Misplaced Pages

Ruthenium(IV) oxide: Difference between revisions

Article snapshot taken from Wikipedia with creative commons attribution-sharealike license. Give it a read and then ask your questions in the chat. We can research this topic together.
Browse history interactively← Previous editContent deleted Content addedVisualWikitext
Revision as of 18:30, 12 May 2011 editLamro (talk | contribs)Autopatrolled, Extended confirmed users84,272 edits {{Ruthenium compounds}}← Previous edit Latest revision as of 03:55, 12 December 2024 edit undoTerraFrost (talk | contribs)Extended confirmed users3,528 editsm →Aspirational and niche applications: clean up sentenceTag: 2017 wikitext editor 
(50 intermediate revisions by 35 users not shown)
Line 1: Line 1:
{{chembox {{chembox
| Verifiedfields = changed
⚫ | verifiedrevid = 416243255
| Watchedfields = changed
⚫ | ImageFile = Ruthenium(IV)-oxide-unit-cell-3D-vdW.png
⚫ | verifiedrevid = 428796180
⚫ | ImageSize = 200px
| IUPACName = Ruthenium(IV) oxide | ImageFile = Ruthenium(IV)-oxide-unit-cell-3D-vdW.png
⚫ | ImageSize =
⚫ | OtherNames = Ruthenium dioxide
⚫ | IUPACName = Ruthenium(IV) oxide
⚫ | Section1 = {{Chembox Identifiers
⚫ | OtherNames = Ruthenium dioxide
⚫ | CASNo = 12036-10-1
⚫ |Section1={{Chembox Identifiers
⚫ | CASNo_Ref = {{cascite}}
⚫ | CASNo = 12036-10-1
⚫ | CASNo_Ref = {{cascite|correct|CAS}}
| PubChem = 82848
| EINECS = 234-840-6
| InChI = 1S/2O.Ru
| SMILES = O==O
}} }}
| Section2 = {{Chembox Properties |Section2={{Chembox Properties
| Formula = RuO<sub>2</sub> | Formula = RuO<sub>2</sub>
| MolarMass = 133.07 g/mol | MolarMass = 133.0688 g/mol
| Appearance = blue-black solid | Appearance = blue-black solid
| Density = 6.97 g/cm<sup>3</sup> | Density = 6.97 g/cm<sup>3</sup>
| Solubility = insoluble | Solubility = insoluble
| BoilingPt = 1200 °C subl. | BoilingPtC = 1200
| BoilingPt_notes = sublimates
| MagSus = +162.0·10<sup>−6</sup> cm<sup>3</sup>/mol
}} }}
| Section3 = {{Chembox Structure |Section3={{Chembox Structure
| CrystalStruct = ] (tetragonal), ] | CrystalStruct = ] (tetragonal), ]
| SpaceGroup = ''P''4<sub>2</sub>/''mnm'', No. 136 | SpaceGroup = ''P''4<sub>2</sub>/''mnm'', No. 136
| Coordination = Octahedral (Ru<sup>IV</sup>); trigonal planar (O<sup>2–</sup>) | Coordination = Octahedral (Ru<sup>IV</sup>); trigonal planar (O<sup>2−</sup>)
| LattConst_a = | LattConst_a =
| LattConst_c = | LattConst_c =
}} }}
| Section7 = {{Chembox Hazards |Section7={{Chembox Hazards
⚫ | FlashPt = Non-flammable
| EUIndex = not listed
⚫ | FlashPt = Non-flammable
⚫ }}
⚫ | Section8 = {{Chembox Related
⚫ | OtherAnions = ]
⚫ | OtherCations = ]
⚫ | OtherFunctn = ]
⚫ | Function = ] ]s
| OtherCpds =
}} }}
⚫ |Section8={{Chembox Related
⚫ | OtherAnions = ]
⚫ | OtherCations = ]
⚫ | OtherFunction = ]
⚫ | OtherFunction_label = ] ]s
| OtherCompounds =
⚫ }}
}} }}
'''Ruthenium(IV) oxide''' is the ] with the formula ]]. This black solid is the most common oxide of ]. It is widely used as an ] for producing chlorine, chlorine oxides, and O<sub>2</sub>.<ref>{{cite journal | last=Mills | first=Andrew | title=Heterogeneous redox catalysts for oxygen and chlorine evolution | journal=Chemical Society Reviews | publisher=Royal Society of Chemistry (RSC) | volume=18 | year=1989 | issn=0306-0012 | doi=10.1039/cs9891800285 | page=285}}</ref> Like many dioxides, RuO<sub>2</sub> adopts the ] structure.<ref>Wyckoff, R.W.G.. ''Crystal Structures'', Vol. 1. Interscience, John Wiley & Sons: 1963.</ref><ref>{{Wells4th}}</ref>
'''Ruthenium(IV) oxide''' (]]) is a black ] containing the rare metal ] and ]. The most often
used O<sub>2</sub> catalyst is ruthenium(IV) oxide, however care must be taken since hydrates of this oxide exist.<ref>Mills, A.; ''Chem. Sot. Rev.,'''''1989''', ''18'', 285.</ref>

