Chemical and Photochemical Water Oxidation Mediated by an Efficient Single‐Site Ruthenium Catalyst

Abdel‐Magied, Ahmed F.; Shatskiy, Andrey; