Polyoxometalates applications

Conclusions and Perspectives in Polyoxometallate Application in Heterogeneous Oxidation Catalysis... 

The applications of polyoxometalates in catalytic dehalogenation of halocar-bons have been succinctly reviewed by Hill and coworkers [188]. This reaction involves the photocatalytic transformation of organic halides coupled with the oxidation of sacrificial organic reductants (secondary alcohols or tertiary amides) (Eq. (9)) [189, 190] ... 

The versatility and accessibility of polyoxometalates (POMs) have led to the various applications in the fields of structural chemistry, analytical chemistry, surface science, medicine, electrochemistry, photochemistry, and catalysis. Especially, POMs have received much attention in the area of oxidation and acid catalysis [25-31]. Several categories of POMs are formed by proper selection of the starting components and by the adjustment of pH and temperature. Typical examples are shown in Figure 13.1 (i) isopolyoxometalates of the general formula, MxO> 1, produced by condensation... 

Pope, M. T. Muller, A. (Eds.) Polyoxometalate Chemistry from Topology via Self-Assembly to Applications , Kluwer Academic Publishers Dordrecht, 2001. 

A convenient application uses an inorganic salt (e.g., a polyoxometallate)" or a semiconductor oxide as the sensitizer. Such materials are often chemically more stable with respect to organic molecules, and again can be conveniently used for the generation of a radical from unconventional precursors. 

Iu search for efficieut aud greeuer processes over the past few years various heterogeneous catalysts such as titanium incorporated mesoporous molecular sieves [45,46], Schiff-base complexes supported on zeolite [47] and Zn(II)-Al(III) layered double hydroxide (LDH) [48], oxomolybdenum(VI) complexes supported on MCM-41 and MCM-48 [49], polyoxometallate supported materials [50], Co and Mn-AlPO s [51] etc. have been developed and studied for the catalytic epoxidatiou of a-pinene. Many of these processes suffer from drawbacks and limited applicability due to the poor conversion and also the selectivities. Sacrificial aldehydes are often used as an oxygen acceptor in such processes to achieve reasonable yield and selectivities but, this procedure leads to an increase in the E-factors and decrease in the atom economy [51]. 

Polyoxometalates undoubtedly have enormous catalytic potential in liquid phase selective oxidation of organic compounds. Various strategies for immobilization of POMs on solid matrices have been developed during the past two decades and opened new opportunities for practical applications. The most developed and widely used technique is electrostatic... 

The interest in the redox, catalytic, and electrocatalytic properties of unsubstituted and substituted polyoxometalates arouses much attention [2-15] because they are a versatile family of molecular metal-oxide clusters with applications in catalysis as well as in medicine and material science. Such versatility must be traced to at least two main characteristics. First, the size and mass of these unique molecular oxides place their solution chemistry in an intermediate position between small molecule solution chemistry and infinite lattice solid-state chemistry. Second, their redox behaviors may be very flexible and finely tuned on purpose, by changing smoothly their composition, with a... 

M. T. Pope and A. Muller (eds), Polyoxometalate Chemistry From Topology via Self-Assembly to Industrial Applications, Kluwer, Dordrecht, 2001. 

Polyoxometalates are important catalysts but they are also finding application in optical, electrical, and magnetic devices. Mixed-metal polyoxometalates with vanadium(V) in the polyoxoanion core confers enhanced properties to such structures, principally in their ability to form essentially infinite networks that can be utilized as coatings or as other thin film materials. Additionally, these materials have tunable electromagnetic and photochromic properties. In combination with organic polymers, so-called hybrid polymers, special electrochemical properties are conferred, making possible such electrical storage devices such as capacitors and batteries that utilize the redox properties of the polyoxometalate [7],... 

The present chapter reviews the structural chemistry (Section 2) and properties and applications (Section 3) of polyoxometalates that incorporate one or more rare-earth elements. In most cases these are discrete anionic entities within the crystal and in solution, but there are also extended lattices in which POM groups are linked by rare-earth cations. Solids which can best be described as mixed oxides, or which appear to be salts of common polyoxometalate architectures such as the... 

Applications of spectroscopic methods in studies of polyoxometalates and their complexes with lanthanide (III) ions Lis (2000)... 

Polyoxometalates are important reagents in analytical chemistry and they also find applications in catalysis, molecular biology, materials sciences, and medicine. A recent study of nine Ndm polyoxometalates (POM) showed their aqueous 5 mM solutions to be weakly luminescent, whereas no luminescence at all is seen for the aquo ion. In particular, the bis(POM) complexes better protect the Ndm ion from nonradiative deactivations, for instance t(4F3/2) = 411 6nsfor[Nd(PWn039)2]11- and67 2 ns for [Nd(As4W4oOi4o)]25 (But et al., 2005). 

Previous Volumes in this Series have described, in general, practical tips for performing topical reactions. Volume 2 was however dedicated specifically to Catalysis by Polyoxometalates . The present Volume features recent advances in the application of microporous and mesoporous solid catalysts to fine chemical synthesis, a field that is receiving increasing attention because of its high potential for the development of green processes for the synthesis of fine chemicals. 

Polyoxometalates (POMs), also known as heteropolyacids (HPA),3 are a class of compounds formed from negatively charged inorganic metal-oxygen building blocks. When charge-balanced with cationic species, POMs self-assemble into unusual 3D structures with specific topological and electronic properties.214 POMs are commonly formed from polyanions of early transition metals such as W, Mo or V. These anions can be substituted with other transition metals. The diversities in POMs composition and structure make them attractive for many applications, particularly as Bronsted acid and redox catalysts. For example,... 

A relatively recent field of study, which, will be expanded upon later, is that of transition metal substituted polyoxometallates.43 The fact that they are, in most cases, completely inorganic means that they are inherently robust to oxidative degradation, hence, offering good prospects for industrial application. 

Polyoxometalates have found applications in analytical and clinical chemistry, catalysis (including photocatalysis), biochemistry (electron transport inhibition), medicine (antitumoral, antiviral, and even anti-HIV activity), and solid-state device [19,20], Recently, three-dimensional ordered materials are modified by the incorporation of POM into wall structures using a direct synthesis approach [21,22], The motivation for the work lies in the novel properties that POM is introduced into silica networks [19,20], The incorporation is that the POM is linked to silica matrix by covalent grafting. A class of POM that are particularly attractive for the preparation of hybrid materials are the lacunary POM. Lacunary POMs include the mono and divacant unsaturated Keggin fragments [X" W,039]< ">- (X"+=B Ge P [22], [ Y -SiWioOgg] [21], Lacunary... 

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