Wireless electrochemical modification of catalytic activity on a mixed protonic-electronic conductor

A novel approach to electrochemical modification of catalytic activity using a wireless configuration has been undertaken. This paper presents preliminary results on the modification of a platinum catalyst film supported on a pellet of Sr_0.97Ce_0.9Yb_0.1O_3-δ (SCYb), considered to be a mixed protonic-electronic conductor under reducing conditions. The wireless configuration utilises the mixed ionic and electronic conductivity of the supporting membrane to supply an ionic promoting species to the catalyst surface. Control of the flux of this species is achieved by adjusting the effective hydrogen chemical potential difference across the membrane in a dual-chamber reactor with one chamber acting as the "reaction side" and the other as the "sweep side". The reaction rate can be promoted by up to a factor of 1.6, for temperatures around 500 °C and low reactant concentrations, when hydrogen is introduced on the sweep side of the membrane reactor. The use of helium, moist helium and oxygen in helium as sweep gases did not modify the reaction rate. © 2007 Elsevier B.V. All rights reserved.

Remote control of the activity of a Pt catalyst supported on a mixed ionic electronic conducting membrane

A novel configuration for the in situ control of the catalytic activity of a polycrystalline Pt catalyst supported on a mixed ionic electronic conducting (MIEC) substrate is investigated. The modification of the catalytic activity is achieved by inducing the reverse spillover of oxygen promoting species from the support onto the catalyst surface, thus modifying the chemisorptive bond energy of the gas phase adsorbed reactants. This phenomenon is known as Electrochemical Promotion of Catalysis (EPOC). In this work we investigate the use of a wireless system that takes advantage of the mixed ionic electronic conductivity of the catalyst support (internally short-circuiting the system) in a dual chamber reactor. In this wireless configuration, the reaction takes place in one chamber of the membrane reactor while introduction of the promoting species is achieved by the use of an appropriate sweep gas (and therefore control of the oxygen chemical potential difference across the membrane) on the other chamber. Experimental results have shown that the catalytic rate can be enhanced by using an oxygen sweep, while a hydrogen sweep can reverse the changes. Total rate enhancement ratios of up to 3.5 were measured. © 2008 Elsevier B.V. All rights reserved.

On the Origin of Steep I-V Nonlinearity in Mixed-Ionic-Electronic-Conduction-Based Access Devices

Numerical modeling is used to explain the origin of the large ON/OFF ratios, ultralow leakage, and high ON-current densities exhibited by back-end-of-the-line-friendly access devices based on copper-containing mixed-ionic-electronic-conduction (MIEC) materials. Hall effect measurements confirm that the electronic current is hole dominated; a commercial semiconductor modeling tool is adapted to model MIEC. Motion of large populations of copper ions and vacancies leads to exponential increases in hole current, with a turn-ON voltage that depends on material bandgap. Device simulations match experimental observations as a function of temperature, electrode aspect ratio, thickness, and device diameter.

Electrochemical performance of mixed ionic-electronic conducting oxides as anodes for solid oxide fuel cell

Mixed ionic-electronic conducting (MIEC) oxides, SrFeCo0.5Ox, SrCo0.8Fe0.2O3-delta and La0.6Sr0.4Fe0.8Co0.2O3-delta have been synthesized and prepared on yttria-stabilized zirconia as anodes for solid oxide fuel cells. Power output measurements show that the anodes composed of such kinds of oxides exhibit modest electrochemical activities to both H-2 and CH4 fuels, giving maximum power densities of around 0.1 W/cm(2) at 950 degrees C. Polarization and AC impedance measurements found that large activation overpotentials and ohmic resistance drops were the main causes for the relative inferior performance to the Ni-YSZ anode. While interlayered with an Ni-YSZ anode, a significant improvement in the electrochemical performance was observed. in particular, for the SrFeCo0.5Ox oxide interlayered Ni-YSZ anode, the maximum power output reaches 0.25 W/cm2 on CH,, exceeding those of both SrFeCo0.5Ox and the Ni-YSZ, as anodes alone. A synergetic effect of SrFeCo0.5Ox and the Ni-YSZ has been observed. Future work is needed to examine the long-term stability of MIEC oxide electrodes under a very reducing environment. (C) 1999 Elsevier Science B.V. All rights reserved.

