Transition-metal
sulfides are prodigiously studied materials with
a 100-year history in the development of catalysts and hierarchal
structures found throughout the energy industry. A constructive subset
of these compounds are the Group VI tetrathiometallates of the form
[MS4]2–(where M = Mo or W) that are used
as building blocks in a variety of complex chalcogenide-based materials.
Originally used as structural motifs for building nitrogenase model
clusters, these salts have since been incorporated into commercially
relevant products, such as pharmaceuticals, unsupported catalysts,
porous networks for separations, and solar cell components. Tetrathiometallate
anions are advantageous as metal sulfide constructs, because of their
simple synthesis and solubility in aqueous or polar hydrocarbon solvents
made tunable by selection of the proper cation. This minireview will
provide historical context of [MS4]2– salts used in the preparation of conventional sulfide materials
and discuss their relevance to areas related to the energy transition.
Examples of the latter include their use as catalysts for crude oil
conversion, as porous structures for gas separations or contaminant
removal, and in electrodes for photoelectrochemical devices.