RESUMO
CO2 capture and conversion are a key research field for the transition towards an economy only based on renewable energy sources. In this regard, hydride materials are a potential option for CO2 methanation since they can provide hydrogen and act as a catalytic species. In this work, Mg2NiH4 complex hydride is synthesized by in situ monitoring of mechanical milling under a hydrogen atmosphere from a 2MgH2:Ni stoichiometric mixture. Temperature and pressure evolution is monitored, and the material is characterized, during milling in situ, thus providing a good insight into the synthesis process. The cubic polymorph of Mg2NiH4 (S.G. Fm3[combining macron]m) starts to be formed in the early beginning of the mechanical treatment due to the mechanical stress induced by the milling process. Then, after 25 hours of milling, Mg2NiH4 with a monoclinic (S.G. C12/c1) structure appears. The formation of the monoclinic polymorph is most likely related to the stress release that follows the continuous refinement of the material's microstructure. At the end of the milling process, after 60 hours, the as-milled material is composed of 90.8 wt% cubic Mg2NiH4, 5.7 wt% monoclinic Mg2NiH4, and 3.5 wt% remnant Ni. The as-milled Mg2NiH4 shows high reactivity for CO2 conversion into CH4. Under static conditions at 400 °C for 5 hours, the interactions between as-milled Mg2NiH4 and CO2 result in total CO2 consumption and in the formation of the catalytic system Ni-MgNi2-Mg2Ni/MgO. Experimental evidence and thermodynamic equilibrium calculations suggest that the global methanation mechanism takes place through the adsorption of C and the direct solid gasification towards CH4 formation.
RESUMO
Nanosized lithiated titanium oxide (LixTiO2) noticeably improves the kinetic behaviour of 2LiBH4 + MgH2. The presence of LixTiO2 reduces the time required for the first dehydrogenation by suppressing the intermediate reaction to Li2B12H12, leading to direct MgB2 formation.
RESUMO
The Ca(BH4)2-Mg2NiH4 system presented here is, to the best of our knowledge, the first described Ca(BH4)2-based hydride composite that reversibly transfers boron from the Ca-based compound(s) to the reaction partner. The ternary boride MgNi2.5B2 is formed upon dehydrogenation and the formation of Ca(BH4)2 upon rehydrogenation is confirmed.
RESUMO
New insights into the reaction pathways of different potassium/magnesium amide-hydride based systems are discussed. In situ SR-PXD experiments were for the first time performed in order to reveal the evolution of the phases connected with the hydrogen releasing processes. Evidence of a new K-N-H intermediate is shown and discussed with particular focus on structural modification. Based on these results, a new reaction mechanism of amide-hydride anionic exchange is proposed.
RESUMO
Reactive hydride composites (RHCs) are very promising hydrogen storage materials for future applications due to their reduced reaction enthalpies and high gravimetric capacities. At present, the materials' functionality is limited by the reaction kinetics. A significant positive influence can be observed with addition of transition-metal-based additives. To understand the effect of these additives, the chemical state and changes during the reaction as well as the microstructural distribution were investigated using x-ray absorption near-edge structure (XANES) spectroscopy and anomalous small-angle x-ray scattering (ASAXS). In this work, zirconium- and vanadium-based additives were added to 2LiBH4-MgH2 composites and 2LiH-MgB2 composites and measured in the vicinity of the corresponding absorption edge. The measurements reveal the formation of finely distributed zirconium diboride and vanadium-based nanoparticles. The potential mechanisms for the observed influence on the reaction kinetics are discussed.
Assuntos
Hidrogênio/química , Hidrogênio/isolamento & purificação , Modelos Químicos , Nanoestruturas/química , Nanotecnologia/métodos , Vanádio/química , Zircônio/química , Simulação por Computador , Fontes de Energia Elétrica , Nanoestruturas/ultraestrutura , Tamanho da PartículaRESUMO
NaAlH(4) is the archetypical complex hydride for hydrogen storage. The extraordinary effect of dopants on the sorption kinetics triggered the investigation of this empirical finding. In this paper, a short review of the state of the art is given. To gain further understanding of the mechanisms involved we label the interacting species during the sorption process. This was experimentally realized by hydrogen-deuterium exchange measurements during the decomposition of NaAlH(4) followed by thermogravimetry, Raman spectroscopy and mass spectrometry. By these experiments we are able to obtain specific information on the diffusing species and formation of intermediates. The activation energy of tracer diffusion in NaAlH(4) is found to be 0.28 eV. The results are evidence for a vacancy-mediated desorption process of NaAlH(4).
Assuntos
Compostos de Alumínio/química , Medição da Troca de Deutério , Deutério/química , Hidrogênio/química , Compostos de Sódio/química , Catálise , Simulação por Computador , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz , Análise Espectral Raman , TermogravimetriaRESUMO
NASA: Advances in the use of automated cockpits are examined. Crashes at Nagoya and Toulouse in 1994 and incidents at Manchester, England, and Paris Orly are used as examples of cockpit automation versus manual operation of aircraft. Human factors researchers conclude that flight management systems (FMS) should have fewer modes and less authority. Reducing complexity and authority override systems of FMS can provide pilots with greater flexibility during crises. Aircraft discussed include Boeing 737-300 and 757-200, Airbus A300-600 and A310, McDonnell Douglas MD-11, and Tarom A310-300.^ieng