Electrochemical promotion of catalysis controlled by chemical potential difference across a mixed ionic-electronic conducting ceramic membrane - An example of wireless NEMCA

A La_0.6Sr_0.4Co_0.2F_0.8O₃ mixed ionic electronic conducting (MIEC) membrane was used in a dual chamber reactor for the promotion of the catalytic activity of a platinum catalyst for ethylene oxidation. By controlling the oxygen chemical potential difference across the membrane, a driving force for oxygen ions to migrate across the membrane and backspillover onto the catalyst surface is established. The reaction is then promoted by the formation of a double layer of oxide anions on the catalyst surface. Thelectronic conductivity of the membrane material eliminates the need for an external circuit to pump the promoting oxide ion species through the membrane and onto the catalyst surface. This renders this "wireless" system simpler and more amenable for large-scale practical application. Preliminary experiments show that the reaction rate of ethylene oxidation can indeed be promoted by almost one order of magnitude upon exposure to an oxygen atmosphere on the sweep side of the membrane reactor, and thus inducing an oxygen chemical potential difference across the membrane, as compared to the rate under an inert sweep gas. Moreover, the rate does not return to its initial unpromoted value upon cessation of the oxygen flow on the sweep side, but remains permanently promoted. A number of comparisons are drawn between the classical electrochemical promotion that utilises an external circuit and the "wireless" system that utilises chemical potential differences. In addition a 'surface oxygen capture' model is proposed to explain the permanent promotion of the catalyst activity. © 2007 Springer Science+Business Media, LLC.

In situ modification of a Pt catalyst supported on a mixed ionic-electronic conducting membrane

The electrochemical promotion of a platinum catalyst for ethylene oxidation on a dual chamber membrane reactor was studied. The catalyst was supported on a La_0.6Sr_0.4Co_0.2Fe_0.803 membrane. Due the supporting membrane's electronic conductivity it is possible to promote the reaction by controlling the oxygen chemical potential difference across the membrane. Upon establishment of an oxygen potential difference across the membrane, oxygen species can migrate and spillover onto the catalyst surface, modifying the catalytic activity. Initial experiments showed an overall promotion of approximately one order of magnitude of the reaction rate of ethylene, under an oxygen atmosphere on the sweep side of the membrane reactor, as compared with the rate under an inert sweep gas. The reaction rate can keep its promoted state even after the flow of oxygen on the sweep side was interrupted. This behavior caused further promotion with every experiment cycle. The causes of permanent promotion and on demonstrating controllable promotion of the catalytic activity are presented. This is an abstract of a paper presented at the AIChE Annual Meeting (San Francisco, CA 11/12-17/2006).

Mixed ionic-electronic YSZ/Ni composite for SOFC anodes with high electrical conductivity

The preparation of the ZrO(2):8 mol % Y(2)O(3)/NiO (YSZ/NiO) composites by a modified liquid mixture technique is reported. Nanometric NiO particles dispersed over the yttria-stabilized zirconia (YSZ) were prepared, resulting in dense sintered specimens with no solid solution formation between the oxides. Such a feature allowed for the electrical characterization of the composites in a wide range of relative volume fraction, temperature, and oxygen partial pressure. The main results indicate that the composites have high electrical conductivity, and the transport properties in these mixed ionic-electronic (MIEC) composites are strongly dependent on the relative volume fraction of the phases, microstructure, and temperature. These parameters should hence be taken into consideration for the optimized design of MIEC composites for electrochemical applications. In this context, the composite was reduced under H(2) for the preparation of high-conductivity YSZ/Ni cermets for use as solid oxide fuel cell anode material with relatively low metal content. (c) 2005 the Electrochemical Society. [DOI:10.1149/1.2149312] All rights reserved.

Hydrogen-permeation characteristics of a SrCeO3-based ceramic separation membrane:Thermal, ageing and surface-modification effects

Dense ceramics with mixed protonic-electronic conductivity are of considerable interest for the separation and purification of hydrogen and as electrochemical reactors. In this work, the hydrogen permeability of a Sr_0.97Ce_0.9Yb_0.1O_{3 - δ} (SCYb) membrane with a porous Pt catalytic layer on the hydrogen feed-exposed side has been studied over the temperature range 500-804 °C employing Ar as the permeate sweep gas. A SiO₂-B₂O₃-BaO-MgO-ZnO-based glass-ceramic sealant was successfully employed to seal the membrane to the dual-chamber reactor. After 14 h of exposure to 10% H₂:90% N₂ at 804 °C, the H₂ flux reached a maximum of 33 nmol cm^{- 2} s^{- 1}, over an order of magnitude higher than that obtained on membranes of similar thickness without surface modification. The permeation rate then decreased slowly and moderately on annealing at 804 °C over a further 130 h. Thereafter, the flux was both reproducible and stable on thermal cycling in the range 600-804 °C. The results indicate an important role of superficial activation processes in the flux rate and suggest that hydrogen fluxes can be further optimised in cerate-based perovskites. © 2009 Elsevier B.V. All rights reserved.

