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'''Molybdenum disulfide''' is the [[inorganic chemistry|inorganic compound]] composed of only two elements: [[molybdenum]] and [[sulfur]]. Its [[chemical formula]] is '''{{chem|MoS|2}}'''.
'''Molybdenum disulfide''' is the [[inorganic chemistry|inorganic compound]] composed of only two elements: [[molybdenum]] and [[sulfur]]. Its [[chemical formula]] is '''{{chem|MoS|2}}'''.


The compound is classified as a metal di[[chalcogenide]]. It is a silvery black solid that occurs as the mineral [[molybdenite]], the principal ore for molybdenum.<ref name=ullmann>Sebenik, Roger F. ''et al''. (2005) "Molybdenum and Molybdenum Compounds", ''Ullmann's Encyclopedia of Chemical Technology''. Wiley-VCH, Weinheim. {{DOI| 10.1002/14356007.a16_655}}</ref> {{chem|MoS|2}} is relatively unreactive. It is unaffected by dilute [[acid]]s and [[oxygen]]. In appearance and feel, molybdenum di[[sulfide]] is similar to [[graphite]]. It is widely used as a solid [[lubricant]] because of its low [[friction]] properties and robustness. Bulk {{chem|MoS|2}} is a diamagnetic, [[indirect bandgap]] semiconductor similar to [[silicon]], with a bandgap of 1.23 eV.<ref name=band/>
The compound is classified as a metal di[[chalcogenide]]. It is a silvery black solid that occurs as the mineral [[molybdenite]], the principal ore for molybdenum.<ref name=ullmann>Sebenik, Roger F. ''et al''. (2005) "Molybdenum and Molybdenum Compounds", ''Ullmann's Encyclopedia of Chemical Technology''. Wiley-VCH, Weinheim. {{DOI| 10.1002/14356007.a16_655}}</ref> {{chem|MoS|2}} is relatively unreactive. It is unaffected by dilute [[acid]]s and [[oxygen]]. In appearance and feel, molybdenum di[[sulfide]] is similar to [[graphite]]. It is widely used as a solid [[lubricant]] because of its low [[friction]] properties and robustness. Bulk {{chem|MoS|2}} is a diamagnetic, [[indirect bandgap]] semiconductor similar to [[silicon]], with a bandgap of 1.23 eV.<ref name=band/>


== Production ==
== Production ==
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===Intercalation reactions===
===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.<ref>T. Stephenson, Z. Li, B. Olsen and D. Mitlin, "Lithium Ion Battery Applications of Molybdenum Disulfide (Mos2) Nanocomposites" Energy Environ. Sci., 2014, volume 7, 209-31. {{DOI|10.1039/C3EE42591F}}.</ref><ref>{{cite journal | last1 = Benavente | first1 = E. | last2 = Santa Ana | first2 = M. A. | last3 = Mendizabal | first3 = F. | last4 = Gonzalez | first4 = G. | year = 2002 | title = Intercalation chemistry of molybdenum disulfide | journal = Coordination Chemistry Reviews | volume = 224 | pages = 87–109 | doi = 10.1016/S0010-8545(01)00392-7 }}</ref> One example is lithiated material, {{chem|Li|x}}{{chem|MoS|2}}.<ref>{{cite book|title =Progress in intercalation research| author = Müller-Warmuth, W. and Schöllhorn, R. | url={{Google books|id=IyB_rPo3osUC|page=50|plainurl=yes}} |publisher= Springer| year = 1994| isbn =0-7923-2357-2}}</ref> With [[n-Butyllithium|butyl lithium]], the product is {{chem|LiMoS|2}}.<ref name=ullmann/>
Molybdenum disulfide is a host for formation of [[intercalation compounds]]. This behavior is relevant to its use as a cathode material in batteries.<ref>T. Stephenson, Z. Li, B. Olsen and D. Mitlin, "Lithium Ion Battery Applications of Molybdenum Disulfide (Mos2) Nanocomposites" Energy Environ. Sci., 2014, volume 7, 209-31. {{DOI|10.1039/C3EE42591F}}.</ref><ref>{{cite journal | last1 = Benavente | first1 = E. | last2 = Santa Ana | first2 = M. A. | last3 = Mendizabal | first3 = F. | last4 = Gonzalez | first4 = G. | year = 2002 | title = Intercalation chemistry of molybdenum disulfide | journal = Coordination Chemistry Reviews | volume = 224 | pages = 87–109 | doi = 10.1016/S0010-8545(01)00392-7 }}</ref> One example is lithiated material, {{chem|Li|x}}{{chem|MoS|2}}.<ref>{{cite book|title =Progress in intercalation research|author1=Müller-Warmuth, W. |author2=Schöllhorn, R. |lastauthoramp=yes | url={{Google books|id=IyB_rPo3osUC|page=50|plainurl=yes}} |publisher= Springer| year = 1994| isbn =0-7923-2357-2}}</ref> With [[n-Butyllithium|butyl lithium]], the product is {{chem|LiMoS|2}}.<ref name=ullmann/>


