Electron conductor membranes

The use of a mixed oxygen ion-electronic conductor membrane for oxygen separation with direct reforming of methane, followed by the use of a mixed protonic-electronic membrane conductor for hydrogen extraction has also been proposed in the literature [34]. The products are thus pure hydrogen and synthesis gas with reduced hydrogen content, the latter suitable, for example, in the Fish-er-Tropsch synthesis of methanol [34]. 

Solid mixed ionic-electronic conductors (MIECs) exhibit both ionic and electronic (electron-hole) conductivity. Naturally, in any material there are in principle nonzero electronic and ionic conductivities (a i, a,). It is customary to limit the use of the term MIEC to those materials in which a, and 0, 1 do not differ by more than two orders of magnitude. It is also customary to use the term MIEC if a, and Ogi are not too low (o, a i 10 S/cm). Obviously, there are no strict rules. There are processes where the minority carriers play an important role despite the fact that 0,70 1 exceeds those limits and a, aj,i< 10 S/cm. In MIECs, ion transport normally occurs via interstitial sites or by hopping into a vacant site or a more complex combination based on interstitial and vacant sites, and electronic (electron/hole) conductivity occurs via delocalized states in the conduction/valence band or via localized states by a thermally assisted hopping mechanism. With respect to their properties, MIECs have found wide applications in solid oxide fuel cells, batteries, smart windows, selective membranes, sensors, catalysis, and so on. 

From an electrochemical viewpoint, biological systems are highly branched circuits consisting of ionic conductors of aqueous electrolyte solutions and highly selective membranes. These circuits lack metallic conductors, but it has been found relatively recently that they contain sections that behave like electronic conductors (i.e., sections in which electrons can be transferred over macroscopic distances, owing to a peculiar relay-type mechanism). 

It is well known that dense ceramic membranes made of the mixture of ionic and electron conductors are permeable to oxygen at elevated temperatures. For example, perovskite-type oxides (e.g., La-Sr-Fe-Co, Sr-Fe-Co, and Ba-Sr-Co-Fe-based mixed oxide systems) are good oxygen-permeable ceramics. Figure 2.11 depicts a conceptual design of an oxygen membrane reactor equipped with an OPM. A detail of the ceramic membrane wall... 

Silver sulphide exists in two modifications, a-Ag2 S, the cubic form, which is an electronic conductor and is stable above 176°C, and monoclinic/l-AgjS, an ionic conductor, which is stable at lower temperatures [316]. In this latter modification, Ag is almost the only charge carrier [141, 325,428], The good conductivity and negligible solubility of the compact membrane make the Ag2 S ISE one of the most reliable sensors. 

The principles of the fuel cell are illustrated in Figure 1.1. The electrochemical cell consists of two electrodes, an anode and a cathode, which are electron conductors, separated by an electrolyte [e.g. a proton exchange membrane (PEM) in a PEMFC or in a DAFC], which is an ion conductor (as the result of proton migration and diffusion inside the PEM). An elementary electrochemical cell converts directly the chemical... 

When the conducting polymer is used as ion-to-electron transducer in the form of an intermediate layer between the electronic conductor and the ion-selective membrane it does not significantly influence the sensitivity and selectivity of the ISE, but it allows high potential stability [75]. For example, microfabricated solid-state K+-ISEs with polypyrrole as ion-to-electron transducer was found to show even better long-term potential stability than those based on a hydrogel contact [58]. The potential of the polypyrrole-based K+-ISE was slightly more sensitive to the oxygen concentration of the sample in comparison to... 

Colloids of semiconductors are also quite interesting for the transmembrane PET, as they possess both the properties of photosensitizers and electron conductors. Fendler and co-workers [246-250] have shown that it is possible to fix the cadmium sulfide colloid particles onto the membranes of surfactant vesicles and have investigated the photochemical and photocatalytic reactions of the fixed CdS in the presence of various electron donors and acceptors. Note, that there is no vectorial transmembrane PET in these systems. The vesicle serves only as the carrier of CdS particles which are selectively fixed either on the inner or on the outer vesicle surface and are partly embedded into the membrane. However, the size of the CdS particle is 20-50 A, i.e. this particle can perhaps span across the notable part of the membrane wall. Therefore it seems attractive to use the photoconductivity of CdS for the transmembrane PET. Recently Tricot and Manassen [86] have reported the observation of PET across CdS-containing membranes (see System 32 of Table 1), but the mechanism of this process has not been elucidated. Note, that metal sulfide semiconductor photosensitizers can be deposited also onto planar BLMs [251],... 

Electrocapillaric Becquerel phenomenon - Becque-rel [i] discovered the phenomenon that at membranes separating a metal solution containing a metal ion, e.g., of copper nitrate, from a solution of sodium sulfide, a metal salt (e.g., copper sulfide) precipitates on which crystals of the metal grow into the metal solution and sulfide is oxidized on the side of the sodium sulfide solution. The effect is only observed when the precipitated salt is a semiconductor. The effect is due to the formation of a —> galvanic cell with the semiconductor as the electronic conductor bridging the two solutions and some electrolyte pores in the membrane forming the ionic conductor [ii]. 

It is obvious that a highly permeable membrane material must exhibit large con-ductivies for both ionic and electronic charge carriers. Partial conductivities of various, so-called mixed ionic electronic conductors (MIEC), as calculated or directly obtained from Refs. 9-21, are presented in Figure 2. 

Although powder routes have been successfully developed for synthesis of catalysts used in low temperature fuel cells, electrodeposition offers the highest noble metal utilization and is preferred over the alternative chemical methods. Electrodeposition enables the formation of catalyst particles on specific sites where they can be essentially utilized, i.e., the triple phase boundary where the membrane (ionic conductor), electrode (electronic conductor), and reactants meet. Powder methods do not guarantee that all catalyst particles are in contact with both electrode and membrane materials, and therefore, a portion of catalyst particles may remain inactive. 

In this section, a brief overview is given of major membrane concepts and materials. Besides membranes made from a mixed ionic-electronic conductor (MIEC), other membranes incorporating an oxygen ion conductor are briefly discussed. Data from oxygen permeability measurements on selected membrane materials are presented. 

Ceramic electrochemical reactors are currently undergoing intense investigation, the aim being not only to generate electricity but also to produce chemicals. Typically, ceramic dense membranes are either pure ionic (solid electrolyte SE) conductors or mixed ionic-electronic conductors (MIECs). In this chapter we review the developments of cells that involve a dense solid electrolyte (oxide-ion or proton conductor), where the electrical transfer of matter requires an external circuitry. When a dense ceramic membrane exhibits a mixed ionic-electronic conduction, the driving force for mass transport is a differential partial pressure applied across the membrane (this point is not considered in this chapter, although relevant information is available in specific reviews). 

In response to other needs in the energy and transportation sector, membranes are evolving that transport molecular species, ions, electrons, and combinations of these species. For example, mixed oxide ion-electronic conductors that become the wall of tubular reactors will soon move out of the laboratory and be used to oxidize methane by transport of oxygen from the air side to the fuel side, where the methane is converted to carbon monoxide and hydrogen. This technology eliminates the need for huge and expensive air separation plants to supply oxygen. 

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