Characterization and Activity Analysis of Catalytic Water Oxidation Induced by Hybridization of [(OH2)(terpy)Mn(μ-O)2Mn(terpy)(OH2)]3+ and Clay Compounds

Narita, Komei; Kawamata, Takayuki; Sone, Koji; Shimizu, Ken‐ichi; Yagi, Masayuki

doi:10.1021/jp063679n

Cited by 80 publications

(80 citation statements)

References 29 publications

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“…52, 53 In contrast, increasing the loading of Mn catalysts within a layered material enhances the rate of oxygen generation. 45 Thus, the incorporation of recently reported Mn catalysts 41 into these polymer layers may lead to practical success at higher catalyst concentration. The potential of this approach has been demonstrated by our own recent work on a photocatalytic assembly that utilised a bio-inspired cubane cluster as water oxidation catalyst.…”

Section: Discussionmentioning

confidence: 99%

Molecular water-oxidation catalysts for photoelectrochemical cells

et al. 2009

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Photoelectrochemical cells that efficiently split water into oxygen and hydrogen, "the fuel of the future", need to combine robust water oxidation catalysts at the anode (2H(2)O -> O-2 + 4H(+) + 4e(-)) with hydrogen reduction catalysts at the cathode (2H(+) + 2e(-) -> H-2). Both sets of catalysts will, ideally, operate at low overpotentials and employ light-driven or light-assisted processes. In this Perspective article, we focus on significant efforts to develop solid state materials and molecular coordination complexes as catalyst for water oxidation. We briefly review the field with emphasis on the various molecular catalysts that have been developed and then examine the activity of molecular catalysts in water oxidation following their attachment to conducting electrodes. For such molecular species to be useful in a solar water-splitting device it is preferable that they are securely and durably affixed to an electrode surface. We also consider recent developments aimed at combining the action of molecular catalysts with light absorption so that light driven water oxidation may be achieved. Photoelectrochemical cells that efficiently split water into oxygen and hydrogen, "the fuel of the future", need to combine robust water oxidation catalysts at the anode (2H 2 O → O 2 + 4H + + 4e -) with hydrogen reduction catalysts at the cathode (2H + + 2e -→ H 2 ). Both sets of catalysts will, ideally, operate at low overpotentials and employ light-driven or light-assisted processes. In this Perspective article, we focus on significant efforts to develop solid state materials and molecular coordination complexes as catalyst for water oxidation. We briefly review the field with emphasis on the various molecular catalysts that have been developed and then examine the activity of molecular catalysts in water oxidation following their attachment to conducting electrodes. For such molecular species to be useful in a solar water-splitting device it is preferable that they are securely and durably affixed to an electrode surface. We also consider recent developments aimed at combining the action of molecular catalysts with light absorption so that light driven water oxidation may be achieved.

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Section: Discussionmentioning

confidence: 99%

Molecular water-oxidation catalysts for photoelectrochemical cells

et al. 2009

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“…Catalytic turnover is not attained when Ce(IV) is used as the oxidant due to the low pH required for use of Ce(IV) as an oxidant which causes deactivation of the catalyst [96]. In contrast to the single-turnover oxygen evolution by the homogeneous system using Ce(IV), 7 has been shown to evolve oxygen catalytically using Ce(IV) when it is supported on a clay mineral [97,98]. The dramatic improvement of 7 in heterogeneous versus homogenous systems with Ce(IV) is proposed to be the result of the stabilizing clay environment which prevents the dimer from dissociating into monomers.…”

Section: [(Tpy)(h 2 O)mn(o) 2 Mn(h 2 O)(tpy)] 3+ -mentioning

confidence: 99%

Functional models for the oxygen-evolving complex of photosystem II

Cady

Crabtree

Brudvig

2008

Coordination Chemistry Reviews

387

255

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In the last ten years, a number of advances have been made in the study of the oxygen-evolving complex (OEC) of photosystem II (PSII). Along with this new understanding of the natural system has come rapid advance in chemical models of this system. The advance of PSII model chemistry is seen most strikingly in the area of functional models where the few known systems available when this topic was last reviewed has grown into two families of model systems. In concert with this work, numerous mechanistic proposals for photosynthetic water oxidation have been proposed. Here, we review the recent efforts in functional model chemistry of the oxygen-evolving complex of photosystem II.

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“…The presence of the trifluoroacetate ligands may prevent the formation of a possible Mn V O species. Despite these solution studies, Yagi has shown that these water oxidation catalysts are effective when placed on a clay surface [157].…”

Section: Proposed Catalytic Dinuclear Mn Modelsmentioning

confidence: 99%

Reflections on small molecule manganese models that seek to mimic photosynthetic water oxidation chemistry

Mullins

Pecoraro

2008

Coordination Chemistry Reviews

327

252

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Recent advances in the study of the Oxygen Evolving Complex (OEC) of Photosystem II (PSII) include structural information attained from several X-ray crystallographic (XRD) and spectroscopic (XANES and EXAFS) investigations. The possible structural features gleaned from these studies have enabled synthetic chemists to design more accurate model complexes, which in turn, offer better insight into the possible pathways used by PSII to drive photosynthetic water oxidation catalysis. Mononuclear model compounds have been used to advance the knowledge base regarding the physical properties and reactivity of high-valent (Mn(IV) or Mn(V)) complexes. Such investigations have been especially important in regard to the manganyl (Mn(IV)=O or Mn(V)≡O) species, as there are no reports, to date, of any structural characterized multinuclear model compounds that incorporate such a functionality. Dinuclear and trinuclear model compounds have also been thoroughly studied in attempts to draw further comparison to the physical properties observed in the natural system and to design systems of catalytic relevance. As the reactive center of the OEC has been shown to contain an oxo-Mn(4)Ca cluster, exact structural models necessitate a tetranuclear Mn core. The number of models that make use of Mn(4) clusters has risen substantially in recent years, and these models have provided evidence to support and refute certain mechanistic proposals. Further work is needed to adequately address the rationale for Ca (and Cl) in the OEC and to determine the sequence of events that lead to O(2) evolution.

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Characterization and Activity Analysis of Catalytic Water Oxidation Induced by Hybridization of [(OH₂)(terpy)Mn(μ-O)₂Mn(terpy)(OH₂)]³⁺ and Clay Compounds

Cited by 80 publications

References 29 publications

Molecular water-oxidation catalysts for photoelectrochemical cells

Molecular water-oxidation catalysts for photoelectrochemical cells

Functional models for the oxygen-evolving complex of photosystem II

Reflections on small molecule manganese models that seek to mimic photosynthetic water oxidation chemistry

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