== Applications ==
== Applications ==

=== Lubricant ===
=== Lubricant ===
{{chem|MoS|2}} with particle sizes in the range of 1–100&nbsp;µm is a common [[dry lubricant]].<ref>{{citation| last=Claus| first= F. L. |year= 1972| title=Solid Lubricants and Self-Lubricating Solids| publisher= Academic Press| location= New York}}</ref> Few alternatives exist that confer high lubricity and stability at up to 350&nbsp;°C in oxidizing environments. Sliding friction tests of {{chem|MoS|2}} using a [[pin on disc tester]] at low loads (0.1–2 N) give friction coefficient values of <0.1.<ref>{{cite book| author =Miessler, G. L. and Tarr, D. A. | title =Inorganic Chemistry, 3rd Ed| publisher= Pearson/Prentice Hall publisher| isbn = 0-13-035471-6| year =2004}}</ref><ref>{{cite book| | last1=Shriver| first1= D. F.| last2= Atkins| first2= P. W.| last3= Overton| first3= T. L.| last4= Rourke| first4= J. P.| last5= Weller| first5= M. T.| last6= Armstrong| first6= F. A. | title =Inorganic Chemistry| publisher = W. H. Freeman| location= New York| year = 2006| isbn = 0-7167-4878-9}}</ref>
{{chem|MoS|2}} with particle sizes in the range of 1–100&nbsp;µm is a common [[dry lubricant]].<ref>{{citation| last=Claus| first= F. L. |year= 1972| title=Solid Lubricants and Self-Lubricating Solids| publisher= Academic Press| location= New York}}</ref> Few alternatives exist that confer high lubricity and stability at up to 350&nbsp;°C in oxidizing environments. Sliding friction tests of {{chem|MoS|2}} using a [[pin on disc tester]] at low loads (0.1–2 N) give friction coefficient values of <0.1.<ref>{{cite book|author1=Miessler, G. L. |author2=Tarr, D. A. |lastauthoramp=yes | title =Inorganic Chemistry, 3rd Ed| publisher= Pearson/Prentice Hall publisher| isbn = 0-13-035471-6| year =2004}}</ref><ref>{{cite book| last1=Shriver| first1= D. F.| last2= Atkins| first2= P. W.| last3= Overton| first3= T. L.| last4= Rourke| first4= J. P.| last5= Weller| first5= M. T.| last6= Armstrong| first6= F. A. | title =Inorganic Chemistry| publisher = W. H. Freeman| location= New York| year = 2006| isbn = 0-7167-4878-9}}</ref>


{{chem|MoS|2}} is often a component of blends and composites that require low friction. A variety of [[oil]]s and [[grease (lubricant)|grease]]s 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 engine]]s. When added to [[plastic]]s, {{chem|MoS|2}} forms a [[composite material|composite]] with improved strength as well as reduced friction. Polymers filled with {{chem|MoS|2}} include [[nylon]] (with the [[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]].
{{chem|MoS|2}} is often a component of blends and composites that require low friction. A variety of [[oil]]s and [[grease (lubricant)|grease]]s 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 engine]]s. When added to [[plastic]]s, {{chem|MoS|2}} forms a [[composite material|composite]] with improved strength as well as reduced friction. Polymers filled with {{chem|MoS|2}} include [[nylon]] (with the [[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]].
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=== Catalysis ===
=== Catalysis ===
{{chem|MoS|2}} is employed as a co[[catalyst]] for desulfurization in [[petrochemistry]], for example, [[hydrodesulfurization]].The effectiveness of the {{chem|MoS|2}} catalysts is enhanced by [[Doping (semiconductor)|doping]] with small amounts of [[cobalt]] or [[nickel]] The intimate mixture of these sulfides is [[catalyst support|supported]] on [[alumina]]. Such catalysts are generated in situ by treating molybdate/cobalt or nickel-impregnated alumina with {{chem|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.<ref>{{cite book| last1= Topsøe| first1= H.| last2= Clausen| first2= B. S.| last3= Massoth| first3= F. E. | title =Hydrotreating Catalysis, Science and Technology| publisher = Springer-Verlag| location= Berlin| year = 1996}}</ref>
{{chem|MoS|2}} is employed as a co[[catalyst]] for desulfurization in [[petrochemistry]], for example, [[hydrodesulfurization]].The effectiveness of the {{chem|MoS|2}} catalysts is enhanced by [[Doping (semiconductor)|doping]] with small amounts of [[cobalt]] or [[nickel]] The intimate mixture of these sulfides is [[catalyst support|supported]] on [[alumina]]. Such catalysts are generated in situ by treating molybdate/cobalt or nickel-impregnated alumina with {{chem|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.<ref>{{cite book| last1= Topsøe| first1= H.| last2= Clausen| first2= B. S.| last3= Massoth| first3= F. E. | title =Hydrotreating Catalysis, Science and Technology| publisher = Springer-Verlag| location= Berlin| year = 1996}}</ref>


