Zinc oxide surface structures

Besides supported (transition) metal catalysts, structure sensitivity can also be observed with bare (oxidic) support materials, too. In 2003, Hinrichsen et al. [39] investigated methanol synthesis at 30 bar and 300 °C over differently prepared zinc oxides, namely by precipitation, coprecipitation with alumina, and thermolysis of zinc siloxide precursor. Particle sizes, as determined by N2 physisorpt-ion and XRD, varied from 261 nm for a commercial material to 7.0 nm for the thermolytically obtained material. Plotting the areal rates against BET surface areas (Figure 3) reveals enhanced activity for the low surface area zinc... 

Experimental results clearly demonstrate that catalytic reaction of dehydration of alcohols on zinc oxide proceeds via formation of radicals. Emission of hydrogen atoms from the catalyzer surface may be associated with structure relaxation of the catalyzer surface excited during the reaction [26]. 

The electronic microscopy method on the EM-125 (fig. 1) for definition of ZnCFO particles size and characteristic of its surface was applied. Known zinc oxide was chosen as the object of comparison. The electronic photos of powders testify, that new composite and zinc oxide have external similarity under the form of particles, wide range on dispersiveness (0,4-6,0 microns for zinc oxide, fig. la 0,3-6,0 microns for ZnCFO, fig. lb) also contain as crystal as amorphous phases in their structure. 

Feltz, A. Martin, A. (1987) Solid-state reactivity and mechanisms in oxide systems. 11 Inhibition of zinc ferrite formation in zinc oxide - a-iron(lll) oxide mixtures with a large excess of a-iron(lll) oxide. In Schwab, G.M. (ed.) Reactivity of solids. Elsevier, 2 307—313 Fendorf, S. Fendorf, M. (1996) Sorption mechanisms of lanthanum on oxide minerals. Clays Clay Miner. 44 220-227 Fendorf, S.E. Sparks, D.L. (1996) X-ray absorption fine structure spectroscopy. In Methods of Soil Analysis. Part 3 Chemical Methods. Soil Sd. Soc. Am., 377-416 Fendorf, S.E. Eick, M.J. Grossl, P. Sparks, D.L. (1997) Arsenate and chromate retention mechanisms on goethite. 1. Surface structure. Environ. Sci. Techn. 31 315-320 Fendorf, S.E. Li,V. Gunter, M.E. (1996) Micromorphologies and stabilities of chromiu-m(III) surface precipitates elucidated by scanning force microscopy. Soil Sci. Soc. Am. J. 60 99-106... 

As will be discussed later in this section, most of the investigations on zinc oxide have been done on specimens whose structure allows the surface effects to be large. 

Figure 1 is an energy level diagram showing a proposed model for the band structure of zinc oxide. The valence band and conduction band are shown separated by a forbidden gap. Two levels which correspond to the trapping of two electrons by the interstitial zinc are indicated in the forbidden gap. Surface levels associated with adsorbed oxygen are shown. 

As in the case of normal supported catalysts, we tried with this inverse supported catalyst system to switch over from the thin-layer catalyst structure to the more conventional powder mixture with a grain size smaller than the boundary layer thickness. The reactant in these studies (27) was methanol and the reaction its decomposition or oxidation the catalyst was zinc oxide and the support silver. The particle size of the catalyst was 3 x 10-3 cm hence, not the entire particle in contact with silver can be considered as part of the boundary layer. However, a part of the catalyst particle surface will be close to the zone of contact with the metal. Table VI gives the activation energies and the start temperatures for both methanol reactions, irrespective of the exact composition of the products. 

In order to mimic the attack of ZDDP onto the oxide surface (FeO), the structure of the possible complexes formed between an O2 ion and ZDDP was examined. The oxide anion was allowed to interact with the positively charged atoms (zinc and phosphorus), and partially negatively charged sulfur atoms of the additive molecule. The heats of complex formation (Oxide ion + ZDDP -ZDDP Oxide) and total energies determined for each complex were reported (Armstrong et al., 1998). 

Zincite is usually colored red or orange by manganese impurities. Photographs of zincite are shown in Fig. 1.2. Zinc oxide crystals exhibit several typical surface orientations. The most important surfaces are the (0001) and (0001) (basal plane), (1010) and (1120) (prism planes) and (1121) (pyramidal plane) crystal faces. In principle, the (0001) planes are terminated by Zn atoms only, while the (0001) surfaces are terminated by oxygen atoms only. However, this simple picture does not hold in reality (see description of the surface structure in Sect. 4.2.1 of this book). Nevertheless, the etching behavior is noticeably different for these two surfaces [17] (see also Chap. 8). 

This book is devoted to the properties, preparation and applications of zinc oxide (ZnO) as an transparent electrode material. It focuses on ZnO for thin film solar cell applications and hopefully inspires also readers from related fields. The book is structured into three parts to serve both as an overview as well as a data collection for students, engineers and scientists. The first part, Chaps. 1-4, provide an overview of the application and fundamental material properties of ZnO films and their surface and interfaces properties. Chaps. 5-7 review thin film deposition techniques applied for ZnO preparation on lab scale but also for large area production. Finally, Chaps. 8 and 9 are devoted to applications of ZnO in silicon- and chalcopyrite-based thin film solar cells, respectively. One should note that the application of CVD grown ZnO in silicon thin film cells is discussed earlier in Chap. 6. 

In a similar experiment, 2.5 g of zinc oxide prepared by precipitation from zinc nitrate solution by sodium carbonate, calcination, and attempted reduction under similar conditions as previously employed, gave a catalyst of surface area of 40 m2/g, which yielded less than 10 9 kg of methanol per square meter of the catalyst per hour under the standard conditions used for the testing of the copper catalyst. The zinc oxide was in its wurtzitic crystal modification as in most laboratory as well as industrial catalysts, was free of surface impurities, and had a morphology shown in Fig. 4. Details of the pore structure of this catalyst are given in reference (38). 

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