Molybdenum ion

Molybdenum disulfide has a layered structure. Each layer is a sandwich consisting of between two layers of ions (Fig. 9.5). The sulfur ions form trigonal prisms and half of the prisms contain a molybdenum ion in the middle. The chemical reactivity of M0S2 is associated with the edges of the sandwich, whereas the basal planes are much less reactive. The edges form the sites where gases adsorb and where the catalytic activity resides. 

A number of molybdenum-containing hydroxylases catalyzing the first hydrox-ylation step of N-containing compounds have been characterized thoroughly (e.g., carbazole [314], quinoline [327], and indole [350]). The enzyme s redox-active has been described as a molybdenum ion site coordinated to a distinct pyranopterin cofactor (two different [2Fe2S] centers) and in most cases, flavin adenine dinucleotide centers. This active center transfers electrons from the N-heterocyclic substrate to an electron acceptor, which for many molybdenum hydroxylases is still unknown [350],... 

Cover Illustration Atomic force microscopy image of molybdenum oxide particles on flat, silicon dioxide substrate, which serves as a model system for a supported catalyst. The area shown corresponds to one square micrometer the maximum difference in height is approximately 10 nanometer. The superimposed curve is the secondary ion mass spectrum of the model catalyst, showing the caracteristic isotopic patterns of single molybdenum ions and of molybdenum oxide cluster ions. 

Another idea is to use a mediator such as molybdenum ions - or vanadium ions. Nakajima et clL. have proposed that a qrcling reaction involving lVfo(III)<—>Nfo(IV) mediates the methanol oxidation and have fovmd 100-200 mV gain to be achieved at lower cuirent densities. 

Nitrate reductase (NADH) [EC 1.6.6.1], also known as assimilatory nitrate reduetase, eatalyzes the reaction of NADH with nitrate to produee NAD+, nitrite, and water. This enzyme uses FAD or FMN, heme, and a molybdenum ion as eofaetors. (2) Nitrate reductase (NAD(P)H) [EC 1.6.6.2], also known as assimilatory nitrate reduetase, eatalyzes the reaetion of NAD(P)H with nitrate to produee NAD(P)+, nitrite, and water. This enzyme uses FAD or FMN, heme, and a molybdenum ion as eofaetors. (3) Nitrate reductase (NADPH) [EC 1.6.6.3] eatalyzes the reaetion of NADPH with nitrate to produee NADP+, nitrite, and water. This enzyme uses FAD, heme, and a molybdenum ion as cofactors. (4) Nitrate reduetase (eytoehrome) [EC 1.9.6.1] catalyzes the reaetion of nitrate with ferroeytochrome to produce nitrite and ferrieytoehrome. (5) Nitrate reductase (ac-eeptor) [EC 1.7.99.4], also known as respiratory nitrate... 

Nitrogenase (ferredoxin) [EC 1.18.6.1] catalyzes the reaction of three reduced ferredoxin molecules with protons, N2, and n ATP molecules to produce three oxidized ferredoxin molecules, two ammonia molecules, n ADP molecules, and n orthophosphate molecules where n is between 12 and 18. This iron-sulfur system also uses either molybdenum or vanadium ions. (2) Nitrogenase (flavodoxin) [EC 1.19.6.1] catalyzes the reaction of six reduced flavodoxin molecules with protons, N2, and n ATP molecules to produce six oxidized flavodoxin molecules, two ammonia molecules, n ADP molecules, and n orthophosphate molecules. This system uses iron-sulfur and molybdenum ions. 

Iron molybdates were investigated by several authors. It is generally observed that iron is reduced first (Fe3+ - Fe2+), while deeper reduction is required to reduce the molybdenum ions as well. Both cations occur in partially reduced states during the reaction with butene. Pernicone [254] concludes from his ESR work that under stationary reaction conditions the iron ions stay in the reduced state and that the redox process only involves Mo6+ and Mos+. However, Trifiro and Pasquon [318] and Matsu ura and Schuit [207] are of the opinion that reoxidation initially may lead to Fe3+ which in turn (rapidly) oxidizes the Mos+ ions at the hydrocarbon reaction sites of the catalyst. However, direct evidence is not provided. 

Molybdenum forms many other complexes. Of particular interest are the octacyano complexes, containing eight cyanide ions. CN. coordinated to a single tetravalent of pentavalenl molybdenum ion. MolCN)) and Mo(CN)MOg . the latter being exceptionally stable, and both form oclacyanomolybdic acids H, Mo(CN)R 3H-0 and R((Mo[Pg.1039]

In addition to the microscopic redox processes of bismuth ions and molybdenum ions, the combination of these conductivity measurements leads to the conclusion that the macroscopic, bulk conductivity properties of the bismuth molybdate catalyst affect the catalytic reaction. 

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