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.

A sucessão ecológica em ambientes florestais em restauração: estrutura e dinâmica da regeneração natural

Ecological restoration aims to restore the self-sustainability potential of degraded environments. The successional trajectory of areas in restoration may differ from the reference ecosystem on a number of factors, especially the disturbance history of the area and management techniques applied in order to reverse the degradation scenario. In this sense, the objective of this study was to characterize the dynamics of natural regeneration and the structure of the regenerating community in an area of ecological restoration for 25 years on the right bank of the Rio Grande in the Power Station in Camargos that belongs to the Companhia Energetica de Minas Gerais - CEMIG, Nazareno, MG, in order to identify the current state of environmental regeneration. In November 2014, there was the first community inventory of seedlings existing in regeneration subplots (2 x 2 m) within the inclusion criteria (height ≥ 10 cm and DBH <5 cm), divided into 44 subplots (11 plots) in two areas, one area in restoration (REF) and a fragment of native vegetation (FRAG). In October 2015, the second sampling was carried out, in which individuals were resampled and recruits and dead individuals quantified. The parameters abundance, floristic similarity, density, dominance, importance value, equability, richness and diversity were analyzed in both samples. The dynamics was evaluated for the number of individuals and basal area in the period of 2014-2015 and individuals distributed according to height. The history of usage area provoked different behavior between the study environments; the patterns of the FRAG and REF communities along the years allowed the distinction between environments and demonstrated great environmental diversity, with differences in the abundance of species, floristic similarity, richness, diversity, vertical structure and dynamics parameters. In the REF area, there was a considerable increase in the density of individuals along the years and the establishment of different species. In this sense, the evaluation of natural regeneration in REF has shown that resilience is gradually being resumed, a necessary condition to support the potential for environmental self-sustainability. However, given the disturbance history, it can be concluded that the environment moves to an alternative state, which is possibly different from that prior to degradation.