Dispersion, solid electrolytes

Santhosh P, Manesh KM, Gopalan A, Lee K-P (2007) Novel amperometric carbon monoxide sensor based on multi-wedl carbon nanotubes grafted with polydiphenylamine-fabrication and performance. Sens Actuators B 125 92-99 Shai K, Wagner J (1982) Enhanced ionic conduction in dispersed solid electrolyte systems (DSES) and/or multiphase systems Agl-Al Oj, Agl-SiO, Agl-Ely ash, and Agl-AgBr. J Sohd State Chem 42 107-119 Shimizu Y, Yamashita N (2000) Solid electrolyte CO sensor using NASICON and perovskite-type oxide electrode. Sens Actuators B 64 102-106... 

The addition of MgO leads to the formation of a naiTow range of solid solutions at high temperamre, which decompose to precipitate inclusions of tetragonal Zr02 dispersed in cubic zirconia. The material, which functions as a solid electrolyte, has the added advantage that the inclusions stop the propagation of any cracks which may arise from rapid temperature change. 

It is interesting to note that the recently announced Fujifilm development of convertible oxide electrodes results in the formation of a microstructure containing fine dispersions of both Li-Sn alloys and Li20. The latter is known to be a lithiumtransporting solid electrolyte. Thus these electrodes can be thought of as having a... 

It will also be shown that the absolute electrode potential is not a property of the electrode but is a property of the electrolyte, aqueous or solid, and of the gaseous composition. It expresses the energy of solvation of an electron at the Fermi level of the electrolyte. As such it is a very important property of the electrolyte or mixed conductor. Since several solid electrolytes or mixed conductors based on ZrC>2, CeC>2 or TiC>2 are used as conventional catalyst supports in commercial dispersed catalysts, it follows that the concept of absolute potential is a very important one not only for further enhancing and quantifying our understanding of electrochemical promotion (NEMCA) but also for understanding the effect of metal-support interaction on commercial supported catalysts. 

Consequently the absolute potential is a material property which can be used to characterize solid electrolyte materials, several of which, as discussed in Chapter 11, are used increasingly in recent years as high surface area catalyst supports. This in turn implies that the Fermi level of dispersed metal catalysts supported on such carriers will be pinned to the Fermi level (or absolute potential) of the carrier (support). As discussed in Chapter 11 this is intimately related to the effect of metal-support interactions, which is of central importance in heterogeneous catalysis. 

Most of the electrochemical promotion studies surveyed in this book have been carried out with active catalyst films deposited on solid electrolytes. These films, typically 1 to 10 pm in thickness, consist of catalyst grains (crystallites) typically 0.1 to 1 pm in diameter. Even a diameter of 0.1 pm corresponds to many (-300) atom diameters, assuming an atomic diameter of 3-10 10 m. This means that the active phase dispersion, Dc, as already discussed in Chapter 11, which expresses the fraction of the active phase atoms which are on the surface, and which for spherical particles can be approximated by ... 

The electrochemical promotion of 1-butene isomerization to 2-butene (cis-and trans-) using Nafion as the solid electrolyte and finely dispersed Pd deposited on carbon as the electrode has been described in section 9.2.2.14,15 Faradaic efficiency, A, values up to 28 were obtained in this remarkable study. The Pd dispersion is near complete on the high surface area C support.14,15... 

This study, in conjunction with that discussed in 12.2.1.2, show that when using aqueous electrolytes or Nafion saturated with H20, the induction of NEMCA on finely dispersed noble metal catalysts is rather straightforward. The role of the electronically conducting porous C support is only to conduct electrons and to support the finely dispersed catalyst. The promoting species can reach the active catalyst via the electrolyte or via the aqueous film without having to migrate on the surface of the support, as is the case when using ceramic solid electrolytes. 

Electrochemical Promotion of Particulate Matter (Soot) Combustion Using a Ceria-Gadolinia Solid Electrolyte and a Dispersed Perovskite Catalyst... 

