Molybdenum disulfide

Last updated
Molybdenum disulfide
MoS2chips.jpg
Molybdenite-3D-balls.png
Names
IUPAC name
Molybdenum disulfide
Other names
Molybdenum(IV) sulfide
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.013.877 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
RTECS number
  • QA4697000
UNII
  • InChI=1S/Mo.2S Yes check.svgY
    Key: CWQXQMHSOZUFJS-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/Mo.2S/rMoS2/c2-1-3
    Key: CWQXQMHSOZUFJS-FRBXWHJUAU
  • S=[Mo]=S
Properties
MoS2
Molar mass 160.07 g·mol−1
Appearanceblack/lead-gray solid
Density 5.06 g/cm3 [1]
Melting point 2,375 °C (4,307 °F; 2,648 K) [2]
insoluble [1]
Solubility decomposed by aqua regia, hot sulfuric acid, nitric acid
insoluble in dilute acids
Band gap 1.23 eV (indirect, 3R or 2H bulk) [3]
~1.8 eV (direct, monolayer) [4]
Structure
hP6, P6
3
/mmc
, No. 194 (2H)

hR9, R3m, No 160 (3R) [5]

a = 0.3161 nm (2H), 0.3163 nm (3R), c = 1.2295 nm (2H), 1.837 (3R)
Trigonal prismatic (MoIV)
Pyramidal (S2−)
Thermochemistry
Std molar
entropy
(S298)
62.63 J/(mol·K)
−235.10 kJ/mol
−225.89 kJ/mol
Hazards
Safety data sheet (SDS) External MSDS
Related compounds
Other anions
Molybdenum(IV) oxide
Molybdenum diselenide
Molybdenum ditelluride
Other cations
Tungsten disulfide
Related lubricants
Graphite
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Molybdenum disulfide (or moly) is an inorganic compound composed of molybdenum and sulfur. Its chemical formula is MoS2.

Contents

The compound is classified as a transition metal dichalcogenide. It is a silvery black solid that occurs as the mineral molybdenite, the principal ore for molybdenum. [6] MoS2 is relatively unreactive. It is unaffected by dilute acids and oxygen. In appearance and feel, molybdenum disulfide is similar to graphite. It is widely used as a dry lubricant because of its low friction and robustness. Bulk MoS2 is a diamagnetic, indirect bandgap semiconductor similar to silicon, with a bandgap of 1.23 eV. [3]

Production

Molybdenite Molly Hill molybdenite.JPG
Molybdenite

MoS2 is naturally found as either molybdenite, a crystalline mineral, or jordisite, a rare low temperature form of molybdenite. [7] Molybdenite ore is processed by flotation to give relatively pure MoS2. The main contaminant is carbon. MoS2 also arises by thermal treatment of virtually all molybdenum compounds with hydrogen sulfide or elemental sulfur and can be produced by metathesis reactions from molybdenum pentachloride. [8]

Structure and physical properties

Electron microscopy of antisites (a, Mo substitutes for S) and vacancies (b, missing S atoms) in a monolayer of molybdenum disulfide. Scale bar: 1 nm. MoS2 antisites&vacancies.jpg
Electron microscopy of antisites (a, Mo substitutes for S) and vacancies (b, missing S atoms) in a monolayer of molybdenum disulfide. Scale bar: 1 nm.

Crystalline phases

All forms of MoS2 have a layered structure, in which a plane of molybdenum atoms is sandwiched by planes of sulfide ions. These three strata form a monolayer of MoS2. Bulk MoS2 consists of stacked monolayers, which are held together by weak van der Waals interactions.

