On the character of solid solutions in ruthenium-titanium oxide anodes

Roginskaya, Yu. E.; Belova, I.D.; Galyamov, B. Sh.; Chibirova, F. Kh.; Shiprina, R.R.

doi:10.1016/0254-0584(89)90038-2

Cited by 20 publications

(10 citation statements)

References 9 publications

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“…Further XPS characterization of the Ti adlayers on the disordered, oxygen deficient RuO 2 surface (Ti 3p 3/2 region) evidenced the coexistence of a mixture of species including different oxidation states, such as TiO 2 , Ti(OH) 3 , Ti 2 O 3 , TiO, confirming and complementing the FT-ATR data (Ti 3+ species at the polished wafer surface (3985 cm -1 , 3735 cm -1 , 2105 cm -1 ), [10]. formation mechanism with rutile TiO 2 based wafer with 0.1% TiO 2 based slurry heterogeneous catalysts At molecular/atomic level, the rutile TiO 2 surface (high concentration of Ti-OH, pronounced Lewis acid/base character) has the most appropriate and desired functionality able to activate these particles to be energetically involved in several fundamental types of interactions, including H 2 O 2 chemisorption and its catalytically induced decomposition into high energy oxygen-centered radicals (hydroxyl, superoxide).…”

Section: Figuresupporting

confidence: 60%

Mechanistic Investigations of Ruthenium Polishing Enabled by Heterogeneous Catalysis With Titania-based Slurries

2010

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Difficulties and challenges have been widely encountered in the chemical mechanical planarization (CMP) of noble metals used as diffusion barrier films due to hardness, chemical inertness and toxic oxidation products, in particular for Ru polishing. A commercial CMC Ru polishing slurry that successfully addressed the safety concerns was based on a high pH (8.4) polymer-treated α-alumina-based multi-additive slurry containing complexing reagents (carboxylic acids and salts), corrosion inhibitors, surfactants, and hydrogen peroxide as a mild, non-aggressive oxidizer. Recently, our efforts had been redirected towards the development of a new generation of low pH barrier slurries based on an entirely new concept employing unique Lewis acid type abrasives. This class of materials is well known to be highly reactive in dielectrics polishing (ceria, zirconia, titania), but far less is known about their interactions with Ru, Cu or Ta.In this presentation, we will elaborate the unexpected discovery that hard, chemically inert, noble metals such as ruthenium can be polished easily by virtually abrasive-free and/or oxidizer-free TiO 2 based slurries. Of particular importance is the finding that the polymorphic phase of TiO 2 (anatase or rutile), its surface chemistry (functional groups, Lewis acid/base character), pH induced surface modification and reactivity, can all mediate the abrasive particle's adsorption properties, catalytic activity and ultimately, its slurry polishing performance.

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Section: Figuresupporting

confidence: 60%

Mechanistic Investigations of Ruthenium Polishing Enabled by Heterogeneous Catalysis With Titania-based Slurries

2010

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“…The Moscow Institute of Chemical Machine Building has developed methodological bases and created experimental apparatus to investigate the corrosion-electrochemical behavior of metals under controlled conditions of heat and mass exchange [5][6][7].…”

Section: Literaturementioning

confidence: 99%

“…We established [5] that the conclusions that the coatings obtained from chloride solutions were single-phase and that films obtained by the use of alcoholates or other orgamic compounds were multiphase supplemented each other rather than being contradictory~ It has been demonstrated that to form the phase of oxide solid solutions the Ru and Ti components should interact already at the hydrolytic stage. This interaction takes place by means of sorption of anionic chlorohydroxo complexes [Ruz~OH)2Cls] ~-and [Ru2(OH)2CI6(H20)2] 2-by polymer or colloidal forms of hydrated titanium oxide.…”

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confidence: 96%

“…Karpov Scientific Research Institute of Physical Chemistry on the actual composition, structure and electron properties of pyrolytic ruthenium oxide and iridium oxide coatings and also two-and three-component films of composition RuO2-Ti02, IrO2-TiO 2, IrO2-RuO2-TiO 2, etc. have shown [4,5] that all these materials are products of incomplete dehydration of partially hydrated oxides of Ru, Ti, and Ir with an incomplete degree of crystallinity. These results were obtained by transmission electron microscopy and by electron and x-ray diffraction methods.…”

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confidence: 97%

“…Therefore, as a result of pyrolysis, there is formed the phase of rutile solid solutions with a short-range order, where the ruthenium and titanium components are found inthe form of statistically mixed ruthenium oxide and titanium oxide microregions 1.5-2 nm in dimension [5].…”

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Structure and processes of formation of oxide electrocatalysts

