Anatase

Rutile and anatase are used in photocatalysis and as catalyst supports and we describe some important structural features later. The titanium-oxygen system plays a key role in understanding stoichiometric variations. The highest oxide, Ti02, is polymorphic and the four known crystal structures are rutile, anatase, brookite and a high-pressure form similar to a-Pb02. 

Another polymorph of titania with a tetragonal structure a = 3.73 A and c = 9.37 A. Anatase has edge-sharing [Ti06] octahedra joined at the corners so that the oxygen atoms are in a slightly distorted cubic arrangement. At 

---

An example of the time effects in irreversible adsorption of a surfactant system is shown in Fig. XI-8 for barium dinonylnapthalene sulfonate (an oil additive) adsorbing on Ti02 (anatase). Adsorption was ineversible for aged systems, but much less so for those equilibrating for a short time. The adsorption of aqueous methylene blue (note Section XI-4) on TiOi (anatase) was also irreversible [128]. In these situations it seems necessary to postulate at least a two-stage sequence, such as... 

Very finely divided minerals may be difficult to purify by flotation since the particles may a ere to larger, undesired minerals—or vice versa, the fines may be an impurity to be removed. The latter is the case with Ii02 (anatase) impurity in kaolin clay [87]. In carrier flotation, a coarser, separable mineral is added that will selectively pick up the fines [88,89]. The added mineral may be in the form of a floe (ferric hydroxide), and the process is called adsorbing colloid flotation [90]. The fines may be aggregated to reduce their loss, as in the addition of oil to agglomerate coal fines [91]. 

A large variety of organic oxidations, reductions, and rearrangements show photocatalysis at interfaces, usually of a semiconductor. The subject has been reviewed [326,327] some specific examples are the photo-Kolbe reaction (decarboxylation of acetic acid) using Pt supported on anatase [328], the pho-... 

Figure Bl.26.2. Adsorption isothemi for nitrogen on anatase at 77 K showing point B (Harkins W D 1952 The Physical Chemistry of Surface Films (New York Reinliold)).

Figure C2.17.1. Transmission electron micrograph of a Ti02 (anatase) nanocrystal. The mottled and unstmctured background is an amorjihous carbon support film. The nanocrystal is centred in die middle of die image. This microscopy allows for die direct imaging of die crystal stmcture, as well as the overall nanocrystal shape. This titania nanocrystal was syndiesized using die nonhydrolytic niediod outlined in [79].

Figure C2.17.8. Powder x-ray diffraction (PXRD) from amoriDhous and nanocry stalline Ti02 nanocrystals. Powder x-ray diffraction is an important test for nanocrystal quality. In the top panel, nanoparticles of titania provide no crystalline reflections. These samples, while showing some evidence of crystallinity in TEM, have a major amoriDhous component. A similar reaction, perfonned with a crystallizing agent at high temperature, provides well defined reflections which allow the anatase phase to be clearly identified.

Unlike melting and the solid-solid phase transitions discussed in the next section, these phase changes are not reversible processes they occur because the crystal stmcture of the nanocrystal is metastable. For example, titania made in the nanophase always adopts the anatase stmcture. At higher temperatures the material spontaneously transfonns to the mtile bulk stable phase [211, 212 and 213]. The role of grain size in these metastable-stable transitions is not well established the issue is complicated by the fact that the transition is accompanied by grain growth which clouds the inteiyDretation of size-dependent data [214, 215 and 216]. In situ TEM studies, however, indicate that the surface chemistry of the nanocrystals play a cmcial role in the transition temperatures [217, 218]. 

Penn R L and Banfieid J F 1999 Formation of rutiie nuciei at anatase (112) twin interfaces and the phase transformation mechanism in nanocrystaiiine titania Am. Miner. 84 871... 

Zhang H and Banfieid J F 1999 New kinetic modei for the nanocrystaiiine anatase-to-rutiie transformation reveaiing rate dependence on number of particies Am. Miner. 84 528... 

Agrawai A, Cizeron J and Coivin V L 1998 In situ high-temperature transmission eiectron microscopy observations of the formation of nanocrystaiiine TiC from nanocrystaiiine anatase (Ti02) Microsc. Microanal. 4 269... 

Comparison of specific surface of anatase and zinc oxide determined by electron microscopy A ) and by nitrogen adsorption A )... 

The molecular area, calculated from the density of the supercooled liquid at 77 K is a ,(Kr) = 15-2 A, but Beebe found it necessary to adopt the higher value 19-5 A to bring the krypton-based area into line with the area of Harkins reference sample of anatase. ... 

Raman spectroscopy of [INFRARED TECHNOLOGY AND RAMAN SPECTROSCOPY - RAMAN SPECTROSCOPY] pol 14) Titanium dioxide, anatase [1317-70-0]... 

Fig. 16. Two-hquid flotation flow sheet (39). The original ROM is kaolin (white clay) that contains 11% impurity in the form of mica, anatase, and siUca. Treatment produces high purity kaolin and a Ti02-rich fraction. A, Kaolin stockpile D, dispersant (sodium siUcate plus alkah) W, water K, kerosene C, collector (sodium oleate) RK, recycled kerosene S, screen M, inline mixer SPR, separator CFG, centrifuge P, product and T, to waste.

Corning 9617 P-spodumene soHd solution anatase, Ti02 low expansion, high strength, thermal StabiHty, chemical durabiHty electric range tops (opaque)... 

A significant advantage of the PLM is in the differentiation and recognition of various forms of the same chemical substance polymorphic forms, eg, brookite, mtile, and anatase, three forms of titanium dioxide calcite, aragonite and vaterite, all forms of calcium carbonate Eorms I, II, III, and IV of HMX (a high explosive), etc. This is an important appHcation because most elements and compounds possess different crystal forms with very different physical properties. PLM is the only instmment mandated by the U.S. Environmental Protection Agency (EPA) for the detection and identification of the six forms of asbestos (qv) and other fibers in bulk samples. 

Naphthaleneamine. 1-Naphthylamine or a-naphth5iamine/7i5 -i2- can be made from 1-nitronaphthalene by reduction with iron—dilute HCl, or by catalytic hydrogenation it is purified by distillation and the content of 2-naphthylamine can be reduced as low as 8—10 ppm. Electroreduction of 1-nitronaphthalene to 1-naphthylamine using titania—titanium composite electrode has been described (43). Photoinduced reduction of 1-nitronaphthalene on semiconductor (eg, anatase) particles produces 1-naphthylamine in 77% yield (44). 1-Naphthylamine/7J4-J2-. can also be prepared by treating 1-naphthol with NH in the presence of a catalyst at elevated temperature. The sanitary working conditions are improved by gas-phase reaction at... 

Rapid e / h recombination, the reverse of equation 3, necessitates that D andM be pre-adsorbed prior to light excitation of the Ti02 photocatalyst. In the case of a hydrated and hydroxylated Ti02 anatase surface, hole trapping by interfacial electron transfer occurs via equation 6 to give surface-bound OH radicals (43,44). The necessity for pre-adsorbed D andM for efficient charge carrier trapping calls attention to the importance of adsorption—desorption equihbria in... 

The most common stmctures of inorganic pigments ate mtile, anatase, and spinel. 

The concentrated mother Hquor contains a large amount of sulfuric acid in a free form, as titanium oxy-sulfate, and as some metal impurity sulfates. To yield the purest form of hydrated TiOg, the hydrolysis is carried out by a dding crystallizing seeds to the filtrate and heating the mixture close to its boiling temperature, - 109° C. The crystal stmcture of the seeds (anatase or mtile) and their physical properties affect the pigmentary characteristics of the final product. 

---