MoS<sub>2</sub> also finds some use as a [[hydrogenation]] [[catalyst]] for [[organic synthesis]].<ref name=Shigeo>{{cite book|last1=Nishimura|first1=Shigeo|title=Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis|date=2001|publisher=Wiley-Interscience| location= New York| isbn= 9780471396987|pages=43–44 & 240–241|edition=1st|url=https://books.google.com/books?id=RjZRAAAAMAAJ&q=0471396982&dq=0471396982&hl=en&sa=X&ei=BCacVMTgN5LmoASd34KQCQ&ved=0CB8Q6AEwAA}}</ref> Being derived from a common [[transition metal]], rather than [[group 10]] metal like many alternatives, MoS<sub>2</sub> is chosen when catalyst price or resistance to sulfur [[Catalyst poisoning|poisoning]] are of primary concern. MoS<sub>2</sub> is effective for the hydrogenation of [[nitro compounds]] to [[amines]] and can be used produce [[Secondary (chemistry)|secondary]] amines via [[Reductive amination|reductive alkylation]].<ref>{{cite journal|last1=Dovell|first1=Frederick S.| last2= Greenfield| first2= Harold| title=Base-Metal Sulfides as Reductive Alkylation Catalysts|journal=The Journal of Organic Chemistry|date=1964|volume=29|issue=5|pages=1265–1267|doi=10.1021/jo01028a511}}</ref> The catalyst can also can effect [[hydrogenolysis]] of [[organosulfur compounds]], [[aldehyde]]s, [[ketone]]s, [[phenols]], and [[carboxylic acids]] to their respective [[alkane]]s.<ref name=Shigeo /> The catalyst suffers from rather low activity however, often requiring hydrogen [[pressure]]s above 95 [[Atmosphere (unit)|atm]] and temperatures above 185&nbsp;°C.
MoS<sub>2</sub> also finds some use as a [[hydrogenation]] [[catalyst]] for [[organic synthesis]].<ref name=Shigeo>{{cite book|last1=Nishimura|first1=Shigeo|title=Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis|date=2001|publisher=Wiley-Interscience| location= New York| isbn= 9780471396987|pages=43–44 & 240–241|edition=1st|url=https://books.google.com/books?id=RjZRAAAAMAAJ&q=0471396982&dq=0471396982&hl=en&sa=X&ei=BCacVMTgN5LmoASd34KQCQ&ved=0CB8Q6AEwAA}}</ref> Being derived from a common [[transition metal]], rather than [[group 10]] metal like many alternatives, MoS<sub>2</sub> is chosen when catalyst price or resistance to sulfur [[Catalyst poisoning|poisoning]] are of primary concern. MoS<sub>2</sub> is effective for the hydrogenation of [[nitro compounds]] to [[amines]] and can be used produce [[Secondary (chemistry)|secondary]] amines via [[Reductive amination|reductive alkylation]].<ref>{{cite journal|last1=Dovell|first1=Frederick S.| last2= Greenfield| first2= Harold| title=Base-Metal Sulfides as Reductive Alkylation Catalysts|journal=The Journal of Organic Chemistry|date=1964|volume=29|issue=5|pages=1265–1267|doi=10.1021/jo01028a511}}</ref> The catalyst can also can effect [[hydrogenolysis]] of [[organosulfur compounds]], [[aldehyde]]s, [[ketone]]s, [[phenols]], and [[carboxylic acids]] to their respective [[alkane]]s.<ref name=Shigeo /> The catalyst suffers from rather low activity however, often requiring hydrogen [[pressure]]s above 95 [[Atmosphere (unit)|atm]] and temperatures above 185&nbsp;°C.
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===Microelectronics===
===Microelectronics===
As in [[graphene]], the layered structures of {{chem|MoS|2}} and other [[transition metal]] dichalcogenides exhibit rich electronic and optical properties<ref name="nano">{{Cite journal | last1 = Wang | first1 = Q. H. | last2 = Kalantar-Zadeh | first2 = K. | last3 = Kis | first3 = A. | last4 = Coleman | first4 = J. N. | last5 = Strano | first5 = M. S. | title = Electronics and optoelectronics of two-dimensional transition metal dichalcogenides | doi = 10.1038/nnano.2012.193 | journal = Nature Nanotechnology | volume = 7 | issue = 11 | pages = 699–712 | year = 2012 | pmid = 23132225| pmc = }}</ref> that can differ from those in bulk.<ref name=promising>{{cite journal| first1=R. |last1=Ganatra |first2= Q. |last2= Zhang| title= Few-Layer MoS<sub>2</sub>: A Promising Layered Semiconductor| journal= ACS Nano| year= 2014| volume= 8| pages= 4074–99| doi=10.1021/nn405938z| accessdate= May 24, 2016}}</ref> Whereas bulk {{chem|MoS|2}} has an indirect band gap of 1.2 eV, [[Transition Metal Dichalcogenide monolayers|{{chem|MoS|2}} monolayers]] have a direct 1.8 eV [[band gap|electronic bandgap]],<ref name= Splendiani>{{cite journal|last1=Splendiani| first1=A.| last2= Sun| first2= L.| last3= Zhang| first3=Y.| last4= Li| first4= T.| last5= Kim| first5= J.|last6=Chim|first6=J.|last7=F.|year=2010|title=Emerging Photoluminescence in Monolayer MoS<sub>2</sub>|journal=Nano Letters|volume=10|issue=4|pages=1271–1275| doi=10.1021/nl903868w| pmid=20229981|bibcode=2010NanoL..10.1271S|last8=Wang|first8=Feng}}</ref> allowing the production of switchable transistors<ref name="Radisavljevic" /> and [[photodetectors]].<ref>{{cite journal | last1 = Lopez-Sanchez | first1 = O. | last2 = Lembke | first2 = D. | last3 = Kayci | first3 = M. | last4 = Radenovic | first4 = A. | last5 = Kis | first5 = A. | year = 2013 | title = Ultrasensitive photodetectors based on monolayer MoS<sub>2</sub> | journal = Nature Nanotechnology | volume = 8 | issue = 7| pages = 497–501 | doi = 10.1038/nnano.2013.100 | pmid = 23748194 | bibcode = 2013NatNa...8..497L }}</ref><ref name=promising /><ref>{{cite journal| first1=C. N. R. |last1= Rao| first2= H. S. S. |last2=Ramakrishna Matte |first3=U. |last3=Maitra| title= Graphene Analogues of Inorganic Layered Materials| journal= Angew. Chem.| edition= International| year= 2013| volume= 52| pages= 13162–85|doi=10.1002/anie.201301548}}</ref>
As in [[graphene]], the layered structures of {{chem|MoS|2}} and other [[transition metal]] dichalcogenides exhibit rich electronic and optical properties<ref name="nano">{{Cite journal | last1 = Wang | first1 = Q. H. | last2 = Kalantar-Zadeh | first2 = K. | last3 = Kis | first3 = A. | last4 = Coleman | first4 = J. N. | last5 = Strano | first5 = M. S. | title = Electronics and optoelectronics of two-dimensional transition metal dichalcogenides | doi = 10.1038/nnano.2012.193 | journal = Nature Nanotechnology | volume = 7 | issue = 11 | pages = 699–712 | year = 2012 | pmid = 23132225| pmc = }}</ref> that can differ from those in bulk.<ref name=promising>{{cite journal| first1=R. |last1=Ganatra |first2= Q. |last2= Zhang| title= Few-Layer MoS<sub>2</sub>: A Promising Layered Semiconductor| journal= ACS Nano| year= 2014| volume= 8| pages= 4074–99| doi=10.1021/nn405938z| accessdate= May 24, 2016}}</ref> Whereas bulk {{chem|MoS|2}} has an indirect band gap of 1.2 eV, [[Transition Metal Dichalcogenide monolayers|{{chem|MoS|2}} monolayers]] have a direct 1.8 eV [[band gap|electronic bandgap]],<ref name= Splendiani>{{cite journal|last1=Splendiani| first1=A.| last2= Sun| first2= L.| last3= Zhang| first3=Y.| last4= Li| first4= T.| last5= Kim| first5= J.|last6=Chim|first6=J.|last7=F.|year=2010|title=Emerging Photoluminescence in Monolayer MoS<sub>2</sub>|journal=Nano Letters|volume=10|issue=4|pages=1271–1275| doi=10.1021/nl903868w| pmid=20229981|bibcode=2010NanoL..10.1271S|last8=Wang|first8=Feng}}</ref> allowing the production of switchable transistors<ref name="Radisavljevic" /> and [[photodetectors]].<ref>{{cite journal | last1 = Lopez-Sanchez | first1 = O. | last2 = Lembke | first2 = D. | last3 = Kayci | first3 = M. | last4 = Radenovic | first4 = A. | last5 = Kis | first5 = A. | year = 2013 | title = Ultrasensitive photodetectors based on monolayer MoS<sub>2</sub> | journal = Nature Nanotechnology | volume = 8 | issue = 7| pages = 497–501 | doi = 10.1038/nnano.2013.100 | pmid = 23748194 | bibcode = 2013NatNa...8..497L }}</ref><ref name=promising /><ref>{{cite journal| first1=C. N. R. |last1= Rao| first2= H. S. S. |last2=Ramakrishna Matte |first3=U. |last3=Maitra| title= Graphene Analogues of Inorganic Layered Materials| journal= Angew. Chem.| edition= International| year= 2013| volume= 52| pages= 13162–85|doi=10.1002/anie.201301548}}</ref>


{{chem|MoS|2}} nanoflakes can be used for solution-processed fabrication of layered memristive and memcapacitive devices through engineering a [[MoOx|{{chem|MoO|x}}]]/{{chem|MoS|2}} heterostructure sandwiched between silver electrodes.<ref name="flexible_memristor">{{Cite journal | doi = 10.1038/nmat4135| pmid = 25384168| title = Layered memristive and memcapacitive switches for printable electronics| journal = Nature Materials| volume = 14| issue = 2| pages = 199| year = 2014| last1 = Bessonov | first1 = A. A. | last2 = Kirikova | first2 = M. N. | last3 = Petukhov | first3 = D. I. | last4 = Allen | first4 = M. | last5 = Ryhänen | first5 = T. | last6 = Bailey | first6 = M. J. A. | bibcode = 2015NatMa..14..199B}}</ref> The {{chem|MoS|2}}-based [[memristor]]s are mechanically flexible, optically transparent and can be produced at low cost.
{{chem|MoS|2}} nanoflakes can be used for solution-processed fabrication of layered memristive and memcapacitive devices through engineering a [[MoOx|{{chem|MoO|x}}]]/{{chem|MoS|2}} heterostructure sandwiched between silver electrodes.<ref name="flexible_memristor">{{Cite journal | doi = 10.1038/nmat4135| pmid = 25384168| title = Layered memristive and memcapacitive switches for printable electronics| journal = Nature Materials| volume = 14| issue = 2| pages = 199| year = 2014| last1 = Bessonov | first1 = A. A. | last2 = Kirikova | first2 = M. N. | last3 = Petukhov | first3 = D. I. | last4 = Allen | first4 = M. | last5 = Ryhänen | first5 = T. | last6 = Bailey | first6 = M. J. A. | bibcode = 2015NatMa..14..199B}}</ref> The {{chem|MoS|2}}-based [[memristor]]s are mechanically flexible, optically transparent and can be produced at low cost.
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[[File:Flex mos2.tif|thumb|Computer rendering of MoS<sub>2</sub>-based flexible transistor.<ref name=UT/>]]
[[File:Flex mos2.tif|thumb|Computer rendering of MoS<sub>2</sub>-based flexible transistor.<ref name=UT/>]]


