An thin film of the di-decatungstosilicate with a tetra-ruthenium(IV)-oxo core and its electrochemical properties

Polyoxometalates containing noble metal ions, such as ruthenium, osmium, rhodium, palladium, platinum, silver and gold, are a structurally diverse class of compounds. They include both classical heteropolyanions (vanadates, molybdates, tungstates) in which noble metals are present as heteroatoms, as well as the recently discovered class of polyoxometalates with noble metal "addenda" atoms. The focus of this Review is on complexes that should, in principle, exist as discrete molecular species in solution, and which are therefore of interest for their reactivity, their future synthetic utility and potential applications, for example, in catalysis or nanoscience.

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“…[99] The analogous anion based on the less-stable g-[PW 10 O 36 ] 7À has been prepared and its catalytic activity examined.…”

Section: Rutheniummentioning

confidence: 99%

Noble Metals in Polyoxometalates

2012

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“…The analogs of the solution phase series of one electron processes associated with oxidation of [Ru III 4 POM] are essentially absent. [Ru IV 4 POM] has been immobilized on graphene and polyethylenimine and has shown well-defined voltammograms when in contact with acidic solutions. However, in the case of [Ru II bpy] 5 [Ru III 4 POM], presumably the [Ru III 4 POM] processes are inhibited by the presence of the [Ru II bpy] cation, and thus, [Ru III bpy] acts as the electron transfer mediator for the oxidation of [Ru III 4 POM] at slightly more positive potentials than 1000 mV to give a multielectron process.…”

Section: Resultsmentioning

confidence: 99%

Mediator Enhanced Water Oxidation Using Rb₄[Ru^II(bpy)₃]₅[{Ru^III₄O₄(OH)₂(H₂O)₄}(γ-SiW₁₀O₃₆)₂] Film Modified Electrodes

et al. 2014

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The water insoluble complex Rb4[Ru(II)(bpy)3]5[{Ru(III)4O4(OH)2(H2O)4}(γ-SiW10O36)2], ([Ru(II)bpy]5[Ru(III)4POM]), was synthesized from Rb8K2[{Ru(IV)4O4(OH)2(H2O)4}(γ-SiW10O36)2] and used for electrocatalytic water oxidation under both thin- and thick-film electrode conditions. Results demonstrate that the [Ru(II)bpy]5[Ru(III)4POM] modified electrode enables efficient water oxidation to be achieved at neutral pH using thin-film conditions, with [Ru(bpy)3](3+)([Ru(III)bpy]) acting as the electron transfer mediator and [Ru(V)4POM] as the species releasing O2. The rotating ring disc electrode (RRDE) method was used to quantitatively determine the turnover frequency (TOF) of the catalyst, and a value of 0.35 s(-1) was obtained at a low overpotential of 0.49 V (1.10 V vs Ag/AgCl) at pH 7.0. The postulated mechanism for the mediator enhanced catalytic water process in a pH 7 buffer containing 0.1 M LiClO4 as an additional electrolyte includes the following reactions (ion transfer for maintaining charge neutrality is omitted for simplicity): [Ru(II)bpy]5[Ru(III)4POM] → [Ru(III)bpy]5[Ru(V)4POM] + 13 e(-) and [Ru(III)bpy]5[Ru(V)4POM] + 2H2O → [Ru(III)bpy]5[Ru(IV)4POM] + O2 + 4H(+). The voltammetry of related water insoluble [Ru(II)bpy]2[S2M18O62] (M = W and Mo) and [Fe(II)Phen]x[Ru(III)4POM] materials has also been studied, and the lack of electrocatalytic water oxidation in these cases supports the hypothesis that [Ru(III)bpy] is the electron transfer mediator and [Ru(V)4POM] is the species responsible for oxygen evolution.

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“…For the former, in sulfate buffer, we can decompose the reduction of the SiW 10 part into two main processes corresponding each to four electrons, two for each SiW 10 moieties [62]. For the latter, the studies have been mainly focused on the oxidation part due to the capability of the Ru cluster to oxidize water into oxygen, but the reduction of the two SiW 10 moieties displays at least one four electron process around −0.4 V versus Ag/AgCl in acidic aqueous medium [63,64].…”

Section: Physical Methodsmentioning

confidence: 99%

Electrochemical properties of the [SiW10O36(M2O2
Kemmegne‐Mbouguen¹,
Floquet²,
Cadot³
2021
Comptes Rendus. Chimie
6
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0
0
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This paper deals with the electrochemical properties of three iso-structural compounds of general formula [SiW 10 O 36 (M 2 O 2 E 2)] 6− (M = Mo or W; E = S or O). A first part is focused on their electrochemical behaviors in aqueous medium. A second part concerns the electrocatalytic properties of these compounds in aqueous medium and the preparation of modified glassy carbon electrodes through a layer-by-layer methodology. This method allowed preparing a multilayer system, which was applied to the electroanalysis of iodate anions in aqueous medium with a limit detection of 6.2 µM.

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An thin film of the di-decatungstosilicate with a tetra-ruthenium(IV)-oxo core and its electrochemical properties

Cited by 21 publications

References 51 publications

Noble Metals in Polyoxometalates

Noble Metals in Polyoxometalates

Mediator Enhanced Water Oxidation Using Rb₄[Ru^II(bpy)₃]₅[{Ru^III₄O₄(OH)₂(H₂O)₄}(γ-SiW₁₀O₃₆)₂] Film Modified Electrodes

Electrochemical properties of the [SiW10O36(M2O2
Kemmegne‐Mbouguen¹,
Floquet²,
Cadot³
2021
Comptes Rendus. Chimie
6
0
0
0
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An thin film of the di-decatungstosilicate with a tetra-ruthenium(IV)-oxo core and its electrochemical properties

Cited by 21 publications

References 51 publications

Noble Metals in Polyoxometalates

Noble Metals in Polyoxometalates

Mediator Enhanced Water Oxidation Using Rb4[RuII(bpy)3]5[{RuIII4O4(OH)2(H2O)4}(γ-SiW10O36)2] Film Modified Electrodes

Electrochemical properties of the [SiW10O36(M2O2Kemmegne‐Mbouguen1, Floquet2, Cadot3 2021Comptes Rendus. Chimie6000View full textAdd to dashboardCite

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Mediator Enhanced Water Oxidation Using Rb₄[Ru^II(bpy)₃]₅[{Ru^III₄O₄(OH)₂(H₂O)₄}(γ-SiW₁₀O₃₆)₂] Film Modified Electrodes

Electrochemical properties of the [SiW10O36(M2O2
Kemmegne‐Mbouguen¹,
Floquet²,
Cadot³
2021
Comptes Rendus. Chimie
6
0
0
0
View full text Add to dashboard Cite