Titanium, Manganese, and Zirconium Dioxides

The dioxides of titanium (TiO2), manganese (MnO2), and zirconium (ZrO2) are important materials because of their technological uses. TiO2 is used mainly as white pigment. Because of its semiconducting properties, TiO2, in its nanomaterial form, is also used as an active component of photocells and photocatalysis for self-cleaning glasses and cements . MnO2 is used primarily in electrode materials. ZrO2 is used in refractory ceramics, abrasive materials, and stabilized zirconia as ionic conductive materials stable at high temperature. Many of these properties are, of course, dependent on particle size and shape (§ Chap. 1). Dioxides of other tetravalent elements with interesting properties have been studied elsewhere in this book, especially VO2, which exhibits a metal–isolator transition at 68°C, used, for instance, in optoelectronics (§ 4.1.5), and silica, SiO2 (§ 4.1.4), which is likely the most ubiquitous solid for many applications and uses. Aqueous chemistry is of major interest in synthesizing these oxides in the form of nanoparticles from inorganic salts and under simple, cheap, and envi­ronmental friendly conditions. However, as the tetravalent elements have re­stricted solubility in water (§ 2.2), metal–organic compounds such as titanium and zirconium alkoxides are frequently used in alcoholic solution as precursors for the synthesis of TiO2 and ZrO2 nanoparticles. An overview of the conversion of alkoxides into oxides is indicated about silica formation (§ 4.1.4), and since well-documented works have already been published, these compounds are not considered here. The crystal structures of most MO2 dioxides are of TiO2 rutile type for hexacoordinated cations (e.g., Ti, V, Cr, Mn, Mo, W, Sn, Pb) and CaF2 fluorite type for octacoordinated, larger cations (e.g., Zr, Ce), but polymorphism is common. Some dioxides of elements such as chromium and tin form only one crystal­line phase. So, hydrolysis of SnCl4 or acidification of stannate [Sn(OH)6]2− leads both to the same rutile-type phase, cassiterite, SnO2. Many other dioxides are polymorphic, especially TiO2, which exists in three main crystal phases: anatase, brookite, and rutile; and MnO2, which gives rise to a largely diversified crystal chemistry.