Heterogeneous POM-based catalysts

The examples of dative binding of catalytically active POMs to acquire heterogeneous POM-based catalysts can be found in the literature quite rarely compared to the examples of electrostatic attachment which were discussed in the previous section. 

To reduce the environmental impact of POM-based catalysts, many different techniques of immobilization/heterogenization of these compounds have been developed. This final section outlines some relevant examples of the preparation of hybrid POM-based materials that could be useful to further expand the catalytic applications of POMs. 

Abstract The catalytic oxidation is an area of the key technologies for converting petroleum-based feedstocks to useful chemicals such as diols, epoxides, alcohols, and carbonyl compounds. Many efficient homogeneous and heterogeneous oxidation systems based on polyoxometalates (POMs) with green oxidants such as H2O2 and O2 have been developed. This chapter summarizes the remarkable oxidation catalyses by POMs with multimetallic active sites. The multifunctionality of multimetallic active sites in POMs such as cooperative activation of oxidants, simultaneous activation of oxidants and substrates, stabilization of reaction intermediates, and multielectron transfer leads to their remarkable activities and selec-tivities in comparison with the conventional monometallic complexes. Finally, the future opportunities for the development of shape- and stereoselective oxidation by POM-based catalysts are described. 

However, styrene and cyclohexene gave complex product mixtures, and 1-octene did not react under the same reaction conditions. Thus, the activity of this catalyst is intrinsically low. Jacobs and co-workers [159,160] applied Veturello s catalyst [PO WCKOj ]3- (tethered on a commercial nitrate-form resin with alkylammonium cations) to the epoxidation of allylic alcohols and terpenes. The regio- and diastereoselectivity of the parent homogeneous catalysts were preserved in the supported catalyst. For bulky alkenes, the reactivity of the POM catalyst was superior to that of Ti-based catalysts with large pore sizes such as Ti-p and Ti-MCM-48. The catalytic activity of the recycled catalyst was completely maintained after several cycles and the filtrate was catalytically inactive, indicating that the observed catalysis is truly heterogeneous in nature. 

A networked supramolecular POM-based hybrid catalyst has been synthesized by Ikegami and coworkers via the self-assembly of [PWi2O40]3 and non-crosslinked copolymer based on N-isopropylacrylamide (NIPAM) and ammonium cations (Figure 6.7) [124, 125]. This heterogeneous NIPAM-POM hybrid catalyst showed very high catalytic activity for the epoxidation of allylic alcohols with H202 (e.g., up to 35 000 TON for phytol). In addition, the oxygenation of amines and sulfide could be... 

Zr- and Ti-based POMs have been suggested as molecular models for the well-known heterogeneous titanium silicalite catalyst, TS-1, with major industrial appeal in the field of H2O2 activation and selective oxidation. In some cases, POMs... 

As mentioned in Sect. 2, many efficient homogeneous and heterogeneous oxidation systems based on POMs have been developed. Among them, some POM catalysts with multimetallic active sites show remarkable activity and selectivity in comparison with the conventional monometalhc complexes. According to the proposed reaction mechanisms, the oxidation catalyses by multimetallic active sites of POMs are classified into the following four categories (1) cooperative activation of oxidants, (2) simultaneous activation of oxidants and substrates, (3) stabihzation of reaction intermediates, and (4) multielectron transfer (Fig. 1). In Sect. 3, we focus on the selective oxidations by multimetallic active sites of POM-based molecular catalysts. 

Various types of POMs are effective catalysts for the H202- and 02-based environment-friendly oxidations. Most of these oxidations are carried out in homogeneous systems and share common drawbacks, that is, catalyst/product separation and catalyst recycling are very difficult. The heterogenization of POMs can improve the catalyst recovery and recycling. This chapter focuses on the development of (1) homogeneous catalysts with POMs and (2) the heterogenization for liquid phase-oxidations. 

The technique has been fruitfully used to characterize acid and basic sites in many catalysts, in particular for zeoHtes and metal oxides [143]. It has also been applied for POMs [144]. It consists of measuring the differential heats of adsorption when adsorbing successive increments of a basic probe molecule such as ammonia or pyridine for acidity characterization or of an acid probe molecule such as GO2 or SO2 to characterize basicity. The technique produces a histogram of the acid-base strength as a function of coverage, in particular when heterogeneity in strength exists. The data should then be compared with ammonia or pyridine desorption data from IR and thermal desorption experiments (see above). 

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