Extension of electrochemically active sites in SOFCs and SOECs

Solid oxide fuel (SOFCs) and electrolyzer (SOECs) cells have been promoted as promising technologies for the stabilization of fuel supply and usage in future green energy systems. SOFCs are devices that produce electricity by the oxidation of hydrogen or hydrocarbon fuels with high efficiency. Conversely, SOECs can offer the reverse reaction, where synthetic fuels can be generated by the input of renewable electricity. Due to this similar but inverse nature of SOFCs and SOECs, these devices have traditionally been constructed from comparable materials. Nonetheless, several limitations have hindered the entry of SOFCs and SOECs into the marketplace. One of the most debilitating is associated with chemical interreactions between cell components that can lead to poor longevities at high working temperatures and/or depleted electrochemcial performance. Normally such interreactions are countered by the introduction of thin, purely ionic conducting, buffer layers between the electrode and electrolyte interface. The objective of this thesis is to assess if possible improvements in electrode kinetics can also be obtained by modifying the transport properties of these buffer layers by the introduction of multivalent cations. The introduction of minor electronic conductivity in the surface of the electrolyte material has previously been shown to radically enhance the electrochemically active area for oxygen exchange, reducing polarization resistance losses. Hence, the current thesis aims to extend this knowledge to tailor a bi-functional buffer layer that can prevent chemical interreaction while also enhancing electrode kinetics.The thesis selects a typical scenario of an yttria stabilized zirconia electrolyte combined with a lanthanide containing oxygen electrode. Gadolinium, terbium and praseodymium doped cerium oxide materials have been investigated as potential buffer layers. The mixed ionic electronic conducting (MIEC) properties of the doped-cerium materials have been analyzed and collated. A detailed analysis is further presented of the impact of the buffer layers on the kinetics of the oxygen electrode in SOFC and SOEC devices. Special focus is made to assess for potential links between the transport properties of the buffer layer and subsequent electrode performance. The work also evaluates the electrochemical performance of different K2NiF4 structure cathodes deposited onto a peak performing Pr doped-cerium buffer layer, the influence of buffer layer thickness and the Pr content of the ceria buffer layer. It is shown that dramatic increases in electrode performance can be obtained by the introduction of MIEC buffer layers, where the best performances are shown to be offered by buffer layers of highest ambipolar conductivity. These buffer layers are also shown to continue to offer the bifunctional role to protect from unwanted chemical interactions at the electrode/electrolyte interface.

X-ray absorption spectroscopy study on La0.6Sr0.4CoO3 and La0.6Sr0.4Co1¡yFeyO3 nanotubes and nanorods for IT-SOFC cathodes.

In the last years, extensive research has been devoted to develop novel materials and structures with high electrochemical performance for intermediate-temperatures solid-oxide fuel cells (IT-SOFCs) electrodes. In recent works, we have investigated the structural and electrochemical properties of La0:6Sr0:4CoO3 (LSCO) and La0:6Sr0:4Co1¡yFeyO3 (LSCFO) nanostructured cathodes, finding that they exhibit excellent electrocatalytic properties for the oxygen reduction reaction [1,2]. These materials were prepared by a pore-wetting technique using polycarbonate porous membranes as templates. Two average pore sizes were used: 200 nm and 800 nm. Our scanning electronic microscopy (SEM) study showed that the lower pore size yielded nanorods, while nanotubes were obtained with the bigger pore size. All the samples were calcined at 1000oC in order to produce materials with the desired perovskite-type crystal structure. In this work, we analyze the oxidation states of Co and Fe and the local atomic order of LSCO and LSCFO nanotubes and nanowires for various compositions. For this pur- pose we performed XANES and EXAFS studies on both Co and Fe K edges. These measurements were carried out at the D08B-XAFS2 beamline of the Brazilian Synchrotron Light Laboratory (LNLS). XANES spectroscopy showed that Co and Fe only change slightly their oxidation state upon Fe addition. Surprisingly, XANES results indicated that the content of oxygen vacancies is low, even though it is well-known that these materials are mixed ionic-electronic conductors. EXAFS results were consistent with those expected according to the rhombohedral crystal structure determined in previous X-ray powder dffraction investigations. [1] M.G. Bellino et al, J. Am. Chem. Soc. 129 (2007) 3066 [2] J.G. Sacanell et al., J. Power Sources 195 (2010) 1786

Structural and reduction studies of ZrO2-CeO2:Ni for application in SOFC anodes.