RuO<sub>2</sub> is generally used as a ] in various industrial applications or an ] in ] processes. RuO<sub>2</sub> is highly reactive with ] agents, due to its ] properties.

==Structure and physical properties==
Ruthenium(IV) oxide takes on the ] crystal structure<ref> Wyckoff, R.W.G.. ''Crystal Structures'', Vol. 1. Interscience, John Wiley & Sons: 1963.</ref><ref>{{Wells4th}}</ref>, similar to ] and several other metal oxides. Due to its structure, ruthenium(IV) oxide easily forms hydrates.

Ruthenium(IV) oxide is a (nearly black) purple crystalline solid at room temperature. The hydrates of RuO<sub>2</sub> have a blue color to them.

Ruthenium oxide has great capacity to store charge when used in aqueous solutions.<ref> Matthey, Johnson. ''Platinum Metals Review.'' '''2002''', ''46'', 3, 105</ref> Average capacities of ruthenium(IV) oxide have reached 650&nbsp;F/g when in H<sub>2</sub>SO<sub>4</sub> solution and annealed at temperatures lower than 200&nbsp;°C.<ref> Kim,Il-Hwan; Kim, Kwang-Bum; ''Electrochem. Solid-State Lett.,'' '''2001''', ''4'', 5,A62-A64</ref> In attempts to optimise its capacitive properties, prior work has looked at the hydration of ruthenium oxide, its crystallinity and particle size.


==Preparation== ==Preparation==
It is usually prepared by oxidation of ]. Nearly stoichiometric single crystals of RuO<sub>2</sub> can be obtained by ], using O<sub>2</sub> as the transport agent:<ref>{{cite journal | last1=Schäfer | first1=Harald | last2=Schneidereit | first2=Gerd | last3=Gerhardt | first3=Wilfried | title=Zur Chemie der Platinmetalle. RuO2 Chemischer Transport, Eigenschaften, thermischer Zerfall | journal=Zeitschrift für anorganische und allgemeine Chemie | publisher=Wiley | volume=319 | issue=5–6 | year=1963 | issn=0044-2313 | doi=10.1002/zaac.19633190514 | pages=327–336 | language=de}}</ref><ref>{{cite book | last1 = Rogers | first1 = D. B. | last2 = Butler | first2 = S. R. | last3 = Shannon | first3 = R. D. | title = Inorganic Syntheses | year = 1972 | chapter = Single Crystals of Transition-Metal Dioxides | volume = XIII | pages = 135–145 | doi = 10.1002/9780470132449.ch27 | isbn = 9780470132449 }}</ref>
There are various ways in preparing ruthenium(IV) oxide.
The following processes described below are for preparing RuO<sub>2</sub> as a film.