Crystalline MoS2 exists in one of two phases, 2H-MoS2 and 3R-MoS2, where the "H" and the "R" indicate hexagonal and rhombohedral symmetry, respectively. In both of these structures, each molybdenum atom exists at the center of a trigonal prismatic coordination sphere and is covalently bonded to six sulfide ions. Each sulfur atom has pyramidal coordination and is bonded to three molybdenum atoms. Both the 2H- and 3R-phases are semiconducting. [10]

A third, metastable crystalline phase known as 1T-MoS2 was discovered by intercalating 2H-MoS2 with alkali metals. [11] This phase has trigonal symmetry and is metallic. The 1T-phase can be stabilized through doping with electron donors such as rhenium, [12] or converted back to the 2H-phase by microwave radiation. [13] The 2H/1T-phase transition can be controlled via the incorporation of S vacancies. [14]

Allotropes

Nanotube-like and buckyball-like molecules composed of MoS2 are known. [15]

Exfoliated MoS2 flakes

While bulk MoS2 in the 2H-phase is known to be an indirect-band gap semiconductor, monolayer MoS2 has a direct band gap. The layer-dependent optoelectronic properties of MoS2 have promoted much research in 2-dimensional MoS2-based devices. 2D MoS2 can be produced by exfoliating bulk crystals to produce single-layer to few-layer flakes either through a dry, micromechanical process or through solution processing.

Micromechanical exfoliation, also pragmatically called "Scotch-tape exfoliation", involves using an adhesive material to repeatedly peel apart a layered crystal by overcoming the van der Waals forces. The crystal flakes can then be transferred from the adhesive film to a substrate. This facile method was first used by Konstantin Novoselov and Andre Geim to obtain graphene from graphite crystals. However, it can not be employed for a uniform 1-D layers because of weaker adhesion of MoS2 to the substrate (either Si, glass or quartz); the aforementioned scheme is good for graphene only. [16] While Scotch tape is generally used as the adhesive tape, PDMS stamps can also satisfactorily cleave MoS2 if it is important to avoid contaminating the flakes with residual adhesive. [17]

Liquid-phase exfoliation can also be used to produce monolayer to multi-layer MoS2 in solution. A few methods include lithium intercalation [18] to delaminate the layers and sonication in a high-surface tension solvent. [19] [20]

Mechanical properties

MoS2 excels as a lubricating material (see below) due to its layered structure and low coefficient of friction. Interlayer sliding dissipates energy when a shear stress is applied to the material. Extensive work has been performed to characterize the coefficient of friction and shear strength of MoS2 in various atmospheres. [21] The shear strength of MoS2 increases as the coefficient of friction increases. This property is called superlubricity. At ambient conditions, the coefficient of friction for MoS2 was determined to be 0.150, with a corresponding estimated shear strength of 56.0 MPa (megapascals). [21] Direct methods of measuring the shear strength indicate that the value is closer to 25.3 MPa. [22]

The wear resistance of MoS2 in lubricating applications can be increased by doping MoS2 with Cr. Microindentation experiments on nanopillars of Cr-doped MoS2 found that the yield strength increased from an average of 821 MPa for pure MoS2 (at 0% Cr) to 1017 MPa at 50% Cr. [23] The increase in yield strength is accompanied by a change in the failure mode of the material. While the pure MoS2 nanopillar fails through a plastic bending mechanism, brittle fracture modes become apparent as the material is loaded with increasing amounts of dopant. [23]

The widely used method of micromechanical exfoliation has been carefully studied in MoS2 to understand the mechanism of delamination in few-layer to multi-layer flakes. The exact mechanism of cleavage was found to be layer dependent. Flakes thinner than 5 layers undergo homogenous bending and rippling, while flakes around 10 layers thick delaminated through interlayer sliding. Flakes with more than 20 layers exhibited a kinking mechanism during micromechanical cleavage. The cleavage of these flakes was also determined to be reversible due to the nature of van der Waals bonding. [24]

In recent years, MoS2 has been utilized in flexible electronic applications, promoting more investigation into the elastic properties of this material. Nanoscopic bending tests using AFM cantilever tips were performed on micromechanically exfoliated MoS2 flakes that were deposited on a holey substrate. [17] [25] The yield strength of monolayer flakes was 270 GPa, [25] while the thicker flakes were also stiffer, with a yield strength of 330 GPa. [17] Molecular dynamic simulations found the in-plane yield strength of MoS2 to be 229 GPa, which matches the experimental results within error. [26]