MoS<sub>2</sub> has been investigated as a component of [[flexible circuits]].<ref name=":0">{{Cite journal|title = Large-Area Monolayer MoS2 for Flexible Low-Power RF Nanoelectronics in the GHz Regime|url = http://onlinelibrary.wiley.com/doi/10.1002/adma.201504309/abstract|journal = Advanced Materials|date = 2015-12-01|issn = 1521-4095|pages = n/a–n/a|doi = 10.1002/adma.201504309|language = en|first = Hsiao-Yu|last = Chang|first2 = Maruthi Nagavalli|last2 = Yogeesh|first3 = Rudresh|last3 = Ghosh|first4 = Amritesh|last4 = Rai|first5 = Atresh|last5 = Sanne|first6 = Shixuan|last6 = Yang|first7 = Nanshu|last7 = Lu|first8 = Sanjay Kumar|last8 = Banerjee|first9 = Deji|last9 = Akinwande}}</ref><ref name=UT>{{Cite journal|title = Two-dimensional flexible nanoelectronics|url = http://www.nature.com/ncomms/2014/141217/ncomms6678/full/ncomms6678.html|journal = Nature Communications|date = 2014-12-17|pages = 5678|volume = 5|doi = 10.1038/ncomms6678|language = en|first = Deji|last = Akinwande|first2 = Nicholas|last2 = Petrone|first3 = James|last3 = Hone}}</ref>
MoS<sub>2</sub> has been investigated as a component of [[flexible circuits]].<ref name=UT>{{Cite journal|title = Two-dimensional flexible nanoelectronics|url = http://www.nature.com/ncomms/2014/141217/ncomms6678/full/ncomms6678.html|journal = Nature Communications|date = 2014-12-17|pages = 5678|volume = 5|doi = 10.1038/ncomms6678|language = en|first = Deji|last = Akinwande|first2 = Nicholas|last2 = Petrone|first3 = James|last3 = Hone}}</ref><ref name=":0">{{Cite journal|title = Large-Area Monolayer MoS2 for Flexible Low-Power RF Nanoelectronics in the GHz Regime|url = http://onlinelibrary.wiley.com/doi/10.1002/adma.201504309/abstract|journal = Advanced Materials|date = 2015-12-01|issn = 1521-4095|pages = n/a–n/a|doi = 10.1002/adma.201504309|language = en|first = Hsiao-Yu|last = Chang|first2 = Maruthi Nagavalli|last2 = Yogeesh|first3 = Rudresh|last3 = Ghosh|first4 = Amritesh|last4 = Rai|first5 = Atresh|last5 = Sanne|first6 = Shixuan|last6 = Yang|first7 = Nanshu|last7 = Lu|first8 = Sanjay Kumar|last8 = Banerjee|first9 = Deji|last9 = Akinwande}}</ref>


===Photonics and photovoltaics===
===Photonics and photovoltaics===

Revision as of 18:54, 3 June 2016

Molybdenum disulfide
Molybdenum disulfide
Names
IUPAC name
Molybdenum disulfide
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.013.877 Edit this at Wikidata
RTECS number
  • QA4697000
  • InChI=1S/Mo.2S checkY
    Key: CWQXQMHSOZUFJS-UHFFFAOYSA-N checkY
  • InChI=1/Mo.2S/rMoS2/c2-1-3
    Key: CWQXQMHSOZUFJS-FRBXWHJUAU
  • S=[Mo]=S
Properties
MoS
2
Molar mass 160.07 g/mol[1]
Appearance black/lead-gray solid
Density 5.06 g/cm3[1]
Melting point 1,185 °C (2,165 °F; 1,458 K) decomposes
insoluble[1]
Solubility decomposed by aqua regia, hot sulfuric acid, nitric acid
insoluble in dilute acids
Band gap 1.23 eV (2H)[2]
Structure
hP6, space group P6
3/mmc, No 194 (2H)

hR9, space group R3m, No 160 (3R)[3]

a = 0.3161 nm (2H), 0.3163 nm (3R), c = 1.2295 nm (2H), 1.837 (3R)
Trigonal prismatic (MoIV)
Pyramidal (S2−)
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).
☒N verify (what is checkY☒N ?)