⚫ :RuO<sub>2</sub> + O<sub>2</sub> {{eqm}} RuO<sub>4</sub>
1. The ] (CVD) of RuO<sub>2</sub> from suitable volatile ruthenium compounds.<ref> Pizzini, S.; Buzzancae, g.; ''Mat. Res. Bull.'', '''1972,''' ''7'', 449-462.</ref>


Films of RuO<sub>2</sub> can be prepared by ] (CVD) from volatile ruthenium compounds.<ref>{{cite journal | last1=Pizzini | first1=S. | last2=Buzzanca | first2=G. | last3=Mari | first3=C. | last4=Rossi | first4=L. | last5=Torchio | first5=S. | title=Preparation, structure and electrical properties of thick ruthenium dioxide films | journal=Materials Research Bulletin | publisher=Elsevier BV | volume=7 | issue=5 | year=1972 | issn=0025-5408 | doi=10.1016/0025-5408(72)90147-x | pages=449–462}}</ref> RuO<sub>2</sub> can also be prepared through ] from a solution of ruthenium trichloride.<ref>{{Cite journal | last1 = Lee | first1 = S. | doi = 10.1016/j.ssi.2003.08.035 | title = Electrochromism of amorphous ruthenium oxide thin films | journal = Solid State Ionics | volume = 165 | issue = 1–4 | pages = 217–221 | year = 2003 | url = https://zenodo.org/record/1259365 }}</ref>
2. The ], or heating of ruthenium halides, suitably deposited on the substrate by spraying on the heated substrate a solution of the halide . The most commonly used halide is ] to form RuO<sub>2</sub>.<br />
This technique has in fact been developed by Schafer for the preparation
of nearly stoichiometric RuO<sub>2</sub> single crystals.<ref> Schafer, H., ''Z.an.allg. Chem.'' '''1963''', ''319'', 327</ref>


Electrostatically stabilized hydrosols of pristine ruthenium dioxide hydrate have been prepared by exploiting the autocatalytic reduction of ruthenium tetroxide in aqueous solution. The resulting particle populations may be controlled to comprise substantially monodisperse, uniform spheres with diameters in the range 40nm - 160nm.<ref>{{ cite journal |author1=McMurray, H. N. | title = Uniform colloids of ruthenium dioxide hydrate evolved by the surface-catalyzed reduction of ruthenium tetroxide| journal = The Journal of Physical Chemistry | year = 1993 | volume = 97 | issue = 30 | pages = 8039–8045 | doi = 10.1021/j100132a038}}</ref>
Both process follow the same reaction mechanism:
⚫ :Ru<sup>+(IV)</sup> + O<sub>2</sub> (heat)→ RuO<sub>2</sub>
<br />
High temperature flashes of heat up to 1500&nbsp;°C can remove all oxides and contaminants, and form a new oxide layer on the ruthenium.

3. Another way to prepare RuO<sub>2</sub> is through ]. Films can be electroplated from a solution of RuCl<sub>3</sub><sup>.</sup>xH<sub>2</sub>O. Pt gauze was used
as the counter electrode and Ag/AgCl as the reference electrode.<ref>Lee, Se-Hee; Liu, Ping.; ''Solid State Ionics'' '''2003''', ''165'', 217-221.</ref>