Bertolazzi and coworkers also characterized the failure modes of the suspended monolayer flakes. The strain at failure ranges from 6 to 11%. The average yield strength of monolayer MoS2 is 23 GPa, which is close to the theoretical fracture strength for defect-free MoS2. [25]

The band structure of MoS2 is sensitive to strain. [27] [28] [29]

Chemical reactions

Molybdenum disulfide is stable in air and attacked only by aggressive reagents. It reacts with oxygen upon heating forming molybdenum trioxide:

2 MoS2 + 7 O2 → 2 MoO3 + 4 SO2

Chlorine attacks molybdenum disulfide at elevated temperatures to form molybdenum pentachloride:

2 MoS2 + 7 Cl2 → 2 MoCl5 + 2 S2Cl2

Intercalation reactions

Molybdenum disulfide is a host for formation of intercalation compounds. This behavior is relevant to its use as a cathode material in batteries. [30] [31] One example is a lithiated material, LixMoS2. [32] With butyl lithium, the product is LiMoS2. [6]

Applications

Lubricant

A tube of commercial graphite powder lubricant with molybdenum disulfide additive (called "molybdenum") Graphite moly.jpg
A tube of commercial graphite powder lubricant with molybdenum disulfide additive (called "molybdenum")

Due to weak van der Waals interactions between the sheets of sulfide atoms, MoS2 has a low coefficient of friction. MoS2 in particle sizes in the range of 1–100 μm is a common dry lubricant. [34] Few alternatives exist that confer high lubricity and stability at up to 350 °C in oxidizing environments. Sliding friction tests of MoS2 using a pin on disc tester at low loads (0.1–2 N) give friction coefficient values of <0.1. [35] [36]

MoS2 is often a component of blends and composites that require low friction. For example, it is added to graphite to improve sticking. [33] A variety of oils and greases are used, because they retain their lubricity even in cases of almost complete oil loss, thus finding a use in critical applications such as aircraft engines. When added to plastics, MoS2 forms a composite with improved strength as well as reduced friction. Polymers that may be filled with MoS2 include nylon (trade name Nylatron), Teflon and Vespel. Self-lubricating composite coatings for high-temperature applications consist of molybdenum disulfide and titanium nitride, using chemical vapor deposition.

Examples of applications of MoS2-based lubricants include two-stroke engines (such as motorcycle engines), bicycle coaster brakes, automotive CV and universal joints, ski waxes [37] and bullets. [38]

Other layered inorganic materials that exhibit lubricating properties (collectively known as solid lubricants (or dry lubricants)) includes graphite, which requires volatile additives and hexagonal boron nitride. [39]

Catalysis

Fingerprint revealed by molybdenum disulfide Molybdenum disulfide - 17.jpg
Fingerprint revealed by molybdenum disulfide

MoS2 is employed as a cocatalyst for desulfurization in petrochemistry, for example, hydrodesulfurization. The effectiveness of the MoS2 catalysts is enhanced by doping with small amounts of cobalt or nickel. The intimate mixture of these sulfides is supported on alumina. Such catalysts are generated in situ by treating molybdate/cobalt or nickel-impregnated alumina with H
2
S
or an equivalent reagent. Catalysis does not occur at the regular sheet-like regions of the crystallites, but instead at the edge of these planes. [40]

MoS2 finds use as a hydrogenation catalyst for organic synthesis. [41] It is derived from a common transition metal, rather than group 10 metal as are many alternatives, MoS2 is chosen when catalyst price or resistance to sulfur poisoning are of primary concern. MoS2 is effective for the hydrogenation of nitro compounds to amines and can be used to produce secondary amines via reductive amination. [42] The catalyst can also effect hydrogenolysis of organosulfur compounds, aldehydes, ketones, phenols and carboxylic acids to their respective alkanes. [41] The catalyst suffers from rather low activity however, often requiring hydrogen pressures above 95 atm and temperatures above 185 °C.

