A fascinating aspect of many of the selenium- and tellurium-containing compounds described in this volume is that they are built up from octahedral Mo6 clusters which are surrounded by eight other atoms X in the form of a cube: Mo6X8. The Mo atoms occupy the centers of the faces of the X8 cube. The interesting variety in the substiution of the X positions can be encountered throughout the whole volume. The X atoms can be of a single element as in Mo6Te8, but can also be statistically occupied by two elements, e.g., in Mo6(Te,S)8, or even by more elements as in Mo6(Te,Se)8-yIy. In addition, there are channels with vacant positions between the Mo6X8 clusters in the diagonal direction of the X8 cube. These vacant positions offer more possibilities for the fantasy of the chemist.
This volume describes preparation and properties of the enormous number of molybdenum oxide sulfide ions. The monomeric anions display an impressive range of colors - yellow to a deep reddish orange - which in 1826 fascinated Berzelius. Nowadays, however, the stimulus for research and development springs from bioinorganic chemistry. Numerous molybdenum chalcogenide halides are known: the most investigated have been those containing Mo6 clusters. In addition, the volume contains the binary molybdenum selenides; of these, the most important is the heavily studied MoSe2. Among the molybdenum dichalcogenides, MoSe2 shows the most promising photoelectrochemical properties, making it attractive for use in electrochemical solar cells. All binary molybdenum selenides reversibly intercalate a variety of metals - of importance for use in rechargeable batteries.
The Molybdenum Supplement Volume B/7 covers binary molybdenum sulfides and sulfide ions, the most prominent being molybdenum sulfide MoS2 on account of its numerous practical applications. It is a dry lubricant material and has become indispensable in high-vacuum and space applications. Semiconducting MoS2 photoelectrodes have achieved sizable solar energy conversions in photoelectrochemical cells. Its capability to reversibly intercalate lithium ions enables the construction of low-weight, high efficiency, secondary batteries. MoS2 doped with cobalt is useful as a catalyst of the hydrosulfurization of organic compounds. All these remarkable properties are related to its layered structure built up of covalently bound SMoS sheets held together by only weak van der Waals forces.
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