Titanium redox properties

One-electron reduction or oxidation of organic compounds provides a useful method for the generation of anion radicals or cation radicals, respectively. These methods are used as key processes in radical reactions. Redox properties of transition metals can be utilized for the efficient one-electron reduction or oxidation (Scheme 1). In particular, the redox function of early transition metals including titanium, vanadium, and manganese has been of synthetic potential from this point of view [1-8]. The synthetic limitation exists in the use of a stoichiometric or excess amount of metallic reductants or oxidants to complete the reaction. Generally, the construction of a catalytic redox cycle for one-electron reduction is difficult to achieve. A catalytic system should be constructed to avoid the use of such amounts of expensive and/or toxic metallic reagents. 

Recently, renewed attention has been given to so-called soft chemistry methods of synthesis of new metastable materials [9]. The synthesis of new microporous materials containing transition metals in the framework is of growing interest due to the expected catalytic redox properties [10]. The microporous titanium(IV) silicates [11] discovered have already proven the concept by showing very good catalytic activities and are widely used nowadays [12]. Similarly, hydrothermally synthesized titanium phosphates with open-finmework or layered structures are attracting attention as potential materials with similar properties [13]. 

The vanadium silicalites (with MFI and MEL stmcture) are active oxidation catalyst in gas and liquid phase reactions [180]. As for the titanium silicalites, only the ftamework associated vandium exhibits redox properties [181]. For example, in the hydroxylation of phenol, silicalite impregnated with vanadium compounds is catalytically inactive [182]. The catalytically active vanadium species is speculated to be located in non-tetrahedral positions, most probably chemically bound to the framework. Vanadium bound in that way is not extractable from the lattice [ 183]. A proposed stmcture of the vanadium site is schematically shown in Scheme 21. Note that the Si-O-V bonds are longer than the Si-O-Ti bonds and that V seems to be more exposed. The redox properties are affiliated with the changes in the oxidation state of vanadium between +IV and +V. Vanadium silicates with SiA ratios ranging from 40 to 160 have been reported and these high values suggest (in accordance with V MAS-NMR measurements) that the V sites are isolated in the lattice. 

The electrochemical behavior, in non-aqueous solvents, of some mono- and bis-Cp oxo homo- and heteropoly-nuclear titanium derivatives containing oxo bridges between different metals has been investigated (Scheme 347). Cyclic voltammetry, square wave voltammetry, and polarography have been used to determine and compare the redox properties of these compounds.829... 

The syntheses of bis-Gp 2,3-quinoxaline-dithiolato titanium(iv) and bis-Cp 1,2-ethenedithiolato titanium derivatives have been described (Cp =CsH3PhMe). The redox properties of these compounds in neutral solutions have been studied. All the compounds exhibit a reversible one-electron reduction process, the potential of which is... 

The most common photocatalytic processes, in terms of both mechanistic analysis and practical use, involve insoluble semiconductor metal oxides or sulfides, which upon irradiation undergo dual interfacial electron transfer between the excited semiconductor surface and adsorbed donor (D) and/or acceptor (A) molecules (Scheme 6.291). Titanium dioxide (Ti02) is a particularly popular photocatalyst due to its good redox properties (see also Special Topic 6.29), high stability, low toxicity and low price. 

Investigation of the sol-gel derived bismuih-molybdcnum-titanium xerogel and aerogel mixed oxide as catalyst for the oxidation of butadiene to furan l 14J 15] indicated activities and selectivities comparable to other suitable catalysts. The unique microstructure and good catalytic performance of the bismuth molybdenum oxide particles are attributed to lilania matrix. How ever, these favorable properties are limited to low temperature reaction conditions since both xerogels and aerogels are prone to rapid restructuring at elevated temperatures, which result in the loss of their unique redox properties. 

In this work the effect of Sb or V substitution by Titanium over the redox properties and the catalyst behaviour of solids with nominal composition VSb04, Vo. SbTio.204, VSbo.8Tio.2O4 is studied. In addition, the effect of the Sb content on the deactivation of the catalysts is analysed. 

Doubly substituted analogues of TS-1 have also been reported. Trong et al. (130) synthesized bifunctional molecular sieves with titanium and various trivalent ions, for example, Ti-MFI that also contained, Al, or Ga. Tin and vanadium have also been incorporated into the titanium silicalite structure (33,131) by a primary synthesis method. The incorporation of a second metal changes the redox properties of the materials as well as their morphology. Incorporation of tin into titanium silicalite improved the epoxidation selectivity of the catalyst compared with that of (mono-substituted) TS-1. 

The ion-exchange technique allows to prepare VO modified titanium phosphates. Different vanadium loadings can be obtained by properly controlling the operating exchange conditions and precursor phase. Vanadyl modified titanium phosphates catalysts were found active and selective towards SCR reaction, either as hydrogen or pyrophosphate phase. The results obtained in this paper indicate that the activity of the materi s can be relate to vanadyl species whose redox properties affect the catalytic behaviour. 

In certain solids such as titanium dioxide or cadmium sulfide, the energy of the band gap corresponds to that of light (visible, ultraviolet, or infrared), with the result that the solid, when illuminated, may become electrically conducting or acquire potent chemical redox characteristics because of the promotion of electrons to the conduction band (which is normally unoccupied). These properties have obvious practical significance and are considered at length in Chapter 19. 

Unstabilized chrome yellow pigments have poor lightfastness, and darken due to redox reactions. Recent developments have led to improvements in the fastness properties of chrome yellow pigments, especially toward sulfur dioxide and temperature. This has been achieved by coating the pigment particles with compounds of titanium, cerium, aluminum, antimony, and silicon [3.134] — [3.142]. 

Rekoske and Barteau (68) used TEOM in scaling-up to higher pressure surface-science results dealing with solid reactions related to redox cycles. These authors investigated reduction kinetics and reaction on titanium oxide (69,70). Recent applications also include the investigation of carbon nanofibers (9) and hydrogen adsorption properties of single-walled carbon nanotubes (71). 

Photochemistry of Titanium Dioxide Colloids. Another semiconductor colloid used in our studies is titanium dioxide which has a band gap of 3.2 eV. As in the case of cadmium sulfide, excitation of aqueous suspensions of this particle leads to electron-hole pair separation which can be intercepted with suitable redox reagents. In the absence of externally added solutes, the photogenerated electron-hole pair recombines to give the starting material and the light energy is dissipated to the medium as heat. Two types of TiOj samples are used in this study. TiOj prepared at high temperature (80°C) which behaves very similarly to commercial samples, and TlOj prepared at low temperature (35°C) which has a particle size of 300 100 A radius and shows different properties. 

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