Molybdenum disulfide is the inorganic compound composed of only two elements: molybdenum and sulfur. Its chemical formula is MoS
2.

The compound is classified as a metal dichalcogenide. It is a silvery black solid that occurs as the mineral molybdenite, the principal ore for molybdenum.[4] MoS
2 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 solid lubricant because of its low friction properties and robustness. Bulk MoS
2 is a diamagnetic, indirect bandgap semiconductor similar to silicon, with a bandgap of 1.23 eV.[2]

Production

Molybdenite

Molybdenite ore is processed by flotation to give relatively pure MoS
2, the main contaminant being carbon. MoS
2 also arises by the thermal treatment of virtually all molybdenum compounds with hydrogen sulfide or elemental sulfur and can be produced by metathesis reactions from molybdenum pentachloride.[5]

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.[6]

MoS
2 usually consists of a mixture of two major polytypes of similar structure, 2H and 3R, with the former being more abundant.[3] In 2H-MoS
2, each Mo(IV) center occupies a trigonal prismatic coordination sphere that is bound to six sulfide ligands. Each sulfur centre is pyramidal and is connected to three Mo centres. In this way, the trigonal prisms are interconnected to give a layered structure, wherein molybdenum atoms are sandwiched between layers of sulfur atoms.[7] Because of the weak van der Waals interactions between the sheets of sulfide atoms, MoS
2 has a low coefficient of friction, producing its lubricating properties. Other layered inorganic materials exhibit lubricating properties (collectively known as solid lubricants (or dry lubricants)) include graphite, which requires volatile additives, and hexagonal boron nitride.[8]

Alternative morphologies

Much research is focused on unusual morphologies of MoS2. Multilayer sheets are produced by liquid phase exfoliation.[9][10] Nanotube-like and buckyball-like molecules composed of MoS
2 are known.[11]

The natural amorphous form is known as the rarer mineral jordisite.

Exfoliated MoS2

Two-dimensional, single- or few-layer MoS
2, is a two-dimensional semiconductor, with the band structure very sensitive to strain.[12][13]

Chemical reactions

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

2 MoS
2 + 7 O
2 → 2 MoO
3 + 4 SO
2

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

2 MoS
2 + 7 Cl
2 → 2 MoCl
5 + 2 S
2Cl
2

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.[14][15] One example is lithiated material, Li
xMoS
2.[16] With butyl lithium, the product is LiMoS
2.[4]

Applications

Lubricant

MoS
2 with particle sizes in the range of 1–100 µm is a common dry lubricant.[17] Few alternatives exist that confer high lubricity and stability at up to 350 °C in oxidizing environments. Sliding friction tests of MoS
2 using a pin on disc tester at low loads (0.1–2 N) give friction coefficient values of <0.1.[18][19]

MoS
2 is often a component of blends and composites that require low friction. 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, MoS
2 forms a composite with improved strength as well as reduced friction. Polymers filled with MoS
2 include nylon (with the 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 MoS
2-based lubricants include two-stroke engines (such as motorcycle engines), bicycle coaster brakes, automotive CV and universal joints, ski waxes,[20] and even bullets.[21]

Catalysis

MoS
2 is employed as a cocatalyst for desulfurization in petrochemistry, for example, hydrodesulfurization.The effectiveness of the MoS
2 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
2S 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.[22]

MoS2 also finds some use as a hydrogenation catalyst for organic synthesis.[23] Being derived from a common transition metal, rather than group 10 metal like 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 produce secondary amines via reductive alkylation.[24] The catalyst can also can effect hydrogenolysis of organosulfur compounds, aldehydes, ketones, phenols, and carboxylic acids to their respective alkanes.[23] The catalyst suffers from rather low activity however, often requiring hydrogen pressures above 95 atm and temperatures above 185 °C.

Research

Hydrogen evolution

MoS
2 and related molybdenum sulfides are efficient catalysts for hydrogen evolution, including the electrolysis of water.[25][26]

Microelectronics

As in graphene, the layered structures of MoS
2 and other transition metal dichalcogenides exhibit rich electronic and optical properties[27] that can differ from those in bulk.[28] Whereas bulk MoS
2 has an indirect band gap of 1.2 eV, MoS
2 monolayers have a direct 1.8 eV electronic bandgap,[29] allowing the production of switchable transistors[30] and photodetectors.[31][28][32]

MoS
2 nanoflakes can be used for solution-processed fabrication of layered memristive and memcapacitive devices through engineering a MoO
x/MoS
2 heterostructure sandwiched between silver electrodes.[33] The MoS
2-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.[34]

Computer rendering of MoS2-based flexible transistor.[35]

MoS2 has been investigated as a component of flexible circuits.[35][36]

Photonics and photovoltaics

MoS
2 also possesses mechanical strength, electrical conductivity, and can emit light, opening possible applications such as photodetectors.[37] MoS
2 has been investigated as a component of photoelectrochemical (e.g. for photocatalytic hydrogen production) applications and for microelectronics applications.[30]

See also

Wikimedia Commons has media related to Molybdenum disulfide.

