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| ImageFile = Ruthenium(IV)-oxide-unit-cell-3D-vdW.png |
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| verifiedrevid = 428796180 |
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| IUPACName = Ruthenium(IV) oxide |
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| ImageFile = Ruthenium(IV)-oxide-unit-cell-3D-vdW.png |
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| OtherNames = Ruthenium dioxide |
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| IUPACName = Ruthenium(IV) oxide |
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| Section1 = {{Chembox Identifiers |
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| OtherNames = Ruthenium dioxide |
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| CASNo = 12036-10-1 |
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| CASNo = 12036-10-1 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| PubChem = 82848 |
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| EINECS = 234-840-6 |
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| InChI = 1S/2O.Ru |
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| SMILES = O==O |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| Formula = RuO<sub>2</sub> |
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| Formula = RuO<sub>2</sub> |
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| MolarMass = 133.07 g/mol |
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| MolarMass = 133.0688 g/mol |
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| Appearance = blue-black solid |
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| Appearance = blue-black solid |
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| Density = 6.97 g/cm<sup>3</sup> |
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| Density = 6.97 g/cm<sup>3</sup> |
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| Solubility = insoluble |
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| Solubility = insoluble |
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| BoilingPt = 1200 °C subl. |
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| BoilingPtC = 1200 |
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| BoilingPt_notes = sublimates |
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| MagSus = +162.0·10<sup>−6</sup> cm<sup>3</sup>/mol |
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| Section3 = {{Chembox Structure |
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| CrystalStruct = ] (tetragonal), ] |
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| CrystalStruct = ] (tetragonal), ] |
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| SpaceGroup = ''P''4<sub>2</sub>/''mnm'', No. 136 |
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| SpaceGroup = ''P''4<sub>2</sub>/''mnm'', No. 136 |
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| Coordination = Octahedral (Ru<sup>IV</sup>); trigonal planar (O<sup>2–</sup>) |
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| Coordination = Octahedral (Ru<sup>IV</sup>); trigonal planar (O<sup>2−</sup>) |
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| FlashPt = Non-flammable |
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| EUIndex = not listed |
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| FlashPt = Non-flammable |
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'''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> |
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'''Ruthenium(IV) oxide''' (]]) is a black ] containing the rare metal ] and ]. The most often |
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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> |
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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. |
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==Structure and physical properties== |
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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. |
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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. |
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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 F/g when in H<sub>2</sub>SO<sub>4</sub> solution and annealed at temperatures lower than 200 °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. |
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==Preparation== |
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==Preparation== |
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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> |
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There are various ways in preparing ruthenium(IV) oxide. |
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The following processes described below are for preparing RuO<sub>2</sub> as a film. |
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:RuO<sub>2</sub> + O<sub>2</sub> {{eqm}} RuO<sub>4</sub> |
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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> |
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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> |
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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 /> |
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This technique has in fact been developed by Schafer for the preparation |
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of nearly stoichiometric RuO<sub>2</sub> single crystals.<ref> Schafer, H., ''Z.an.allg. Chem.'' '''1963''', ''319'', 327</ref> |
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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> |
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Both process follow the same reaction mechanism: |
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:Ru<sup>+(IV)</sup> + O<sub>2</sub> (heat)→ RuO<sub>2</sub> |
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High temperature flashes of heat up to 1500 °C can remove all oxides and contaminants, and form a new oxide layer on the ruthenium. |
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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 |
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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> |
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==Uses== |
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==Uses== |
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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> |
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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> |
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RuO<sub>2</sub> can be used as catalyst in many other situations. Noteworthy reactions are the ], ], and various manifestations of ]. |
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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 ]. |
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===Aspirational and niche applications=== |
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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. |
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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 F/g when in ] and annealed at temperatures lower than 200 °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. |
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==Oxidative catalyst== |
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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 °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> |
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RuO<sub>2</sub> can be used as catalyst in multiple reactions. Such noteworthy reactions are the ] and ]. |
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==References== |
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==References== |
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==External links== |
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==External links== |
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{{Commons category|Ruthenium(IV) oxide}} |
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{{Commons category|Ruthenium(IV) oxide}} |
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* {{Webarchive|url=https://web.archive.org/web/20070405104929/http://periodic.lanl.gov/elements/44.html |date=2007-04-05 }} |
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{{Ruthenium compounds}} |
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