Oxygen doping

Reactions (7) and (8) represent the formation of a chloride-doped, oxygen-deficient, subsurface oxide film, which we believe portrays the true nature of the catalyst. Oxygen is then adsorbed on this surface as in reaction (9). The presence of surface and subsurface chloride will tend to inhibit the dissociative adsorption, leaving the associative form as the major reactive species. Ethylene can be reversibly adsorbed on Ag" or irreversibly adsorbed on the two oxygen species [reactions (10), (11), and (13)]. Reactions (11) and (12) lead to ethylene oxide via the intermediates observed by Kilty et al. and also Foice and Bell. With propylene, the hydroperoxide can be formed, which subsequently combusts... 

M.Z. Atashbar, H.T. Sun, B. Gong, W. Wlodarski, R. Lamb, XPS study of Nb-doped oxygen sensing Ti02 thin films prepared by sol-gel method . Thin Solid Films. 326, 238-244,(1998). 

Figure 4-10. Brouwer plot of the effect of water vapour (at constant oxygen pressure) on defect concentrations in acceptor-doped, oxygen deficient M2O3.

In this chapter, I have treated the defect chemistry and thermodynamics of hydration. I have, moreover, put special emphasis on inherently not acceptor-doped—oxygen-deficient systems and their hydration in the ordered or disordered states. Finally, I have discussed the new oxyhydroxide compounds that arise from such hydration and advocated that radically new and better proton conductors may rely on understanding how to stabilize, disorder, dope, and in general control the defect chemistry of such oxyhydroxides. 

Electrochemical Microsensors. The most successful chemical microsensor in use as of the mid-1990s is the oxygen sensor found in the exhaust system of almost all modem automobiles (see Exhaust control, automotive). It is an electrochemical sensor that uses a soHd electrolyte, often doped Zr02, as an oxygen ion conductor. The sensor exemplifies many of the properties considered desirable for all chemical microsensors. It works in a process-control situation and has very fast (- 100 ms) response time for feedback control. It is relatively inexpensive because it is designed specifically for one task and is mass-produced. It is relatively immune to other chemical species found in exhaust that could act as interferants. It performs in a very hostile environment and is reHable over a long period of time (36). 

The doped Zr02 stmctures are used as electrochemical sensors, as, for example, when used to detect oxygen in automotive exhaust (see Exhaust CONTROL, automotive). The sensor voltage is governed by the Nemst equation (eq. 17) where the activities are replaced by oxygen partial pressures and the air inside the chamber is used as reference. 

Strontium titanate [12060-59-2] SrTiO, becomes an n-ty e semiconductor when additional electrons are created on the Ti lattice sites by donor doping or when oxygen is removed from the material through heat treatment in a reducing atmosphere. The mobiUty of the electrons in the conduction band is about 6 crc] j(V-s). On the other hand, when ZnO is reduced, 2inc interstitials are formed and these act as donors, each yielding a free electron. 

Another application is in tire oxidation of vapour mixtures in a chemical vapour transport reaction, the attempt being to coat materials with a tlrin layer of solid electrolyte. For example, a gas phase mixture consisting of the iodides of zirconium and yttrium is oxidized to form a thin layer of ytnia-stabilized zirconia on the surface of an electrode such as one of the lanthanum-snontium doped transition metal perovskites Lai j.Srj.M03 7, which can transmit oxygen as ions and electrons from an isolated volume of oxygen gas. 

In a sense, a superconductor is an insulator that has been doped (contains random defects in the metal oxide lattice). Some of the defects observed via neutron diffraction experiments include metal site substitutions or vacancies, and oxygen vacancies or interstituals (atomic locations between normal atom positions). Neutron diffraction experiments have been an indispensable tool for probing the presence of vacancies, substitutions, or interstituals because of the approximately equal scattering power of all atoms. 

The polymers which have stimulated the greatest interest are the polyacetylenes, poly-p-phenylene, poly(p-phenylene sulphide), polypyrrole and poly-1,6-heptadiyne. The mechanisms by which they function are not fully understood, and the materials available to date are still inferior, in terms of conductivity, to most metal conductors. If, however, the differences in density are taken into account, the polymers become comparable with some of the moderately conductive metals. Unfortunately, most of these polymers also have other disadvantages such as improcessability, poor mechanical strength, instability of the doped materials, sensitivity to oxygen, poor storage stability leading to a loss in conductivity, and poor stability in the presence of electrolytes. Whilst many industrial companies have been active in their development (including Allied, BSASF, IBM and Rohm and Haas,) they have to date remained as developmental products. For a further discussion see Chapter 31. 

Polyacetylene is considered to be the prototypical low band-gap polymer, but its potential uses in device applications have been hampered by its sensitivity to both oxygen and moisture in its pristine and doped states. Poly(thienylene vinylene) 2 has been extensively studied because it shares many of the useful attributes of polyacetylene but shows considerably improved environmental stability. The low band gap of PTV and its derivatives lends itself to potential applications in both its pristine and highly conductive doped state. Furthermore, the vinylene spacers between thiophene units allow substitution on the thiophene ring without disrupting the conjugation along the polymer backbone. 

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