References

  1. ^ a b c Haynes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd ed.). Boca Raton, Florida: CRC Press. p. 4.76. ISBN 1-4398-5511-0.
  2. ^ a b Kobayashi, K.; Yamauchi, J. (1995). "Electronic structure and scanning-tunneling-microscopy image of molybdenum dichalcogenide surfaces". Physical Review B. 51 (23): 17085. doi:10.1103/PhysRevB.51.17085.
  3. ^ a b Schönfeld, B.; Huang, J. J.; Moss, S. C. (1983). "Anisotropic mean-square displacements (MSD) in single-crystals of 2H- and 3R-MoS2". Acta Crystallographica Section B Structural Science. 39 (4): 404. doi:10.1107/S0108768183002645.
  4. ^ a b Sebenik, Roger F. et al. (2005) "Molybdenum and Molybdenum Compounds", Ullmann's Encyclopedia of Chemical Technology. Wiley-VCH, Weinheim. doi:10.1002/14356007.a16_655
  5. ^ Murphy, Donald W.; Interrante, Leonard V.; Kaner; Mansuktto (1995). "Metathetical Precursor Route to Molybdenum Disulfide". Inorganic Syntheses. Inorganic Syntheses. 30: 33–37. doi:10.1002/9780470132616.ch8. ISBN 9780470132616.
  6. ^ Hong, J.; Hu, Z.; Probert, M.; Li, K.; Lv, D.; Yang, X.; Gu, L.; Mao, N.; Feng, Q.; Xie, L.; Zhang, J.; Wu, D.; Zhang, Z.; Jin, C.; Ji, W.; Zhang, X.; Yuan, J.; Zhang, Z. (2015). "Exploring atomic defects in molybdenum disulphide monolayers". Nature Communications. 6: 6293. Bibcode:2015NatCo...6E6293H. doi:10.1038/ncomms7293. PMC 4346634. PMID 25695374.
  7. ^ Wells, A.F. (1984). Structural Inorganic Chemistry. Oxford: Clarendon Press. ISBN 0-19-855370-6.
  8. ^ Bartels, Thorsten (2002). "Lubricants and Lubrication". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley VCH. doi:10.1002/14356007.a15_423. {{cite book}}: Unknown parameter |displayauthors= ignored (|display-authors= suggested) (help)
  9. ^ "Novel exfoliation method developed by NUS chemists paves the way for two-dimensional materials to be used in printable photonics and electronics". science.nus.edu.sg. Faculty of Science, National University of Singapore. January 2, 2014. Retrieved May 24, 2016.
  10. ^ Communications and Marketing (January 29, 2014). "Engineer brings new twist to sodium ion battery technology with discovery of flexible molybdenum disulfide electrodes". K-State Today. Kansas State University. Retrieved May 24, 2016.
  11. ^ Tenne, R.; Redlich, M. (2010). "Recent progress in the research of inorganic fullerene-like nanoparticles and inorganic nanotubes". Chemical Society Reviews. 39 (5): 1423. doi:10.1039/B901466G. PMID 20419198.
  12. ^ Li, H.; Wu, J.; Yin, Z.; Zhang, H. (2014). "Preparation and Applications of Mechanically Exfoliated Single-Layer and Multilayer MoS2 and WSe2 Nanosheets". Acc. Chem. Res. 47: 1067–75. doi:10.1021/ar4002312.
  13. ^ Amorim, B.; Cortijo, A.; De Juan, F.; Grushin, A. G.; Guinea, F.; Gutiérrez-Rubio, A.; Ochoa, H.; Parente, V.; Roldán, R.; San-José, P.; Schiefele, J.; Sturla, M.; Vozmediano, M. A. H.; et al. (2 March 2015). "Novel effects of strains in graphene and other two dimensional materials". arxiv.org. 1503: 747. arXiv:1503.00747. Bibcode:2015arXiv150300747A. Retrieved 12 March 2015.
  14. ^ T. Stephenson, Z. Li, B. Olsen and D. Mitlin, "Lithium Ion Battery Applications of Molybdenum Disulfide (Mos2) Nanocomposites" Energy Environ. Sci., 2014, volume 7, 209-31. doi:10.1039/C3EE42591F.
  15. ^ Benavente, E.; Santa Ana, M. A.; Mendizabal, F.; Gonzalez, G. (2002). "Intercalation chemistry of molybdenum disulfide". Coordination Chemistry Reviews. 224: 87–109. doi:10.1016/S0010-8545(01)00392-7.
  16. ^ Müller-Warmuth, W.; Schöllhorn, R. (1994). Progress in intercalation research. Springer. ISBN 0-7923-2357-2. {{cite book}}: Unknown parameter |lastauthoramp= ignored (|name-list-style= suggested) (help)
  17. ^ Claus, F. L. (1972), Solid Lubricants and Self-Lubricating Solids, New York: Academic Press
  18. ^ Miessler, G. L.; Tarr, D. A. (2004). Inorganic Chemistry, 3rd Ed. Pearson/Prentice Hall publisher. ISBN 0-13-035471-6. {{cite book}}: Unknown parameter |lastauthoramp= ignored (|name-list-style= suggested) (help)
