Phase Chevrel

Cherts CHESS Chevrefeuille Chevrel phase Chevron-Gulf process Chevron process... 

Lower formal oxidation states are stabilized, however, by M-M bonding in ternary chalcogenides such as M MeQn, M4M6Q13 (M = alkali metal M = Re, Tc Q = S, Se) and the recently reported M gMeS. Their structures are all based on the face-capped, octahedral MeXg cluster unit found in Chevrel phases (p. 1018) and in the dihalides of Mo and W... 

Perspectives for fabrication of improved oxygen electrodes at a low cost have been offered by non-noble, transition metal catalysts, although their intrinsic catalytic activity and stability are lower in comparison with those of Pt and Pt-alloys. The vast majority of these materials comprise (1) macrocyclic metal transition complexes of the N4-type having Fe or Co as the central metal ion, i.e., porphyrins, phthalocyanines, and tetraazaannulenes [6-8] (2) transition metal carbides, nitrides, and oxides (e.g., FeCjc, TaOjcNy, MnOx) and (3) transition metal chalcogenide cluster compounds based on Chevrel phases, and Ru-based cluster/amorphous systems that contain chalcogen elements, mostly selenium. 

Fig. 6.1 The fundamental structural unit found in the Chevrel phases (cluster MoeXg full circles Mo atoms) displayed in three ways to emphasize different views of the connectivity. In (a) an octahedron of molybdenums (Mo-Mo = 2.7 A) is encased in a cube of chalcogens (Mo-S 2.45 or Mo-Se 2.6 A). Scheme (b) exhibits the same cluster as consisting of an octahedron with its triangular faces capped by chalcogenides. In (c), the cluster has been reoriented so that a threefold axis is vertical. (Reproduced from [10])...

The different classes of Ru-based catalysts, including crystalline Chevrel-phase chalcogenides, nanostructured Ru, and Ru-Se clusters, and also Ru-N chelate compounds (RuNj), have been reviewed recently by Lee and Popov [29] in terms of the activity and selectivity toward the four-electron oxygen reduction to water. The conclusion was drawn that selenium is a critical element controlling the catalytic properties of Ru clusters as it directly modifies the electronic structure of the catalytic reaction center and increases the resistance to electrochemical oxidation of interfacial Ru atoms in acidic environments. 

We have already referred to the Mo/Ru/S Chevrel phases and related catalysts which have long been under investigation for their oxygen reduction properties. Reeve et al. [19] evaluated the methanol tolerance, along with oxygen reduction activity, of a range of transition metal sulfide electrocatalysts, in a liquid-feed solid-polymer-electrolyte DMFC. The catalysts were prepared in high surface area by direct synthesis onto various surface-functionalized carbon blacks. The intrinsic... 

Lancry E, Levi E, Gofer Y, Levi MD, Aurbach D (2005) The effect of milling on the performance of a MogSg Chevrel phase as a cathode material for rechargeable Mg batteries. J Sohd State Electrochem 9 259-266... 

Alonso-Vante N. 2003. Chevrel phases and chalcogenides. In Vielstich W, Gasteiger HA, Lamm A, editors. Handbook of Fuel Cells—Fundamentals, Technology and Applications. Chichester Wiley. 

The situation is very similar in the Chevrel phases. These are ternary molybdenum chalcogenides A,.[Mo6Xg] (A = metal, X = S, Se) that have attracted much attention because of their physical properties, especially as superconductors. The parent compound is PbMo6Sg it contains Mo6Sg clusters that are linked with each other in such a way that the free coordination sites of one cluster are occupied by sulfur atoms of adjacent clusters (Fig. 13.9). The electric properties of Chevrel phases depend on the number of valence electrons. With 24 electrons per cluster (one electron pair for each edge of the... 

Association of Mo6S8 clusters in the CHEVREL phase PbMo6S8 (stereo image)... 

Just as the Mo6Xg units in the Chevrel phases tolerate a certain lack of electrons (e.g. 20 instead of 24 skeleton electrons), clusters with M6X12 units which have fewer than 16 skeleton electrons are also possible. For example, in Zr6I12 there are only 12 skeleton electrons, and Sc7Cl12 = Sc3+[Sc6C112]3- has only nine. 

Most of the chalcogenide studies have involved binary, ternary, and pseudo ternary metal clusters. The ternary Chevrel-phases can be represented by MxMo6X8 (M = transition metal, X = chalcogen atom), where the transition metal fills the cavities in the Mo6X8 crystal structure. The pseudo-ternary (or pseudo-binary) Chevrel-phase clusters can be represented by MxMo6 xX8, where the Mo atoms are substituted by transition metal atoms.185 The crystal structure of ternary and pseudo ternary Chevrel phases are shown in Fig. 4. The carbonyl-chalcogenide clusters189 192 will be discussed in the next section. 

Fig. 4 The crystal structure of Chevrel phase chalcogenides. The atoms are represented by (Mo), O (chalcogen) and A (site of the metal atoms for the ternary Chevrel phases). For pseudo-binary phases, the Mo is partially substituted by the metal atoms. (181 With kind permission of Springer Science and Business Media).

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