Reaction of Potassium Peroxodisulfate with Water under UV Irradiation

Nagashima, Kunio; Inoue, Masakí; Namiki, Hiroshi

doi:10.5796/electrochemistry.68.651

Cited by 4 publications

(5 citation statements)

References 3 publications

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“…This indicates that the presence of manganese complex is not needed to observe O 2 evolving. Moreover, under UV irradiation, it has been recently shown that S 2 O 8 2- reacts with water to form dioxygen . So, this electron acceptor is not adapted since the O 2 source remains ambiguous.…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, under UV irradiation, it has been recently shown that S 2 O 8 2reacts with water to form dioxygen. 36 So, this electron acceptor is not adapted since the O 2 source remains ambiguous.…”

Section: B Electrochemical Properties Of [Mnmentioning

confidence: 99%

“…20 The 16 O atom of OClexchanges rapidly with 18 O of water making Na 18 OCl unsuitable for H 2 18 O labeling experiments. In the case of oxone, this exchange is slow and the maximum of 36 O 2 obtained is 12%, depending on the relative concentration of 2 and oxone. The rate-limiting step for O 2 evolution is proposed to be the formation of an (H 2 O)Mn IV O 2 -Mn V dO intermediate that can exchange with water and then competitively react with either oxone or water/hydroxide to produce O 2 .…”

Section: Introductionmentioning

confidence: 96%

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Electrochemical and Chemical Formation of [Mn₄^IVO₅(terpy)₄(H₂O)₂]⁶⁺, in Relation with the Photosystem II Oxygen-Evolving Center Model [Mn₂^III,IVO₂(terpy)₂(H₂O)₂]³⁺

et al. 2005

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To examine the real ability of the binuclear di-mu-oxo complex [Mn2(III,IV)O2(terpy)2(H2O)2]3+ (2) to act as a catalyst for water oxidation, we have investigated in detail its redox properties and that of its mononuclear precursor complex [Mn(II)(terpy)2]2+ (1) in aqueous solution. It appears that electrochemical oxidation of 1 allows the quantitative formation of 2 and, most importantly, that electrochemical oxidation of 2 quantitatively yields the stable tetranuclear Mn(IV) complex, [Mn4(IV)O5(terpy)4(H2O)2]6+ (4), having a linear mono-mu-oxo{Mn2(mu-oxo)2}2 core. Therefore, these results show that the electrochemical oxidation of 2 in aqueous solution is only a one-electron process leading to 4 via the formation of a mono-mu-oxo bridge between two oxidized [Mn2(IV,IV)O2(terpy)2(H2O)2]4+ species. 4 is also quantitatively formed by dissolution of the binuclear complex [Mn2(IV,IV)O2(terpy)2(SO4)2] (3) in aqueous solutions. Evidence of this work is that 4 is stable in aqueous solutions, and even if it is a good synthetic analogue of the "dimers-of-dimers" model compound of the OEC in PSII, this complex is not able to oxidize water. As a consequence, since 4 results from an one-electron oxidation of 2, 2 cannot act as an efficient homogeneous electrocatalyst for water oxidation. This work demonstrates that a simple oxidation of 2 cannot produce molecular oxygen without the help of an oxygen donor.

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Section: Resultsmentioning

confidence: 99%

Section: B Electrochemical Properties Of [Mnmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 96%

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Electrochemical and Chemical Formation of [Mn₄^IVO₅(terpy)₄(H₂O)₂]⁶⁺, in Relation with the Photosystem II Oxygen-Evolving Center Model [Mn₂^III,IVO₂(terpy)₂(H₂O)₂]³⁺

et al. 2005

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“…Furthermore, aqueous solutions of S 2 O 8 2À are decomposed under UV irradiation to produce O 2 . [225]…”

Section: Cobalt Oxidesmentioning

confidence: 99%

Splitting Water with Cobalt

2011

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The future of energy supply depends on innovative breakthroughs regarding the design of cheap, sustainable, and efficient systems for the conversion and storage of renewable energy sources, such as solar energy. The production of hydrogen, a fuel with remarkable properties, through sunlight-driven water splitting appears to be a promising and appealing solution. While the active sites of enzymes involved in the overall water-splitting process in natural systems, namely hydrogenases and photosystem II, use iron, nickel, and manganese ions, cobalt has emerged in the past five years as the most versatile non-noble metal for the development of synthetic H(2)- and O(2)-evolving catalysts. Such catalysts can be further coupled with photosensitizers to generate photocatalytic systems for light-induced hydrogen evolution from water.