==Uses== ==Uses==
Ruthenium(IV) oxide is being used as the main component in the catalyst of the Sumitomo-] which produces ] by the oxidation of ].<ref>{{citation | last1=Vogt | first1=Helmut | last2=Balej | first2=Jan | last3=Bennett | first3=John E. | last4=Wintzer | first4=Peter | last5=Sheikh | first5=Saeed Akbar | last6=Gallone | first6=Patrizio | title=Ullmann's Encyclopedia of Industrial Chemistry | chapter=Chlorine Oxides and Chlorine Oxygen Acids | publisher=Wiley-VCH Verlag GmbH & Co. KGaA | publication-place=Weinheim, Germany | date=2000-06-15 | doi=10.1002/14356007.a06_483 | page=| isbn=3527306730 }}</ref><ref>{{cite journal | last=Seki | first=Kohei | title=Development of RuO2/Rutile-TiO2 Catalyst for Industrial HCl Oxidation Process | journal=Catalysis Surveys from Asia | publisher=Springer Science and Business Media LLC | volume=14 | issue=3–4 | date=2010-05-29 | issn=1571-1013 | doi=10.1007/s10563-010-9091-7 | pages=168–175| s2cid=93115959 }}</ref>
RuO<sub>2</sub> is extensively used for the coating of titanium anodes for the electrolytic production of chlorine and for the preparation of ] or ].<ref> De Nora,O.; ''Chem. Eng. Techn.'', '''1970''', ''42'', 222.</ref><ref>Iles, G.S.; ''Platinum Met. Rev.'', '''1967''',''11'',126.</ref>


⚫ RuO<sub>2</sub> can be used as catalyst in many other situations. Noteworthy reactions are the ], ], and various manifestations of ].
Ruthenium(IV) oxide is a versatile catalyst and doping agent. ] can be split by light by using a ] of CdS particles doped with ruthenium(IV) oxide loaded with ruthenium dioxide.<ref> Park, Dae-chul; Baeg, Jin-ook., ''U.S. Pat. Appl. Publ.'', '''2001''',6 pp.</ref> This may be useful in the removal of H<sub>2</sub>S from oil refineries and from other industrial processes. The hydrogen produced could be used to synthesize ammonia, methanol, and possibly fuel a future ].


===Aspirational and niche applications===
Ruthenium (IV) oxide is being used as the main component in the catalyst of the ] which produces ] by the oxidation of ].It can be also used as active material in supercapacitor because has very high charge transfer capability.
RuO<sub>2</sub> is extensively used for the coating of titanium anodes for the electrolytic production of chlorine and for the preparation of ] or ].<ref>{{cite journal | last=De Nora | first=O. | title=Anwendung maßbeständiger aktivierter Titan-Anoden bei der Chloralkali-Elektrolyse | journal=Chemie Ingenieur Technik | publisher=Wiley | volume=42 | issue=4 | year=1970 | issn=0009-286X | doi=10.1002/cite.330420417 | pages=222–226}}</ref><ref>{{cite journal|last1=Iles|first1=G.S.|journal=Platinum Metals Review|year=1967|volume=11|issue=4|page=126|title=Ruthenium Oxide Glaze Resistors|url=https://www.technology.matthey.com/article/11/4/126-129/}}</ref> Ruthenium oxide resistors can be used as sensitive thermometers in the temperature range .02 < T < 4 K. It can be also used as active material in supercapacitor because it has very high charge transfer capability. Ruthenium oxide has great capacity to store charge when used in aqueous solutions.<ref>{{cite journal|last1=Matthey|first1=Johnson|url=http://www.platinummetalsreview.com/article/46/3/105-105-1/|journal=Platinum Metals Review|year=2002|volume=46|issue=3|page=105|title=Nanocrystalline Ruthenium Supercapacitor Material|access-date=2013-09-16|archive-date=2015-09-24|archive-url=https://web.archive.org/web/20150924074119/http://www.platinummetalsreview.com/article/46/3/105-105-1/|url-status=dead}}</ref> Average capacities of ruthenium(IV) oxide have reached 650&nbsp;F/g when in ] and annealed at temperatures lower than 200&nbsp;°C.<ref>Kim,Il-Hwan; Kim, Kwang-Bum; ''Electrochem. Solid-State Lett.,'' '''2001''', ''4'', 5,A62-A64</ref> In attempts to optimise its capacitive properties, prior work has looked at the hydration, crystallinity and particle size of ruthenium oxide.

