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Structural, Physicochemical, and Reactivity Properties of an All-Inorganic, Highly Active Tetraruthenium Homogeneous Catalyst for Water Oxidation.

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Title: Structural, Physicochemical, and Reactivity Properties of an All-Inorganic, Highly Active Tetraruthenium Homogeneous Catalyst for Water Oxidation.
Authors: Geletii, Yurii V.1, Besson, Claire1,2, Yu Hou1, Qiushi Yin1, Musaev, Djamaladdin G.3, Quiñonero, David3, Rui Cao1, HardcastIe, Kenneth I.1, Proust, Anna2,4, Kögerler, Paul5, Hill, Craig L.1 chill@emory.edu
Source: Journal of the American Chemical Society. 12/2/2009, Vol. 131 Issue 47, p17360-17370. 11p.
Subjects: Catalysts, Oxidation, Electrochemical analysis, Surface chemistry, Hydrogen-ion concentration, Volumetric analysis
Abstract: Several key properties of the water oxidation catalyst Rb8K2[{RuIV4O4(OH)2(H2O)4}(γ-SiW10O36)2] and its mechanism of water oxidation are given. The one-electron oxidized analogue [{RuVRuIV3O6(OH2)4}(γ-SiW10O36)2]11- has been prepared and thoroughly characterized. The voltammetric rest potentials, X-ray structures, elemental analysis, magnetism, and requirement of an oxidant (O2) indicate these two complexes contain [RuIV4O6] and [RuVRuIV3O6] cores, respectively. Voltammetry and potentiometric titrations establish the potentials of several couples of the catalyst in aqueous solution, and a speciation diagram (versus electrochemical potential) is calculated. The potentials depend on the nature and concentration of counterions. The catalyst exhibits four reversible couples spanning only ca. 0.5 V in the H2O/O2 potential region, keys to efficient water oxidation at low overpotential and consistent with DFT calculations showing very small energy differences between all adjacent frontier orbitals. The voltammetric potentials of the catalyst are evenly spaced (a Coulomb staircase), more consistent with bulk-like properties than molecular ones. Catalysis of water oxidation by [Ru(bpy)3]3+ has been examined in detail. There is a hyperbolic dependence of O2 yield on catalyst concentration in accord with competing water and ligand (bpy) oxidations. O2 yields, turnover numbers, and extensive kinetics data reveal several features and lead to a mechanism involving rapid oxidation of the catalyst in four one-electron steps followed by rate-limiting H2O oxidation/O2 evolution. Six spectroscopic, scattering, and chemical experiments indicate that the catalyst is stable in solution and under catalytic turnover conditions. However, it decomposes slowly in acidic aqueous solutions (pH < 1.5). [ABSTRACT FROM AUTHOR]
Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Structural, Physicochemical, and Reactivity Properties of an All-Inorganic, Highly Active Tetraruthenium Homogeneous Catalyst for Water Oxidation.
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  Data: Several key properties of the water oxidation catalyst Rb8K2[{RuIV4O4(OH)2(H2O)4}(γ-SiW10O36)2] and its mechanism of water oxidation are given. The one-electron oxidized analogue [{RuVRuIV3O6(OH2)4}(γ-SiW10O36)2]11- has been prepared and thoroughly characterized. The voltammetric rest potentials, X-ray structures, elemental analysis, magnetism, and requirement of an oxidant (O2) indicate these two complexes contain [RuIV4O6] and [RuVRuIV3O6] cores, respectively. Voltammetry and potentiometric titrations establish the potentials of several couples of the catalyst in aqueous solution, and a speciation diagram (versus electrochemical potential) is calculated. The potentials depend on the nature and concentration of counterions. The catalyst exhibits four reversible couples spanning only ca. 0.5 V in the H2O/O2 potential region, keys to efficient water oxidation at low overpotential and consistent with DFT calculations showing very small energy differences between all adjacent frontier orbitals. The voltammetric potentials of the catalyst are evenly spaced (a Coulomb staircase), more consistent with bulk-like properties than molecular ones. Catalysis of water oxidation by [Ru(bpy)3]3+ has been examined in detail. There is a hyperbolic dependence of O2 yield on catalyst concentration in accord with competing water and ligand (bpy) oxidations. O2 yields, turnover numbers, and extensive kinetics data reveal several features and lead to a mechanism involving rapid oxidation of the catalyst in four one-electron steps followed by rate-limiting H2O oxidation/O2 evolution. Six spectroscopic, scattering, and chemical experiments indicate that the catalyst is stable in solution and under catalytic turnover conditions. However, it decomposes slowly in acidic aqueous solutions (pH &lt; 1.5). [ABSTRACT FROM AUTHOR]
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  Data: &lt;i&gt;Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder&#39;s express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.&lt;/i&gt; (Copyright applies to all Abstracts.)
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        Value: 10.1021/ja907277b
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        Text: English
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        PageCount: 11
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    Subjects:
      – SubjectFull: Catalysts
        Type: general
      – SubjectFull: Oxidation
        Type: general
      – SubjectFull: Electrochemical analysis
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      – SubjectFull: Surface chemistry
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      – SubjectFull: Hydrogen-ion concentration
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      – SubjectFull: Volumetric analysis
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      – TitleFull: Structural, Physicochemical, and Reactivity Properties of an All-Inorganic, Highly Active Tetraruthenium Homogeneous Catalyst for Water Oxidation.
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