Research

MoS2 plays an important role in condensed matter physics research. [43]

Hydrogen evolution

MoS2 and related molybdenum sulfides are efficient catalysts for hydrogen evolution, including the electrolysis of water; [44] [45] thus, are possibly useful to produce hydrogen for use in fuel cells. [46]

Oxygen reduction and evolution

MoS2@Fe-N-C core/shell [47] nanosphere with atomic Fe-doped surface and interface (MoS2/Fe-N-C) can be used as a used an electrocatalyst for oxygen reduction and evolution reactions (ORR and OER) bifunctionally because of reduced energy barrier due to Fe-N4 dopants and unique nature of MoS2/Fe-N-C interface.

Microelectronics

As in graphene, the layered structures of MoS2 and other transition metal dichalcogenides exhibit electronic and optical properties [48] that can differ from those in bulk. [49] Bulk MoS2 has an indirect band gap of 1.2 eV, [50] [51] while MoS2 monolayers have a direct 1.8 eV electronic bandgap, [52] supporting switchable transistors [53] and photodetectors. [54] [49] [55]

MoS2 nanoflakes can be used for solution-processed fabrication of layered memristive and memcapacitive devices through engineering a MoOx/MoS2 heterostructure sandwiched between silver electrodes. [56] MoS2-based memristors are mechanically flexible, optically transparent and can be produced at low cost.

The sensitivity of a graphene field-effect transistor (FET) biosensor is fundamentally restricted by the zero band gap of graphene, which results in increased leakage and reduced sensitivity. In digital electronics, transistors control current flow throughout an integrated circuit and allow for amplification and switching. In biosensing, the physical gate is removed and the binding between embedded receptor molecules and the charged target biomolecules to which they are exposed modulates the current. [57]

MoS2 has been investigated as a component of flexible circuits. [58] [59]

In 2017, a 115-transistor, 1-bit microprocessor implementation was fabricated using two-dimensional MoS2. [60]

MoS2 has been used to create 2D 2-terminal memristors and 3-terminal memtransistors. [61]

Valleytronics

Due to the lack of spatial inversion symmetry, odd-layer MoS2 is a promising material for valleytronics because both the CBM and VBM have two energy-degenerate valleys at the corners of the first Brillouin zone, providing an exciting opportunity to store the information of 0s and 1s at different discrete values of the crystal momentum. The Berry curvature is even under spatial inversion (P) and odd under time reversal (T), the valley Hall effect cannot survive when both P and T symmetries are present. To excite valley Hall effect in specific valleys, circularly polarized lights were used for breaking the T symmetry in atomically thin transition-metal dichalcogenides. [62] In monolayer MoS2, the T and mirror symmetries lock the spin and valley indices of the sub-bands split by the spin-orbit couplings, both of which are flipped under T; the spin conservation suppresses the inter-valley scattering. Therefore, monolayer MoS2 have been deemed an ideal platform for realizing intrinsic valley Hall effect without extrinsic symmetry breaking. [63]

Photonics and photovoltaics

MoS2 also possesses mechanical strength, electrical conductivity, and can emit light, opening possible applications such as photodetectors. [64] MoS2 has been investigated as a component of photoelectrochemical (e.g. for photocatalytic hydrogen production) applications and for microelectronics applications. [53]

Superconductivity of monolayers

Under an electric field MoS2 monolayers have been found to superconduct at temperatures below 9.4 K. [65]

See also

Related Research Articles

Sulfide (also sulphide in British English ) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. Sulfide also refers to large families of inorganic and organic compounds, e.g. lead sulfide and dimethyl sulfide. Hydrogen sulfide (H2S) and bisulfide (SH) are the conjugate acids of sulfide.

<span class="mw-page-title-main">Molybdenite</span> Molybdenum disulfide mineral

Molybdenite is a mineral of molybdenum disulfide, MoS2. Similar in appearance and feel to graphite, molybdenite has a lubricating effect that is a consequence of its layered structure. The atomic structure consists of a sheet of molybdenum atoms sandwiched between sheets of sulfur atoms. The Mo-S bonds are strong, but the interaction between the sulfur atoms at the top and bottom of separate sandwich-like tri-layers is weak, resulting in easy slippage as well as cleavage planes. Molybdenite crystallizes in the hexagonal crystal system as the common polytype 2H and also in the trigonal system as the 3R polytype.