==Oxidative catalyst==
RuO<sub>2</sub> by itself is a poor catalyst because without the presence of a hydrate its surface area is greatly decreased. To get pure ruthenium(IV) oxide, it needs to be ] at 900&nbsp;°C. The best catalyst for electrochemical processes is to have some hydrate present, but not a completely hydrous one.<ref>Mills, A.; Davies, H.; ''Inorganica. Chimica. Acta.,'' '''1991''', ''189'', 149-155</ref>
⚫ RuO<sub>2</sub> can be used as catalyst in multiple reactions. Such noteworthy reactions are the ] and ].


==References== ==References==
Line 82: Line 67:
==External links== ==External links==
{{Commons category|Ruthenium(IV) oxide}} {{Commons category|Ruthenium(IV) oxide}}
* * {{Webarchive|url=https://web.archive.org/web/20070405104929/http://periodic.lanl.gov/elements/44.html |date=2007-04-05 }}


{{Ruthenium compounds}} {{Ruthenium compounds}}


] ]
] ]

]
]
]
]
]
]

Latest revision as of 03:55, 12 December 2024

Ruthenium(IV) oxide
Names
IUPAC name Ruthenium(IV) oxide
Other names Ruthenium dioxide
Identifiers
CAS Number
3D model (JSmol)
ECHA InfoCard 100.031.660 Edit this at Wikidata
EC Number
  • 234-840-6
PubChem CID
CompTox Dashboard (EPA)
InChI
  • InChI=1S/2O.Ru
SMILES
  • O==O
Properties
Chemical formula RuO2
Molar mass 133.0688 g/mol
Appearance blue-black solid
Density 6.97 g/cm
Boiling point 1,200 °C (2,190 °F; 1,470 K) sublimates
Solubility in water insoluble
Magnetic susceptibility (χ) +162.0·10 cm/mol
Structure
Crystal structure Rutile (tetragonal), tP6
Space group P42/mnm, No. 136
Coordination geometry Octahedral (Ru); trigonal planar (O)
Hazards
Flash point Non-flammable
Related compounds
Other anions Ruthenium disulfide
Other cations Osmium(IV) oxide
Related ruthenium oxides Ruthenium tetroxide
Supplementary data page
Ruthenium(IV) oxide (data page)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒N verify (what is  ?) Infobox references
Chemical compound

Ruthenium(IV) oxide is the inorganic compound with the formula RuO2. This black solid is the most common oxide of ruthenium. It is widely used as an electrocatalyst for producing chlorine, chlorine oxides, and O2. Like many dioxides, RuO2 adopts the rutile structure.

Preparation

It is usually prepared by oxidation of ruthenium trichloride. Nearly stoichiometric single crystals of RuO2 can be obtained by chemical vapor transport, using O2 as the transport agent:

RuO2 + O2 ⇌ RuO4

Films of RuO2 can be prepared by chemical vapor deposition (CVD) from volatile ruthenium compounds. RuO2 can also be prepared through electroplating from a solution of ruthenium trichloride.

Electrostatically stabilized hydrosols of pristine ruthenium dioxide hydrate have been prepared by exploiting the autocatalytic reduction of ruthenium tetroxide in aqueous solution. The resulting particle populations may be controlled to comprise substantially monodisperse, uniform spheres with diameters in the range 40nm - 160nm.

Uses

Ruthenium(IV) oxide is being used as the main component in the catalyst of the Sumitomo-Deacon process which produces chlorine by the oxidation of hydrogen chloride.

RuO2 can be used as catalyst in many other situations. Noteworthy reactions are the Fischer–Tropsch process, Haber–Bosch process, and various manifestations of fuel cells.

Aspirational and niche applications

RuO2 is extensively used for the coating of titanium anodes for the electrolytic production of chlorine and for the preparation of resistors or integrated circuits. Ruthenium oxide resistors can be used as sensitive thermometers in the temperature range .02 < T < 4 K. It can be also used as active material in supercapacitor because it has very high charge transfer capability. Ruthenium oxide has great capacity to store charge when used in aqueous solutions. Average capacities of ruthenium(IV) oxide have reached 650 F/g when in sulfuric acid and annealed at temperatures lower than 200 °C. In attempts to optimise its capacitive properties, prior work has looked at the hydration, crystallinity and particle size of ruthenium oxide.