  19. ^ Shriver, D. F.; Atkins, P. W.; Overton, T. L.; Rourke, J. P.; Weller, M. T.; Armstrong, F. A. (2006). Inorganic Chemistry. New York: W. H. Freeman. ISBN 0-7167-4878-9.
  20. ^ "On dry lubricants in ski waxes" (PDF). Swix Sport AX. Retrieved 2011-01-06.
  21. ^ "Barrels retain accuracy longer with Diamond Line". Norma. Retrieved 2009-06-06.
  22. ^ Topsøe, H.; Clausen, B. S.; Massoth, F. E. (1996). Hydrotreating Catalysis, Science and Technology. Berlin: Springer-Verlag.
  23. ^ a b Nishimura, Shigeo (2001). Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis (1st ed.). New York: Wiley-Interscience. pp. 43–44 & 240–241. ISBN 9780471396987.
  24. ^ Dovell, Frederick S.; Greenfield, Harold (1964). "Base-Metal Sulfides as Reductive Alkylation Catalysts". The Journal of Organic Chemistry. 29 (5): 1265–1267. doi:10.1021/jo01028a511.
  25. ^ Kibsgaard, Jakob; Jaramillo, Thomas F.; Besenbacher, Flemming (2014). "Building an appropriate active-site motif into a hydrogen-evolution catalyst with thiomolybdate [Mo3S13]2− clusters". Nature Chemistry. 6 (3): 248–253. Bibcode:2014NatCh...6..248K. doi:10.1038/nchem.1853. PMID 24557141.
  26. ^ Laursen, A. B.; Kegnaes, S.; Dahl, S.; Chorkendorff, I. (2012). "Molybdenum Sulfides - Efficient and Viable Materials for Electro- and Photoelectrocatalytic Hydrogen Evolution". Energy Environ. Sci. 5: 5577–91. doi:10.1039/c2ee02618j.
  27. ^ Wang, Q. H.; Kalantar-Zadeh, K.; Kis, A.; Coleman, J. N.; Strano, M. S. (2012). "Electronics and optoelectronics of two-dimensional transition metal dichalcogenides". Nature Nanotechnology. 7 (11): 699–712. doi:10.1038/nnano.2012.193. PMID 23132225.
  28. ^ a b Ganatra, R.; Zhang, Q. (2014). "Few-Layer MoS2: A Promising Layered Semiconductor". ACS Nano. 8: 4074–99. doi:10.1021/nn405938z. {{cite journal}}: |access-date= requires |url= (help)
  29. ^ Splendiani, A.; Sun, L.; Zhang, Y.; Li, T.; Kim, J.; Chim, J.; F.; Wang, Feng (2010). "Emerging Photoluminescence in Monolayer MoS2". Nano Letters. 10 (4): 1271–1275. Bibcode:2010NanoL..10.1271S. doi:10.1021/nl903868w. PMID 20229981.
  30. ^ a b Radisavljevic, B.; Radenovic, A.; Brivio, J.; Giacometti, V.; Kis, A. (2011). "Single-layer MoS2 transistors". Nature Nanotechnology. 6 (3): 147–150. Bibcode:2011NatNa...6..147R. doi:10.1038/nnano.2010.279. PMID 21278752.
  31. ^ Lopez-Sanchez, O.; Lembke, D.; Kayci, M.; Radenovic, A.; Kis, A. (2013). "Ultrasensitive photodetectors based on monolayer MoS2". Nature Nanotechnology. 8 (7): 497–501. Bibcode:2013NatNa...8..497L. doi:10.1038/nnano.2013.100. PMID 23748194.
  32. ^ Rao, C. N. R.; Ramakrishna Matte, H. S. S.; Maitra, U. (2013). "Graphene Analogues of Inorganic Layered Materials". Angew. Chem. 52 (International ed.): 13162–85. doi:10.1002/anie.201301548.
  33. ^ Bessonov, A. A.; Kirikova, M. N.; Petukhov, D. I.; Allen, M.; Ryhänen, T.; Bailey, M. J. A. (2014). "Layered memristive and memcapacitive switches for printable electronics". Nature Materials. 14 (2): 199. Bibcode:2015NatMa..14..199B. doi:10.1038/nmat4135. PMID 25384168.
  34. ^ "Ultrasensitive biosensor from molybdenite semiconductor outshines graphene". R&D Magazine. 4 September 2014.
  35. ^ a b Akinwande, Deji; Petrone, Nicholas; Hone, James (2014-12-17). "Two-dimensional flexible nanoelectronics". Nature Communications. 5: 5678. doi:10.1038/ncomms6678.
  36. ^ Chang, Hsiao-Yu; Yogeesh, Maruthi Nagavalli; Ghosh, Rudresh; Rai, Amritesh; Sanne, Atresh; Yang, Shixuan; Lu, Nanshu; Banerjee, Sanjay Kumar; Akinwande, Deji (2015-12-01). "Large-Area Monolayer MoS2 for Flexible Low-Power RF Nanoelectronics in the GHz Regime". Advanced Materials: n/a–n/a. doi:10.1002/adma.201504309. ISSN 1521-4095.
  37. ^ Coxworth, Ben (September 25, 2014). "Metal-based graphene alternative "shines" with promise". Gizmag. Retrieved September 30, 2014.
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