Phase-supported oxidant

Because x-rays are particularly penetrating, they are very usefiil in probing solids, but are not as well suited for the analysis of surfaces. X-ray diffraction (XRD) methods are nevertheless used routinely in the characterization of powders and of supported catalysts to extract infomration about the degree of crystallinity and the nature and crystallographic phases of oxides, nitrides and carbides [, ]. Particle size and dispersion data are often acquired with XRD as well. 

The anhydride of 1,8-naphthalenedicarboxyHc acid is obtained in ca 95—116 wt % yield by the vapor-phase air-oxidation of acenaphthene at ca 330—450°C, using unsupported or supported vanadium oxide catalysts, with or without modifiers (96). 

Isopropyl Alcohol. Propylene may be easily hydrolyzed to isopropyl alcohol. Eady commercial processes involved the use of sulfuric acid in an indirect process (100). The disadvantage was the need to reconcentrate the sulfuric acid after hydrolysis. Direct catalytic hydration of propylene to 2-propanol followed commercialization of the sulfuric acid process and eliniinated the need for acid reconcentration, thus reducing corrosion problems, energy use, and air pollution by SO2 and organic sulfur compounds. Gas-phase hydration takes place over supported oxides of tungsten at 540 K and 25... 

FIG. 2 Cyclic voltammogram of the ferricenium transfer across the water-DCE interface at lOmVs. The electrochemical cell featured a similar arrangement to Fig. 1(b), but the organic phase contained 2mM of ferrocene. Heterogeneous oxidation of Fc occurred in the presence of 0.2mM CUSO4 in the aqueous phase. Supporting electrolytes were lOmM 02804 and lOmM BTPPATPBCl. The transfer of the standard tetramethylammonium (TMA+) under the same condition is also superimposed. 

Transition metal oxides, rare earth oxides and various metal complexes deposited on their surface are typical phases of DeNO catalysts that lead to redox properties. For each of these phases, complementary tools exist for a proper characterization of the metal coordination number, oxidation state or nuclearity. Among all the techniques such as EPR [80], UV-vis [81] and IR, Raman, transmission electron microscopy (TEM), X-ray absorption spectroscopy (XAS) and NMR, recently reviewed [82] for their application in the study of supported molecular metal complexes, Raman and IR spectroscopies are the only ones we will focus on. The major advantages offered by these spectroscopic techniques are that (1) they can detect XRD inactive amorphous surface metal oxide phases as well as crystalline nanophases and (2) they are able to collect information under various environmental conditions [83], We will describe their contributions to the study of both the support (oxide) and the deposited phase (metal complex). 

Raman spectroscopy has been used for a long time in order to study supported and promoted metal catalysts and oxide catalysts [84] since many information can be obtained (1) identification of different metal oxide phases (2) structural transformations of metal oxide phases (3) location of the supported oxide on the oxide substrate and... 

TOF-SIMS images (Figs. 13.5 and 13.6) illustrate the ability to detect changes in the dispersion (uniform or presence of metal clusters) of the active phase in supported-oxide catalysts. Figure 13.5 shows nearly uniform distribution of molybdenum. The surface contamination with NH4+ ions coming from a precursor, which were not removed during the catalyst preparation process, is also observed. Cobalt clusters in the range of several micrometers are clearly visible in Fig. 13.6. 

B. Better tools available, but no consensus on mechanism or active site—1980 to 2006. Rhodes et al.291 published a comprehensive review on the heterogeneously catalyzed water-gas shift mechanism in 1995. Included in that discussion was the copper/zinc oxide/alumina system. The conclusion was that this system appears to be constructed of small metallic islands of copper resting on a zinc oxide alumina phase. Zinc oxide may exert some impact on catalytic activity, but it was suggested in the review that the contribution is small. It was indicated that strong evidence exists to support either a formate or a redox mechanism, and the authors even suggest the possibility that both mechanisms might occur, though insufficient data exist to determine which mechanism predominates. 

The aqueous phase air oxidation of glycerol with supported noble metal catalysts occurs under mild conditions (60 °C), but is very dependant on the pH of the reaction medium. Relevant data are shown in Fig. 11.3 [48], For Pd, Pt and Bi-promoted Pt the glycerol oxidation rate increases significantly with the pH of the medium, with Pd showing the lower activity. 

The activity of elemental carbon as a metal-free catalyst is well established for a couple of reactions, however, most literature still deals with the support properties of this material. The discovery of nanostructured carbons in most cases led to an increased performance for the abovementioned reasons, thus these systems attracted remarkable research interest within the last years. The most prominent reaction is the oxidative dehydrogenation (ODH) of ethylbenzene and other hydrocarbons in the gas phase, which will be introduced in a separate chapter. The conversion of alcohols as well as the catalytic properties of graphene oxide for liquid phase selective oxidations will also be discussed in more detail. The third section reviews individually reported catalytic effects of nanocarbons in organic reactions, as well as selected inorganic reactions. 

In general, there are two possibilities to prepare nanocarbon-supported metal(oxide) catalysts. The in situ approach grows the catalyst nanoparticles directly on the carbon surface. The ex situ strategy utilizes pre-formed catalyst particles, which are deposited on the latter by adsorption [94]. Besides such solution-based methods, there is also the possibility of gas phase metal (oxide) loading, e.g., by sputtering [95], which is used for preparation of highly loaded systems required for electrochemical applications not considered here. 

Supported Polyoxometalate-Based Heterogeneous Catalysis for Liquid Phase Selective Oxidations... 

A solid-phase sulfur oxidation catalyst has been described in which the chiral ligand is structurally related to Schiff-base type compounds (see also below). A 72% ee was found using Ti(OPr-i)4, aqueous H2O2 and solid-supported hgand 91 . More recently, a heterogeneous catalytic system based on WO3, 30% H2O2 and cinchona alkaloids has been reported for the asymmetric oxidation of sulfides to sulfoxides and kinetic resolution of racemic sulfoxides. In this latter case 90% ee was obtained in the presence of 92 as chiral mediator. ... 

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