Zinc oxide chemical aspects

A seed-assisted chemical reaction at 368 K is found to yield uniform, straight, thin single-crystalline ZnO nanorods on a hectogram scale,181 Zinc oxide nanowires have been synthesized in large quantities using plasma synthesis.1 Variable-aspect-ratio,... 

In natural processes, metal ions are often in high oxidation states (2 or 3), whereas in chemical systems the metals are in low oxidation states (0 or 1). This fact inverts the role of the metal center, such that it acts as a one-electron sink in a natural system, but as a nucleophile in an artificial ones (see other chapters of this book and the review by Aresta et al. [109]). Nevertheless, important biochemical processes such as the reversible enzymatic hydration of C02, or the formation of metal carbamates, may serve as natural models for many synthetic purposes. Starting from the properties of carbonic anhydrase (a zinc metalloenzyme that performs the activation of C02), Schenk et al. proposed a review [110] of perspectives to build biomimetic chemical catalysts by means of high-level DFT or ah initio calculations for both the gas phase and in the condensed state. The fixation of C02 by Zn(II) complexes to undergo the hydration of C02 (Figure 4.17) the use of Cr, Co, or Zn complexes as catalysts for the coordination-insertion reaction of C02 with epoxides and the theoretical aspects of carbamate synthesis, especially for the formation of Mg2+ and Li+ carbamates, are discussed in the review of Schenk... 

Knowledge of the functional role of zinc as a component of metalloen-zymes is much less complete. Zinc differs from iron in several aspects. The known zinc enzymes are colorless, and the doubly ionized atom, having no unpaired electrons, has no paramagnetic moment. The metal has but one stable oxidation state in solution, is tightly bound to the apoenzyme, and can be removed only with severe chemical treatment. In no instance, so far, has the group binding the metal to enzyme been established with certainty. 

Conducting polymers can be prepared by chemical or electrochemical techniques. Electrochemical synthesis provides easier routes when compared with chemical synthesis and allows control over film formation, especially relevant if polymers are required as thin films deposited on the surface of metallic substrates. However, electrochemically synthesized polymers are usually more porous, a feature that requires consideration when a barrier effect is necessary. Another important aspect in the corrosion field is that the application of potential/current necessary to promote electropolymerization may accelerate dissolution (corrosion) of the metal. In some cases, an oxide pre-layer is deposited between the metal and the polymer to promote adhesion and hinder metal dissolution during the electropolymerization process (Tallman et al., 2002 Spinks et al., 2002). Alternatively, the application of layered coatings based on different conducting polymers can be a strategy to overcome the problem of metal dissolution. In the work of Lacroix et al. (2000), a layer of PPy was firstly deposited on zinc and mild steel in neutral conditions, followed by deposition of PANi in an acidic medium, because the direct deposition of PANi on those metallic substrates was not possible in an acidic medium, causing dissolution of the metal. 

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