Thermal and light-induced reduction of the ruthenium complex cation Ru(bpy)33+ in aqueous solution

Ghosh, Pushpito K.; Brunschwig, Bruce S.; Chou, Mei H.; Creutz, Carol; Sutin, Norman

doi:10.1021/ja00329a022

Cited by 249 publications

(323 citation statements)

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“…However, at pH ≥11, a more rapid loss of current response for the catalyst is observed with application of the high positive potentials required for water oxidation. The loss of catalytic activity appears to be due to ligand decomposition, consistent with known reactivity in solution (48,49), and not to surface detachment due to hydrolysis.…”

Section: Ru-oh 2 2+supporting

confidence: 68%

Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation

Vannucci

Alibabaei

Losego

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

136

154

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Enhancing the surface binding stability of chromophores, catalysts, and chromophore-catalyst assemblies attached to metal oxide surfaces is an important element in furthering the development of dye sensitized solar cells, photoelectrosynthesis cells, and interfacial molecular catalysis. Phosphonate-derivatized catalysts and molecular assemblies provide a basis for sustained water oxidation on these surfaces in acidic solution but are unstable toward hydrolysis and loss from surfaces as the pH is increased. Here, we report enhanced surface binding stability of a phosphonate-derivatized water oxidation catalyst over a wide pH range (1-12) by atomic layer deposition of an overlayer of TiO 2 . Increased stability of surface binding, and the reactivity of the bound catalyst, provides a hybrid approach to heterogeneous catalysis combining the advantages of systematic modifications possible by chemical synthesis with heterogeneous reactivity. For the surface-stabilized catalyst, greatly enhanced rates of water oxidation are observed upon addition of buffer bases −H 2 PO − 4 /HPO 2− 4 , B(OH) 3 /B(OH) 2 O − , HPO 2− 4 /PO 3− 4 − and with a pathway identified in which O-atom transfer to OH − occurs with a rate constant increase of 10 6 compared to water oxidation in acid.electrocatalysis | surface stabilization H eterogeneous catalysis plays an important role in industrial chemical processing, fuel reforming, and energy-producing reactions. Examples include the Haber-Bosch process, steam reforming, Ziegler-Natta polymerization, and hydrocarbon cracking (1-8). Research in heterogeneous catalysis continues to flourish (9-15) but iterative design and modification are restricted by limitations in materials preparation and experimental access to surface mechanisms. By contrast, synthetic modification of molecular catalysts is possible by readily available routes; a variety of experimental techniques is available for monitoring rates and mechanism in solution for the investigation of homogeneous catalysis (16-23). Transferring this knowledge and the reactivity of homogeneous molecular catalysts to a surface could open the door to heterogeneous applications in fuel cells, dye sensitized photoelectrochemical cells, and multiphase industrial reactions.Procedures are available for immobilization of organometallic and coordination complexes on the surfaces of solid supports. Common strategies include surface derivatization of metal oxides by carboxylate, phosphonate, and siloxane bindings (24-27), carbongrafted electrodes (28-30), and electropolymerization (31-33). These approaches provide a useful bridge to the interface and a way to translate mechanistic understanding and ease of synthetic modification of solution catalysts to heterogeneous applications with a promise of higher reactivity under milder conditions. A significant barrier to this approach arises from the limited stability of surface binding. Surface-bound carboxylates are typically unstable to hydrolysis in water, whereas phosphonates are unstable in neutral or basic...

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Section: Ru-oh 2 2+supporting

confidence: 68%

Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation

Vannucci

Alibabaei

Losego

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

136

154

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“…It was known that Ru(bpy) 3 3+ is relatively stable in weakly acidic solution, and to be reduced in alkaline solution to form Ru(bpy) 3 2+ through a reaction with hydroxide ion. Because of this reaction, the lifetime of Ru(bpy) 3 3+ complex at pH 10 is greatly reduced in comparison to that at pH 5-7 [36]. However [Ru(bpy) 3 2+ ]* lies about 2.2 V above the ground state, which also has been reported in the previous work [34], indicating that the intermediate involved in the CL step must be a fairly high energetic one.…”

Section: Methodssupporting

confidence: 73%

Chemiluminescent investigation of tris(2,2'-bipyridyl)ruthenium(II) immobilized on a cationic ion-exchange resin and its application to analysis

Lin

Yamada

2002

Analytical and Bioanalytical Chemistry

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Tris-(2, 2'-bipyridyl)ruthenium(II) complex, Ru(bpy) 3 2+ , was immobilized on the Dowex-50 W cationic ion-exchange resin. The chemiluminescent characteristics of Ru(bpy) 3 2+ in solution and in resin form were compared by using batch and flow injection methods. A strong chemiluminescence was observed during the reaction of Ru(bpy) 3 2+ both in solution and in resin with KMnO 4 or Ce(SO 4 ) 2 under acidic or basic conditions. The Ru(bpy) 3 2+ immobilized resin is stable, which can be used at least for 6 months when it reacts with the dilute KMnO 4 solution. Based on this property, Ru(bpy) 3 2+ immobilized in the resin phase was developed as a flow-through chemiluminescent sensor that could be used to determine oxalate, sulfite and ethanol chemically or electronically with Ru(bpy) 3 3+ generation on the surface of resin. The limits of detection were 1×10 -6 M for oxalate, 0.5% (v/v) for ethanol and 1×10 -7 M for sulfite. The method has been successfully applied to determine sulfite in sugar.

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“…Moreover, the back electron transfer could favor the formation of ground state products even if excited state generation is energy sufficient (13,14,38,39).…”

Section: Discussionmentioning

confidence: 99%

“…Chemiluminescence resulting from electron trans-0097-6156/87/0333-0155$06.00/0 © 1987 American Chemical Society fer reactions of transition metal complexes has been observed in a few cases (3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14). However, the electrochemical generation of an appropriate redox pair in situ offers various advantages.…”

mentioning

confidence: 99%

Electrochemiluminescence of Organometallics and Other Transition Metal Complexes

Vogler

Kunkely

1987

ACS Symposium Series

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Thermal and light-induced reduction of the ruthenium complex cation Ru(bpy)33+ in aqueous solution

Cited by 249 publications

References 0 publications

Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation

Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation

Chemiluminescent investigation of tris(2,2'-bipyridyl)ruthenium(II) immobilized on a cationic ion-exchange resin and its application to analysis

Electrochemiluminescence of Organometallics and Other Transition Metal Complexes

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