The structure electrical double layer at the silica-aqueous electrolyte interface was one of the earlier examined of the oxide systems. At the beginning the investigations were performed with application of electrokinetic methods next, with potentiometric titrations. The properties of this system were very important for flotation in mineral processing. Measurements proved that pHpZC and pHiep are equal to 3, but presence of some alkaline or acidic contaminants may change the position of these points on pH scale. Few examples, concerning edl parameters are shown in Table 3. Presented data concern a group of systems of different composition of the liquid phase and solid of a different origin. The latest measurements of this system takes into account the kinetics of the silica dissolution [152], and at zeta measurements, also the porosity of dispersed solid [155]. 

Ionically conducting polymers and their relevance to lithium batteries were mentioned in a previous section. However, there are several developments which contain both ionically conducting materials and other supporting agents which improve both the bulk conductivity of these materials and the properties of the anode (Li)/electrolyte interface in terms of resistivity, passivity, reversibility, and corrosion protection. A typical example is a composite electrolyte system comprised of polyethylene oxide, lithium salt, and A1203 particles dispersed in the polymeric matrices, as demonstrated by Peled et al. [182], By adding alumina particles, a new conduction mechanism is available, which involved surface conductivity of ions on and among the particles. This enhances considerably the overall conductivity of the composite electrolyte system. There are also a number of other reports that demonstrate the potential of these solid electrolyte systems [183],... 

Figure 17. Dependencies of exchange current density jo at various electrodes on the ionic conductivity of various zirconia solid electrolytes (A) SDC (dashed, dash-dotted, and dotted lines) and Ru (0.5 mg/cm )-dispersed SDC anodes in humidified Hi. Reprinted from Ref. 45, Copyright (1997), with permission from The Electrochemical Society, (B) Pt cathodes in Oj, (C) LfCi jsSriu MnO, (LSM, dashed lines) and Pt (0.1 nig/cnr(-dispersed LSM cathodes in Oi. Each jo value was calculated from the polarization resistance (Rp, 2 tm ), since linear relationships were observed between 7 and j for rj < 0.1 V at all the electrodes and 7 ccii between 800 and 1000°C jo = (RT/nF)Rp. Reproduced by Ref. 46, Copyright (1999), by permission from The Electrochemical Society. 

Bhoga. S.S. and Singh. K. (2005) Performance of electr ochemical CO2 gas sensor with NASICON dispersed in a binar y solid electrolyte system. Indian J. Phys.. 79 (7). 725-6. 

It is worth noting that the remarkable effect described for the carbon support porosity on the metal utilization factor and hence on the specific electrocat-alytic activity in methanol electrooxidation was only observed when the catalysts were incorporated in ME As and measured in a single cell. The measurements performed for thin catalytic layers in a conventional electrochemical cell with liquid electrolyte provided similar specific catalytic activities for Pt-Ru/C samples with similar metal dispersions but different BET surface areas of carbon supports [223]. The conclusions drawn from measurements performed in liquid electrolytes are thus not always directly transferable to PEM fuel cells, where catalytic particles are in contact with a solid electrolyte. Discrepancies between the measurements performed with liquid and solid electrolytes may arise from (1) different utilization factors (higher utilization factors are usually expected in the former case), (2) different solubilities and diffusion coefficients, and (3) different electrode structures. Thus, to access the influence of carbon support porosity... 

Decreasing operation temperature of solid oxide fuel cells (SOFCs) and electrocatalytic reactors down to 800-1100 K requires developments of novel materials for electrodes and catalytic layers, applied onto the surface of solid electrolyte or mixed conducting membranes, with a high performance at reduced temperatures. Highly-dispersed active oxide powders can be prepared and deposited using various techniques, such as spray pyrolysis, sol-gel method, co-precipitation, electron beam deposition etc. However, most of these methods are relatively expensive or based on the use of complex equipment. This makes it necessary to search for alternative synthesis and porous-layer processing routes, enabling to decrease the costs of electrochemical cells. Recently, one synthesis technique based on the use... 

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