Molybdenum trioxide describes a family of inorganic compounds with the formula MoO3(H2O)n where n = 0, 1, 2. The anhydrous compound is produced on the largest scale of any molybdenum compound since it is the main intermediate produced when molybdenum ores are purified. The anhydrous oxide is a precursor to molybdenum metal, an important alloying agent. It is also an important industrial catalyst. It is a yellow solid, although impure samples can appear blue or green.

<span class="mw-page-title-main">Chalcogenide</span>

A chalcogenide is a chemical compound consisting of at least one chalcogen anion and at least one more electropositive element. Although all group 16 elements of the periodic table are defined as chalcogens, the term chalcogenide is more commonly reserved for sulfides, selenides, tellurides, and polonides, rather than oxides. Many metal ores exist as chalcogenides. Photoconductive chalcogenide glasses are used in xerography. Some pigments and catalysts are also based on chalcogenides. The metal dichalcogenide MoS2 is a common solid lubricant.

<span class="mw-page-title-main">Tungsten disulfide</span> Chemical compound

Tungsten disulfide is an inorganic chemical compound composed of tungsten and sulfur with the chemical formula WS2. This compound is part of the group of materials called the transition metal dichalcogenides. It occurs naturally as the rare mineral tungstenite. This material is a component of certain catalysts used for hydrodesulfurization and hydrodenitrification.

<span class="mw-page-title-main">Tantalum(IV) sulfide</span> Chemical compound

Tantalum(IV) sulfide is an inorganic compound with the formula TaS2. It is a layered compound with three-coordinate sulfide centres and trigonal prismatic or octahedral metal centres. It is structurally similar to molybdenum disulfide MoS2, and numerous other transition metal dichalcogenides. Tantalum disulfide has three polymorphs 1T-TaS2, 2H-TaS2, and 3R-TaS2, representing trigonal, hexagonal, and rhombohedral respectively.

<span class="mw-page-title-main">Titanium disulfide</span> Inorganic chemical compound

Titanium disulfide is an inorganic compound with the formula TiS2. A golden yellow solid with high electrical conductivity, it belongs to a group of compounds called transition metal dichalcogenides, which consist of the stoichiometry ME2. TiS2 has been employed as a cathode material in rechargeable batteries.

<span class="mw-page-title-main">Molybdenum diselenide</span> Chemical compound

Molybdenum diselenide is an inorganic compound of molybdenum and selenium. Its structure is similar to that of MoS
2
. Compounds of this category are known as transition metal dichalcogenides, abbreviated TMDCs. These compounds, as the name suggests, are made up of a transition metals and elements of group 16 on the periodic table of the elements. Compared to MoS
2
, MoSe
2
exhibits higher electrical conductivity.

<span class="mw-page-title-main">Tungsten diselenide</span> Chemical compound

Tungsten diselenide is an inorganic compound with the formula WSe2. The compound adopts a hexagonal crystalline structure similar to molybdenum disulfide. The tungsten atoms are covalently bonded to six selenium ligands in a trigonal prismatic coordination sphere while each selenium is bonded to three tungsten atoms in a pyramidal geometry. The tungsten–selenium bond has a length of 0.2526 nm, and the distance between selenium atoms is 0.334 nm. It is a well studied example of a layered material. The layers stack together via van der Waals interactions. WSe2 is a very stable semiconductor in the group-VI transition metal dichalcogenides.

<span class="mw-page-title-main">Transition metal dichalcogenide monolayers</span> Thin semiconductors

Transition-metal dichalcogenide (TMD or TMDC) monolayers are atomically thin semiconductors of the type MX2, with M a transition-metal atom (Mo, W, etc.) and X a chalcogen atom (S, Se, or Te). One layer of M atoms is sandwiched between two layers of X atoms. They are part of the large family of so-called 2D materials, named so to emphasize their extraordinary thinness. For example, a MoS2 monolayer is only 6.5 Å thick. The key feature of these materials is the interaction of large atoms in the 2D structure as compared with first-row transition-metal dichalcogenides, e.g., WTe2 exhibits anomalous giant magnetoresistance and superconductivity.

