangeable, interchangeable, available and the speed of its release, its correlations and its effects over productivity (annual average increment – AAI) of eucalyptus plantations, in forest sites cultivated in soils of the state of Rio Grande do Sul; (2) evaluate the initial growth, nutrition and physiological aspects of eucalyptus plants, cultivated with and without the addition of mineral sources of potassium (K), calcium (Ca) and magnesium (MG), in soils obtained from forest sites in the state of Rio Grande do Sul. In the first study, contents of K, Ca and Mg were evaluated in sulfuric digestion extract, boiling nitric acid, ammonium chloride, Mehlich-1 (only K), potassium chloride (Ca and Mg), as well as the release speed of these nutrients in the soil. In the second study, growth variables, nutritional aspects, photosynthetic rate (A) and transpiration rate of the plants (E) grown in distinct soils were evaluated under controlled conditions. The contents of K, Ca and Mg varied between compartments and depths in the studied soil classes, with the highest proportions found in the reserve compartment, indicating the importance of this compartment for the supplement of these nutrients at average and long terms. The great majority of K, Ca and Mg compartments presented significant correlations between each other, showing the dependence between them and the importance of evaluating the contents of these nutrients in the different compartments to adapt the nutritional management of the plants to each soil class, and to obtain continuous productions, minimizing the negative effects to the environment. Plants cultivated in soils that present larger reserves, availability and K, Ca and Mg release kinetics, presented similar height (H), stem diameter (SD) and shoot dry mass (SDM), with or without fertilization with K, Ca and Mg. The plants presented higher leaf content and accumulation of K in all soils fertilized with K, Ca and Mg.