Zirconia-ceria solid-solutions are extensively used as promoters for three-way catalysts, which are applied in the control of NOx, CO and hydrocarbons emission from automotive exhausts. In addition, thesematerials can be used as anodes in solid oxide fuel cells (SOFCs) operated with hydrocarbons. There areonly few works on ZrO2-CeO2 ordered mesoporous materials for catalytic applications and for anodes inSOFCs. The interest in these anodes relies on the fact that ZrO2-CeO2materials are mixed ionic/electronic conductors in reducing atmosphere and, therefore, fuel oxidation is produced on its entire surface, while it only occurs in the [anode/electrolyte/gas] interface (triple-phase boundaries) for electronic conductors. In this work, a synthesis method was developed usingZr and Ce chloride precursors, HCl aqueous solution, Pluronic P123 as the structure directing agent, NH4OH to adjust the pH (3-4) and a Teflon autoclave to perform hydrothermal treatment (80ºC/48 hours). The samples were dried and calcined, until 540ºC in N2and 4 hours in air. The X-ray diffraction data showed that powders with higher CeO2 content are formed by a larger fraction of the cubic CeO2 phase, while for a lower CeO2content the major crystalline structure is the tetragonal ZrO2 phase. The NiO impregnation was made with an ethanol dispersion of Ni(NO3)×6H2O. The resulting powder was calcinated in air until 350ºC for 2 hours. Temperature-programmed reduction (TPR) data were collected in order to evaluate the reduction profiles of ZrO2-x%CeO2:Ni samples in H2/Ar atmosphere. Results showed lower reduction temperatures for all ceria content in samples comparing to a NiO standard.

Mothers' experiences in the elementary school education of their children of mixed heritage /

This study explores the perceptions and experiences of middle-class women, mostly mothers, regarding the elementary school education of their children of mixed heritage. Because it endeavours to provide a forum in which the voices of women are considered a source of valuable information for educators, this study contributes to the fields of feminist and mothering research. Participants assign meanings to their lived experiences (Schon, 1983; van Manen 1997) and contemplate the various ways in which a mixed heritage mayor may not affect a child's schooling. Four main participants were interviewed who are mothers whose children of mixed heritage presently attend public elementary schools in Ontario, Canada. The study had an emergent design, thus allowing the researcher to make decisions as the study progressed. Three additional participants were included in the study to provide a wider perspective on the topic. These 3 additional women were the researcher herself as she explored her self-conceptual baggage (Kirby & McKenna. 1989); the researcher's mother in an attempt to consider the motherline (Lowinsky, 1992); and a volunteer non-mother of mixed ethnicity. The study involved a total of 12 individual interviews of approximately 2 hours in length. The 4 main participants and the researcher were each interviewed twice; the researcher's mother and the volunteer non-mother were each interviewed once. The researcher also attempted a focus group and kept a journal throughout the research process. Much of the analysis centers on women's interpretations of the mixed heritage experience and on their suggestions for elementary school educators. It concludes pondering on the invisibility (Chiong, 1998) of such children within the school system and calling for increased teacher education as a way to bring the mixed heritage experience out of the shadows.

Influence of synthetic method on the properties of La0.5Ba0.5FeO3 SOFC cathode

Power Point presentado en The Energy and Materials Research Conference - EMR2015 celebrado en Madrid (España) entre el 25-27 de febrero de 2015

Sub-nA spatially resolved conductivity profiling of surface and interface defects in ceria films

Spatial variability of conductivity in ceria is explored using scanning probe microscopy (SPM) with galvanostatic control. Ionically blocking electrodes are used to probe the conductivity under opposite polarities to reveal possible differences in the defect structure across a thin film of CeO2. Data suggests the existence of a large spatial inhomogeneity that could give rise to constant phase elements during standard electrochemical characterization, potentially affecting the overall conductivity of films on the macroscale. The approach discussed here can also be utilized for other mixed ionic electronic conductor (MIEC) systems including memristors and electroresistors, as well as physical systems such as ferroelectric tunneling barriers.