In materials science, the term single-layer materials or 2D materials refers to crystalline solids consisting of a single layer of atoms. These materials are promising for some applications but remain the focus of research. Single-layer materials derived from single elements generally carry the -ene suffix in their names, e.g. graphene. Single-layer materials that are compounds of two or more elements have -ane or -ide suffixes. 2D materials can generally be categorized as either 2D allotropes of various elements or as compounds.

A two-dimensional semiconductor is a type of natural semiconductor with thicknesses on the atomic scale. Geim and Novoselov et al. initiated the field in 2004 when they reported a new semiconducting material graphene, a flat monolayer of carbon atoms arranged in a 2D honeycomb lattice. A 2D monolayer semiconductor is significant because it exhibits stronger piezoelectric coupling than traditionally employed bulk forms. This coupling could enable applications. One research focus is on designing nanoelectronic components by the use of graphene as electrical conductor, hexagonal boron nitride as electrical insulator, and a transition metal dichalcogenide as semiconductor.

<span class="mw-page-title-main">Molybdenum ditelluride</span> Chemical compound

Molybdenum(IV) telluride, molybdenum ditelluride or just molybdenum telluride is a compound of molybdenum and tellurium with formula MoTe2, corresponding to a mass percentage of 27.32% molybdenum and 72.68% tellurium.

Platinum diselenide is a transition metal dichalcogenide with the formula PtSe2. It is a layered substance that can be split into layers down to three atoms thick. PtSe2 can behave as a metalloid or as a semiconductor depending on the thickness.

<span class="mw-page-title-main">Niobium diselenide</span> Chemical compound

Niobium diselenide or niobium(IV) selenide is a layered transition metal dichalcogenide with formula NbSe2. Niobium diselenide is a lubricant, and a superconductor at temperatures below 7.2 K that exhibit a charge density wave (CDW). NbSe2 crystallizes in several related forms, and can be mechanically exfoliated into monatomic layers, similar to other transition metal dichalcogenide monolayers. Monolayer NbSe2 exhibits very different properties from the bulk material, such as of Ising superconductivity, quantum metallic state, and strong enhancement of the CDW.

<span class="mw-page-title-main">Hafnium disulfide</span> Chemical compound

Hafnium disulfide is an inorganic compound of hafnium and sulfur. It is a layered dichalcogenide with the chemical formula is HfS2. A few atomic layers of this material can be exfoliated using the standard Scotch Tape technique (see graphene) and used for the fabrication of a field-effect transistor. High-yield synthesis of HfS2 has also been demonstrated using liquid phase exfoliation, resulting in the production of stable few-layer HfS2 flakes. Hafnium disulfide powder can be produced by reacting hydrogen sulfide and hafnium oxides at 500–1300 °C.

<span class="mw-page-title-main">Rhenium disulfide</span> Chemical compound

Rhenium disulfide is an inorganic compound of rhenium and sulfur with the formula ReS2. It has a layered structure where atoms are strongly bonded within each layer. The layers are held together by weak Van der Waals bonds, and can be easily peeled off from the bulk material.

Tony Frederick Heinz is an American physicist.

<span class="mw-page-title-main">Layered materials</span>

In material science, layered materials are solids with highly anisotropic bonding, in which two-dimensional sheets are internally strongly bonded, but only weakly bonded to adjacent layers. Owing to their distinctive structures, layered materials are often suitable for intercalation reactions.

<span class="mw-page-title-main">Tantalum diselenide</span> Chemical compound

Tantalum diselenide is a compound made with tantalum and selenium atoms, with chemical formula TaSe2, which belongs to the family of transition metal dichalcogenides. In contrast to molybdenum disulfide (MoS2) or rhenium disulfide (ReS2), tantalum diselenide does not occur spontaneously in nature, but it can be synthesized. Depending on the growth parameters, different types of crystal structures can be stabilized.

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