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“…Abgesehen davon zersetzt sich S 2 O 8 2À in wässriger Lösung schon bei UV-Bestrahlung unter Bildung von O 2 . [225] Cobaltverbindungen wurden auch in Anoden von photoelektrochemischen Zellen zur O 2 -Erzeugung verwendet, die zumindest teilweise durch die Lichtabsorption eines halbleitenden Substrats angetrieben werden. Für eine optimale Verwertung des einfallenden Lichts zur Wasseroxidation sollten die Katalysatoren hohe Umsatzfrequenzen (in der Größenordnung von 10 s À1 ) und Oberflächendichten (in der Größenordnung von 10 katalytisch aktiven Zentren pro Quadratnanometer) aufweisen; so wäre eine oberflächenspezifische TOF um 100 s À1 nm À2 zu erreichen.…”

Section: Cobaltoxideunclassified

Wasserspaltung mit Cobalt

2011

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Die Energieversorgung der Zukunft kann nur durch grundlegende Neuerungen auf dem Gebiet billiger, nachhaltiger und effizienter Systeme zur Gewinnung und Speicherung von Energie aus erneuerbaren Quellen oder aus Sonnenlicht gesichert werden. Die Erzeugung von Wasserstoff, einem Brennstoff mit bemerkenswerten Eigenschaften, durch die Wasserspaltung mithilfe von Sonnenlicht ist in diesem Zusammenhang ein vielversprechender Ansatz. Während die aktiven Zentren von wasserspaltenden Enzymen – wie Hydrogenasen und Photosystem II – Eisen‐, Nickel‐ und Manganionen enthalten, hat sich Cobalt in den vergangenen fünf Jahren als vielseitigstes unedles Metall bei der Entwicklung synthetischer Katalysatoren zur H2‐ und O2‐Erzeugung durch Reduktion bzw. Oxidation von Wasser bewährt. Solche Katalysatoren lassen sich mit Photosensibilisatoren zu Systemen für die photokatalytische Wasserstofferzeugung aus Wasser koppeln.

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Reaction of Potassium Peroxodisulfate with Water under UV Irradiation

Cited by 4 publications

References 3 publications

Electrochemical and Chemical Formation of [Mn₄^IVO₅(terpy)₄(H₂O)₂]⁶⁺, in Relation with the Photosystem II Oxygen-Evolving Center Model [Mn₂^III,IVO₂(terpy)₂(H₂O)₂]³⁺

Electrochemical and Chemical Formation of [Mn₄^IVO₅(terpy)₄(H₂O)₂]⁶⁺, in Relation with the Photosystem II Oxygen-Evolving Center Model [Mn₂^III,IVO₂(terpy)₂(H₂O)₂]³⁺

Splitting Water with Cobalt

Wasserspaltung mit Cobalt

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Reaction of Potassium Peroxodisulfate with Water under UV Irradiation

Cited by 4 publications

References 3 publications

Electrochemical and Chemical Formation of [Mn4IVO5(terpy)4(H2O)2]6+, in Relation with the Photosystem II Oxygen-Evolving Center Model [Mn2III,IVO2(terpy)2(H2O)2]3+

Electrochemical and Chemical Formation of [Mn4IVO5(terpy)4(H2O)2]6+, in Relation with the Photosystem II Oxygen-Evolving Center Model [Mn2III,IVO2(terpy)2(H2O)2]3+

Splitting Water with Cobalt

Wasserspaltung mit Cobalt

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Electrochemical and Chemical Formation of [Mn₄^IVO₅(terpy)₄(H₂O)₂]⁶⁺, in Relation with the Photosystem II Oxygen-Evolving Center Model [Mn₂^III,IVO₂(terpy)₂(H₂O)₂]³⁺

Electrochemical and Chemical Formation of [Mn₄^IVO₅(terpy)₄(H₂O)₂]⁶⁺, in Relation with the Photosystem II Oxygen-Evolving Center Model [Mn₂^III,IVO₂(terpy)₂(H₂O)₂]³⁺