Ligand Geometry Directs OO Bond‐Formation Pathway in Ruthenium‐Based Water Oxidation Catalyst

Maji, Somnath; Vigara, Laura; Cottone, Francesca; Bozoglián, Fernando; Benet‐Buchholz, Jordi; Llobet, Antoni

doi:10.1002/ange.201201356

Cited by 29 publications

(7 citation statements)

References 32 publications

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“…Although water oxidation catalyst is necessary to extract electrons from water (as an electron source) for producing high energy compounds in artificial photosynthesis, development of an efficient and robust water oxidation catalyst is a bottleneck and very important task to bring a breakthrough in the field. In a recent decade, a variety of metal complexes based on manganese, [4][5][6][7][8] ruthenium [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] and iridium [29][30][31][32], iron [33,34], cupper [35][36][37] and cobalt [38][39][40][41] have been reported as active catalysts for water oxidation. The catalyses by ruthenium complexes are studied most extensively.…”

Section: Introductionmentioning

confidence: 99%

Spectroelectrochemical investigation of electrocatalytic water oxidation by a mononuclear ruthenium complex in a homogeneous solution

Honta

Tajima

Sato

et al. 2015

Journal of Photochemistry and Photobiology A: Chemistry

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investigation of electrocatalytic water oxidation by a mononuclear ruthenium complex in a homogeneous solution, Journal of Photochemistry and Photobiology A: Chemistry http://dx.2 Highlight • Electrocatalytic water oxidation was studied by Potential-step chronocoulospectrometry. • [Ru(EtOtpy)(bpy)OH 2 ] 2+ can work for electrocatalytic water oxidation under weakly acidic conditions. • The rate-determining step for the electrocatalysis is oxidation of Ru IV =O to Ru V =O species. Abstract Electrochemical water oxidation by [Ru(EtOtpy)(bpy)OH 2 ] 2+ (1) (EtOtpy = 4'-ethoxy-2,2':6'2''-terpyridine, bpy = 2,2'-bipydidine) was investigated in a homogeneous solution under weakly acidic conditions (pH = 5.3). The cyclic voltammogram of a 1 aqueous solution showed that successive proton-coupled electron transfer reactions of Ru II -OH 2 / Ru III -OH and Ru III -OH / Ru IV =O redox pairs and high anodic current above 1.1 V vs SCE. Electrocatalytic water oxidation was corroborated by the bulk electrolysis at 1.5 V; the significant amount of O 2 was evolved compared with the blank during the electrolysis. Potential-step chronocoulospectrometry (PSCCS) from 0.0 V to 1.52 V vs SCE was conducted to observe the change of 1 in solution during the electrocatalysis. The in situ UV visible spectral change showed oxidation of 1 (Ru II -OH 2 ) to Ru III -OH and to further oxidation of Ru III -OH to Ru IV =O, and that the Ru IV =O species mainly exists in a steady state after 200 s in the electrocatalysis. The in situ UV visible spectral change in a reverse potential step from 1.52 V to 0.22 V vs SCE exhibited that Ru II -OH 2 completely recovers by 2 electron re-reduction process from the steady state in the electrocatalysis. The observation of Ru IV =O in a steady state suggests that a rate determining step in the catalytic cycle is oxidation of Ru IV =O to Ru V =O rather than the O-O bonding formation by nucleophilic attack of water to Ru V =O in the 3 electrocatalysis in a homogeneous solution.

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Section: Introductionmentioning

confidence: 99%

Spectroelectrochemical investigation of electrocatalytic water oxidation by a mononuclear ruthenium complex in a homogeneous solution

Honta

Tajima

Sato

et al. 2015

Journal of Photochemistry and Photobiology A: Chemistry

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“…In the I2M mechanism (Figure b), the coupling of either two M n + −O oxyl radicals or coupling of one M n + −O oxyl radical with another M n + −O unit of nonradical character affords a peroxo M ( n −1)+ −O−O−M ( n −1)+ intermediate, which releases O 2 and returns to 2M ( n −2)+ −OH 2 , with incorporation of H 2 O . It involves intramolecular and intermolecular pathways. For an example of the former, the dinuclear Ru complex [{Ru II (tpy)(H 2 O)} 2 (μ‐bpp)] 3+ [bpp=3,5‐bis‐(2‐pyridyl)pyrazolate, tpy=2,2′:6′,2′′‐terpyridine] has two Ru centers at close proximity, allowing coupling between them .…”

Section: Mechanistic Pathways For O−o Bond Formationmentioning

confidence: 99%

“…For an example of the former, the dinuclear Ru complex [{Ru II (tpy)(H 2 O)} 2 (μ‐bpp)] 3+ [bpp=3,5‐bis‐(2‐pyridyl)pyrazolate, tpy=2,2′:6′,2′′‐terpyridine] has two Ru centers at close proximity, allowing coupling between them . The intermolecular pathways was proposed for a dinuclear Ru complex, trans ‐[{Ru II (tpym)(H 2 O)} 2 (μ‐bpp)] 3+ , (tpym=tris‐2‐pyridylmethane) . Because the aqua groups are trans to one another, a bimolecular process occurs generating a putative tetranuclear intermediate bridged by a peroxide ligand.…”

Section: Mechanistic Pathways For O−o Bond Formationmentioning

confidence: 99%

Recent Advances in the Development of Molecular Catalyst‐Based Anodes for Water Oxidation toward Artificial Photosynthesis

et al. 2019

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Catalytic water oxidation represents a bottleneck for developing artificial photosynthetic systems that store solar energy as renewable fuels. A variety of molecular water oxidation catalysts (WOCs) have been reported over the last two decades. In view of their applications in artificial photosynthesis devices, it is essential to immobilize molecular catalysts onto the surfaces of conducting/semiconducting supports for fabricating efficient and stable water oxidation anodes/photoanodes. Molecular WOC‐based anodes are essential for developing photovoltaic artificial photosynthesis devices and, moreover, the performance of molecular WOC on anodes will provide important insight into designing extended molecular WOC‐based photoanodes for photoelectrochemical (PEC) water oxidation. This Review concerns recent progress in the development of molecular WOC‐based anodes over the last two decades and looks at the prospects for using such anodes in artificial photosynthesis.

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“…Seine Laufbahn wurde hier vorgestellt, als er den RSEQ‐Bruker‐Preis in Anorganischer Chemie bekommen hatte 8a. In seinem neuesten Beitrag in der Angewandten Chemie berichtet er über rutheniumbasierte Katalysatoren der Wasseroxidation 8b…”

Section: Ausgezeichnet …︁unclassified

Preise der Gesellschaft Deutscher Chemiker: K. Müllen, A. Fürstner, L. F. Nazar, M. Scheer, T. C. Schmidt, R. E. Mulvey, B. Rieger, H. L. Anderson, A. Llobet

2013

Angewandte Chemie

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Ligand Geometry Directs OO Bond‐Formation Pathway in Ruthenium‐Based Water Oxidation Catalyst

Cited by 29 publications

References 32 publications

Spectroelectrochemical investigation of electrocatalytic water oxidation by a mononuclear ruthenium complex in a homogeneous solution

Spectroelectrochemical investigation of electrocatalytic water oxidation by a mononuclear ruthenium complex in a homogeneous solution

Recent Advances in the Development of Molecular Catalyst‐Based Anodes for Water Oxidation toward Artificial Photosynthesis

Preise der Gesellschaft Deutscher Chemiker: K. Müllen, A. Fürstner, L. F. Nazar, M. Scheer, T. C. Schmidt, R. E. Mulvey, B. Rieger, H. L. Anderson, A. Llobet

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