Stabilization of a complex perovskite superstructure under ambient conditions: Influence of cation composition and ordering, and evaluation as an SOFC cathode

Ba1.6Ca2.3Y1.1Fe5O13 is an Fe3+ oxide adopting a complex perovskite superstructure, which is an ordered intergrowth between the Ca2Fe2O5 and YBa2Fe3O8 structures featuring octahedral, square pyramidal, and tetrahedral B sites and three distinct A site environments. The distribution of A site cations was evaluated by combined neutron and X-ray powder diffraction. Consistent with the Fe3+ charge state, the material is an antiferromagnetic insulator with a Néel temperature of 480-485 °C and has a relatively low d.c. conductivity of 2.06 S cm-1 at 700 °C. The observed area specific resistance in symmetrical cell cathodes with the samarium-doped ceria electrolyte is 0.87 Ω cm2 at 700 °C, consistent with the square pyramidal Fe3+ layer favoring oxide ion formation and mobility in the oxygen reduction reaction. Density functional theory calculations reveal factors favoring the observed cation ordering and its influence on the electronic structure, in particular the frontier occupied and unoccupied electronic states. © 2010 American Chemical Society.

Different methods of manufacturing FE-based oxygen carrier particles for reforming via chemical looping, and their effect on performance

Chemical looping combustion (CLC) is a means of combusting carbonaceous fuels, which inherently separates the greenhouse gas carbon dioxide from the remaining combustion products, and has the potential to be used for the production of high-purity hydrogen. Iron-based oxygen carriers for CLC have been subject to considerable work; however, there are issues regarding the lifespan of iron-based oxygen carriers over repeated cycles. In this work, haematite (Fe2O3) was reduced in an N2+CO+CO2 mixture within a fluidised bed at 850°C, and oxidised back to magnetite (Fe3O4) in a H2O+N2 mixture, with the subsequent yield of hydrogen during oxidation being of interest. Subsequent cycles started from Fe3O4 and two transition regimes were studied; Fe3O4↔Fe0.947O and Fe 3O4↔Fe. Particles were produced by mechanical mixing and co-precipitation. In the case of co-precipitated particles, Al was added such that the ratio of Fe:Al by weight was 9:1, and the final pH of the particles during precipitation was investigated for its subsequent effect on reactivity. This paper shows that co-precipitated particles containing additives such as Al may be able to achieve consistently high H2 yields when cycling between Fe3O4 and Fe, and that these yields are a function of the ratio of [CO2] to [CO] during reduction, where thermodynamic arguments suggest that the yield should be independent of this ratio. A striking feature with our materials was that particles made by mechanical mixing performed much better than those made by co-precipitation when cycling between Fe3O4 and Fe0.947O, but much worse than co-precipitated particles when cycling between Fe3O 4 and Fe.

The attrition behaviour of oxygen-carriers under inert and reacting conditions

The attrition of two potential oxygen-carriers for chemical-looping, 100. wt% mechanically-mixed, unsupported iron oxide (400-600 μm diameter) and 25. wt% copper oxide impregnated on alumina (600-900 μm diameter), has been studied. The rates of attrition of batches of these particles whilst they were being fluidised and subjected to successive cycles of reduction and oxidation were determined by measuring the rate of production of fine particles elutriated from the bed, as well as progressive changes in the distribution of particle sizes retained in the bed. The ability of the particles to withstand impacts was also investigated by examining the degree of fragmentation of 1. g of reacted particles of known size on projecting them at a target at various velocities. It was found that the mechanical strength of the iron oxide particles deteriorated significantly after repeated cycles of oxidation and reduction. Thus, the rate of elutriation increased ~35-fold between the 1st and 10th cycle. At an impact velocity of 38. m/s, the amount of fragmentation in the impact test, viz. mass fraction of particles after impact having a size less than that before impact, increased from ~2.3. wt% (fresh particles) to 98. wt% after the 10th cycle. The CuO particles, in comparison, were able to withstand repeated reaction: no signs of increased rates of elutriation or fragmentation were observed over ten cycles. These results highlight the importance of selecting a durable support for oxygen-carriers. © 2011 Elsevier Ltd.

A high performance oxygen storage material for chemical looping processes with CO2 capture

Chemical looping combustion (CLC) is a novel combustion technology that involves cyclic reduction and oxidation of oxygen storage materials to provide oxygen for the combustion of fuels to CO2 and H2O, whilst giving a pure stream of CO2 suitable for sequestration or utilisation. Here, we report a method for preparing of oxygen storage materials from layered double hydroxides (LDHs) precursors and demonstrate their applications in the CLC process. The LDHs precursor enables homogeneous mixing of elements at the molecular level, giving a high degree of dispersion and high-loading of active metal oxide in the support after calcination. Using a Cu-Al LDH precursor as a prototype, we demonstrate that rational design of oxygen storage materials by material chemistry significantly improved the reactivity and stability in the high temperature redox cycles. We discovered that the presence of sodium-containing species were effective in inhibiting the formation of copper aluminates (CuAl2O4 or CuAlO 2) and stabilising the copper phase in an amorphous support over multiple redox cycles. A representative nanostructured Cu-based oxygen storage material derived from the LDH precursor showed stable gaseous O2 release capacity (∼5 wt%), stable oxygen storage capacity (∼12 wt%), and stable reaction rates during reversible phase changes between CuO-Cu 2O-Cu at high temperatures (800-1000 °C). We anticipate that the strategy can be extended to manufacture a variety of metal oxide composites for applications in novel high temperature looping cycles for clean energy production and CO2 capture. © The Royal Society of Chemistry 2013.

Interaction between Fe-based oxygen carriers and n-heptane during chemical looping combustion

Chemical looping combustion (CLC) uses a metal oxide (the oxygen carrier) to provide oxygen for the combustion of a fuel and gives an inherent separation of pure CO2 with minimal energy penalty. In solid-fuel CLC, volatile matter will interact with oxygen carriers. Here, the interaction between iron-based oxygen carriers and a volatile hydrocarbon (n-heptane) was investigated in both a laboratory-scale fluidised bed and a thermogravimetric analyser (TGA). Experiments were undertaken to characterise the thermal decomposition of the n-heptane occurring in the presence and in the absence of the oxygen carrier. In a bed of inert particles, carbon deposition increased with temperature and acetylene appeared as a possible precursor. For a bed of carrier consisting of pure Fe2O3, carbon deposition occurred once the Fe2O3 was fully reduced to Fe. When the Fe2O3 was doped with 10 mol % Al2O3 (Fe90Al), deposition started when the carrier was reduced to a mixture of Fe and FeAl2O4, the latter being very unreactive. Furthermore, when pure Fe2O3 was fully reduced to Fe, agglomeration of the fluidised bed occurred. However, Fe90Al did not give agglomeration even after extended reduction. The results suggest that Fe90Al is promising for the CLC of solid fuels. © 2012 The Combustion Institute. Published by Elsevier Inc. All rights reserved.