Perovskite doping

A second rule is that the oxidation of higher hydrocarbons, especially on perovskites doped with noble metals for increasing activity, may be described by Langmuir-Hinshelwood kinetics, indicating that both oxygen and CH species are adsorbed on the surface sites. On the contrary, for methane, the oxidation proceeds more or less via Rideal-Eley (RD) mechanism, which is in line with the notorious difficulty of this molecule to be activated. Let us review some cases from the literature. 

Okazaki, Y., Mishima, T., Nishimoto, S., Matsuda, M., and Miyake, M. (2008) Photocatalytic activity of Ca3Xi207 layered-perovskite doped with Rh under visible light irradiation. Mater. Lett.,... 

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. 

Good results are obtained with oxide-coated valve metals as anode materials. These electrically conducting ceramic coatings of p-conducting spinel-ferrite (e.g., cobalt, nickel and lithium ferrites) have very low consumption rates. Lithium ferrite has proved particularly effective because it possesses excellent adhesion on titanium and niobium [26]. In addition, doping the perovskite structure with monovalent lithium ions provides good electrical conductivity for anodic reactions. Anodes produced in this way are distributed under the trade name Lida [27]. The consumption rate in seawater is given as 10 g A ar and in fresh water is... 

Maitlis filtration test. To investigate whether the Pd-doped perovskite is the actual catalyst, or a reservoir of soluble Pd, a Maitlis filtration test (10) was performed. The reaction of 4-bromoanisole with 4-phenylboronic acid, catalyzed by BaCeo 95Pdo os02 95, was intemipted at 20 s and 1 min, corresponding to conversions of 16 and 45%, respectively, by filtering the hot reaction mixture to remove the solid perovskite. The filtrates were allowed to cool to room temperature without stirring. After 3 h, the biatyl yields in both samples were estimated to be 100% by H NMR. 

Catalyst recycling. The solid Pd-doped perovskite catalysts are easily filtered from the reaction mixtnre for reuse. The activity of the recycled BaCco 95Pdo.o502 95 catalyst was investigated in the coupling of 4-bromoanisole with 4-phenylboronic acid. The results in Table 27.3 show that high activity was retained even after seven cycles of catalyst use. 

The greater rearrangement of the perovskite stmeture in the catalyst associated with the higher level of Pd-doping may be responsible for the longer indnetion period. After the onset of catalytie activity, the slopes of the two conversion vs. time eurves for X = 0.05 and x = 0.10 in Figure 27. la are very similar, demonstrating that the two catalysts produce the same soluble aetive site in similar amounts. 

Scheme 27.1. Proposed mechanism for Suzuki coupling by Pd-doped perovskite catalysts.

The group of Ley has reported on the use of palladium-doped perovskites as recyclable and reusable catalysts for Suzuki couplings [151]. Microwave-mediated cross-couplings of phenylboronic acid with aryl halides were achieved within 1 h by utilizing the supported catalyst (0.25 mol% palladium) in aqueous 2-propanol (Scheme 7.127). The addition of water was crucial as attempted transformations in non-aqueous mixtures did not proceed. 

Scheme 7.127 Suzuki couplings utilizing palladium-doped perovskite as catalyst.

The most important of these are perovskite structure solids with a formula A2+b4+o3 that can be typified by BaCeC>3 and BaZrCV The way in which defects play a part in H+ conductivity can be illustrated by reference to BaCeCV BaCeC>3 is an insulating oxide when prepared in air. This is converted to an oxygen-deficient phase by doping the Ce4+ sites with trivalent M3+ ions (Sections 8.2 and 8.6). The addition of the lower valence ions is balanced by a population of vacancies. A simple substitution reaction might be formulated ... 

A perovskite structure oxide such as BaZrCLt can be made into a proton conductor by doping so as to introduce ... 

The spinel family of oxides with composition AB2O4 has the A and B cations distributed in octahedral and tetrahedral sites in a close-packed oxygen structure (Supplementary Material SI). Impurity doping can take place by the addition of a dopant to octahedral or tetrahedral sites. In this, the spinel family of compounds is quite different from the A2B04 perovskite-related phases of the previous section in that both cation sites are similar in size and can take the same cations. 

In the materials that follow, the structures are all layered. This structural feature has lead to a description of the doping in terms of charge reservoirs, a different approach to that described previously, and which is detailed below. Structurally the phases are all related to the perovskite-layered structures (Figs. 4.27, 4.28, 4.29, and 4.30). The similarity can be appreciated by comparison of the idealized structures and formulas of some of these materials, Bi2Sr2CuOg... 

Acceptor doping in perovskite oxides gives materials with a vacancy population that can act as proton conductors in moist atmospheres (Section 6.9). In addition, the doped materials are generally p-type semiconductors. This means that in moist atmospheres there is the possibility of mixed conductivity involving three charge carriers (H+, O2-, and h ) or four if electrons, e, are included. 

The situation can be illustrated with respect to the acceptor-doped perovskite structure SrZrC>3, with Y3+ substituted for Zr4+ to give compositions SrZrj YVC>3-0.5.V The doping reaction can be written ... 

The use of this approach can be illustrated by the perovskite structure proton conductor BaYo.2Zro.gO3 g- This material has been investigated for possible use in solid oxide fuel cells, hydrogen sensors and pumps, and as catalysts. It is similar to the BaPr03 oxide described above. The parent phase is Ba2+Zr4+03, and doping with... 

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