Product Code Database
For the purpose of classifying these materials, the chalcogenide is often viewed as a dianion, i.e., sulfide, selenide, Te2−, and polonide. In fact, transition metal chalcogenides are highly covalent, not ionic, as indicated by their semiconducting properties.
Important monochalcogenides include some , notably cadmium sulfide. Many minerals and ores are monosulfides.Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.), Oxford:Butterworth-Heinemann. .
The chalcogen is assigned positive oxidation states for the halides, nitrides, and oxides.
Metal-rich chalcogenides
In most of their chalcogenides, transition metals adopt oxidation states of II or greater. Nonetheless, several examples exist where the metallic atoms far outnumber the chalcogens. Such compounds typically have extensive metal-metal bonding.
Monochalcogenides
Metal monochalcogenides have the formula ME, where M = a transition metal and E = S, Se, Te. They typically crystallize in one of two motifs, named after the corresponding forms of zinc sulfide. In the zinc blende structure, the sulfide atoms pack in a cubic symmetry and the Zn2+ ions occupy half of the tetrahedral holes. The result is a diamondoid framework. The main alternative structure for the monochalcogenides is the wurtzite structure wherein the atom connectivities are similar (tetrahedral), but the crystal symmetry is hexagonal. A third motif for metal monochalcogenide is the nickel arsenide lattice, where the metal and chalcogenide each have octahedral and trigonal prismatic coordination, respectively. This motif is commonly subject to nonstoichiometry."Sulfide Mineralogy: Volume 1" Paul H. Ribbe, editor, 1974, Mineralogical Society of America.
Dichalcogenides
dichalcogenides have the formula ME2, where M = a transition metal and E = S, Se, Te.Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. . The most important members are the sulfides. They are always dark diamagnetic solids, insoluble in all solvents, and exhibit Semiconductor properties. Some are superconductors.
In terms of their electronic structures, these compounds are usually viewed as derivatives of M4+, where M4+ = Ti4+ (d0 configuration), V4+ (d1 configuration), Mo4+ (d2 configuration). Titanium disulfide was investigated in prototype for secondary batteries, exploiting its ability to reversibly undergo intercalation by lithium. Molybdenum disulfide is the subject of thousands of articles and the main ore of molybdenum, termed molybdenite. It is used as a solid lubricant and catalyst for hydrodesulfurization. The corresponding diselenides and even ditellurides are known, e.g., TiSe2, MoSe2, and WSe2.
Transition metals
Transition metal dichalcogenides typically adopt either cadmium diiodide or molybdenum disulfide structures. In the CdI2 motif, the metals exhibit octahedral structures. In the MoS2 motif, which is not observed for dihalides, the metals exhibit trigonal prismatic structures. The strong bonding between the metal and chalcogenide ligands, contrasts with the weak chalcogenide—chalcogenide bonding between the layers. Owing to these contrasting bond strengths, these materials engage in intercalation by alkali metals. The intercalation process is accompanied by charge transfer, reducing the M(IV) centers to M(III). The attraction between electrons and holes in 2D tungsten diselenide is 100s of times stronger than in a typical 3D semiconductor.
Pyrite and related disulfides
In contrast to classical metal dichalcogenides, iron pyrite, a common mineral, is usually described as consisting of Fe2+ and the persulfido anion S22−. The sulfur atoms within the persulfido dianion are bound together via a short S-S bond. "Late" transition metal disulfides (Mn, Fe, Co, Ni) almost always adopt the pyrite or the related marcasite motif, in contrast to early metals (V, Ti, Mo, W) which adopt 4+ oxidation state with two chalcogenide dianions.
Tri- and tetrachalcogenides
Several metals, mainly for the early metals (Ti, V, Cr, Mn groups) also form trichalcogenides. These materials are usually described as M4+(E22−)(E2−) (where E = S, Se, Te). A well known example is niobium triselenide. Amorphous MoS3 is produced by treatment of tetrathiomolybdate with acid:
The mineral patrónite, which has the formula VS4, is an example of a metal tetrachalcogenide. Crystallographic analysis shows that the material can be considered a bis(persulfide), i.e. V4+,(S22−)2.
Main group chalcogenides
Chalcogen derivatives are known for all of the main group elements except the noble gases. Usually, their stoichiometries follow the classical valence trends, e.g. SiS2, boron sulfide, Sb2S3. Many exceptions exist however, e.g. P4S3 and S4N4. The structures of many main group materials are dictated by directional covalent bonding, rather than by close packing.
See also
External links
|
|