Roginskaya¹,

Belova²,

Galyamov³

1991

Chem Petrol Eng

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Catalytically active corrosion-resistant electrode coatings based on compositions of highly conductive oxides of noble metals (Ru, Ir, Pd, and Pt) and oxides of rectifying and other transition metals (Ti, Nb, Ta, Co, Ni, and Fe) [i] are widely used as low-wear anodes in important industrial electrochemical processes (production of chlorine and caustic soda, electrolysis of water to obtain hydrogen, electrolytic polishing of metals, etc.).However, in connection with the development and design of more advanced electrochemical technologies work is in progress on optimization of the properties of oxide coatings of low-wear anodes. In addition, the characteristics of the electrochemistry of oxides of these metals that have been brought to light [2,3], in comparison with the electrochemistry of the metals (Ru, Ir, and Pt), has generated interest in studying the nature and mechanism of electrocatalysis, processes of corrosion of these materials, and of course their structure and physicochemical properties. In studying the structure and electron properties of low-wear anodes attempts were made to determine correlations of the electrochemical properties with the composition and structure of crystalline phases (individual oxides or solid solutions), the microstructure (grain size of crystalline phases and imperfections), magnitude and character of true surface, the heterovalent states of the cations, and the mechanism of electrical conductivity. As a result of these investigations, it has been concluded that the oxide films of low-wear anodes obtained by pyrolysis of salts (primarily chlorides) of Ru, Ti, Ir, Sn, and Nb and deposited on the base from aqueous (alcohol) solutions are fine crystalline products of decomposition of these salts, that the imperfections of the crystallites determine the difference in the electrochemical behavior of single crystal and polycrystalline films (e.g., RuO 2 and Ir02), and that they form the basis of the effect of pyrolysis temperature on the electrochemical properties of low-wear anodes, etc.However, the studies carried out at the L. Ya. Karpov Scientific Research Institute of Physical Chemistry on the actual composition, structure and electron properties of pyrolytic ruthenium oxide and iridium oxide coatings and also two-and three-component films of composition RuO2-Ti02, IrO2-TiO 2, IrO2-RuO2-TiO 2, etc. have shown [4,5] that all these materials are products of incomplete dehydration of partially hydrated oxides of Ru, Ti, and Ir with an incomplete degree of crystallinity. These results were obtained by transmission electron microscopy and by electron and x-ray diffraction methods. The presence of molecules of H20 and OH groups in low-wear anodes was established from the data of derivatography and IR spectroscopy. For example, for ruthenium oxide films it was found that at a pyrolysis temperature of To = 450~ the coating consists of 70% crystalline phase with a rutile structure, the remainder being amorphous hydrated ruthenium oxide. Iridium oxide films obtained under the same pyr...

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Die Elektrochemie des Sauerstoffs als Meilenstein für eine nachhaltige Energieumwandlung

et al. 2013

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Elektrochemie wird eine entscheidende Rolle bei der Einführung von nachhaltigen Lösungen zur Energieversorgung spielen, besonders im Bereich der Umwandlung und Speicherung von elektrischer in chemische Energie in Elektrolysezellen sowie bei der Rückumwandlung und Verwendung der gespeicherten Energie in galvanischen Zellen. Die gemeinsame Herausforderung für beide Prozesse ist die Entwicklung von – bevorzugt leicht verfügbaren – nanostrukturierten Materialien, die diese elektrochemischen Reaktionen mit einem hohen Umsatz und über einen genügend langen Zeitraum katalysieren können. Für die gezielte Entwicklung von Materialien, die diese Voraussetzungen erfüllen, ist es notwendig, die zugrunde liegenden Prozesse und Mechanismen, die unter realen Bedingungen auftreten, vollständig zu verstehen. Eine vielversprechende Strategie, um dieses Verständnis zu erreichen, besteht in der Untersuchung des Einflusses der Materialeigenschaften auf die Aktivität oder Selektivität der Reaktion und die Stabilität unter Anwendungsbedingungen sowie in der Verwendung von komplementären In‐situ‐Techniken zur Untersuchung der Katalysatorstruktur und ‐zusammensetung.

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On the character of solid solutions in ruthenium-titanium oxide anodes

Cited by 20 publications

References 9 publications

Mechanistic Investigations of Ruthenium Polishing Enabled by Heterogeneous Catalysis With Titania-based Slurries

Mechanistic Investigations of Ruthenium Polishing Enabled by Heterogeneous Catalysis With Titania-based Slurries

Structure and processes of formation of oxide electrocatalysts

Die Elektrochemie des Sauerstoffs als Meilenstein für eine nachhaltige Energieumwandlung

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