References

  1. Mills, Andrew (1989). "Heterogeneous redox catalysts for oxygen and chlorine evolution". Chemical Society Reviews. 18. Royal Society of Chemistry (RSC): 285. doi:10.1039/cs9891800285. ISSN 0306-0012.
  2. Wyckoff, R.W.G.. Crystal Structures, Vol. 1. Interscience, John Wiley & Sons: 1963.
  3. Wells, A. F. (1975), Structural Inorganic Chemistry (4th ed.), Oxford: Clarendon Press
  4. Schäfer, Harald; Schneidereit, Gerd; Gerhardt, Wilfried (1963). "Zur Chemie der Platinmetalle. RuO2 Chemischer Transport, Eigenschaften, thermischer Zerfall". Zeitschrift für anorganische und allgemeine Chemie (in German). 319 (5–6). Wiley: 327–336. doi:10.1002/zaac.19633190514. ISSN 0044-2313.
  5. Rogers, D. B.; Butler, S. R.; Shannon, R. D. (1972). "Single Crystals of Transition-Metal Dioxides". Inorganic Syntheses. Vol. XIII. pp. 135–145. doi:10.1002/9780470132449.ch27. ISBN 9780470132449.
  6. Pizzini, S.; Buzzanca, G.; Mari, C.; Rossi, L.; Torchio, S. (1972). "Preparation, structure and electrical properties of thick ruthenium dioxide films". Materials Research Bulletin. 7 (5). Elsevier BV: 449–462. doi:10.1016/0025-5408(72)90147-x. ISSN 0025-5408.
  7. Lee, S. (2003). "Electrochromism of amorphous ruthenium oxide thin films". Solid State Ionics. 165 (1–4): 217–221. doi:10.1016/j.ssi.2003.08.035.
  8. McMurray, H. N. (1993). "Uniform colloids of ruthenium dioxide hydrate evolved by the surface-catalyzed reduction of ruthenium tetroxide". The Journal of Physical Chemistry. 97 (30): 8039–8045. doi:10.1021/j100132a038.
  9. Vogt, Helmut; Balej, Jan; Bennett, John E.; Wintzer, Peter; Sheikh, Saeed Akbar; Gallone, Patrizio (2000-06-15), "Chlorine Oxides and Chlorine Oxygen Acids", Ullmann's Encyclopedia of Industrial Chemistry, Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA, doi:10.1002/14356007.a06_483, ISBN 3527306730
  10. Seki, Kohei (2010-05-29). "Development of RuO2/Rutile-TiO2 Catalyst for Industrial HCl Oxidation Process". Catalysis Surveys from Asia. 14 (3–4). Springer Science and Business Media LLC: 168–175. doi:10.1007/s10563-010-9091-7. ISSN 1571-1013. S2CID 93115959.
  11. De Nora, O. (1970). "Anwendung maßbeständiger aktivierter Titan-Anoden bei der Chloralkali-Elektrolyse". Chemie Ingenieur Technik. 42 (4). Wiley: 222–226. doi:10.1002/cite.330420417. ISSN 0009-286X.
  12. Iles, G.S. (1967). "Ruthenium Oxide Glaze Resistors". Platinum Metals Review. 11 (4): 126.
  13. Matthey, Johnson (2002). "Nanocrystalline Ruthenium Supercapacitor Material". Platinum Metals Review. 46 (3): 105. Archived from the original on 2015-09-24. Retrieved 2013-09-16.
  14. Kim,Il-Hwan; Kim, Kwang-Bum; Electrochem. Solid-State Lett., 2001, 4, 5,A62-A64

External links

Ruthenium compounds
Ru(0)
Ru(I)
Ru(II)
Ru(II,III)
Ru(III)
Ru(IV)
Ru(V)
Ru(VI)
Ru(VII)
Ru(VIII)
Categories: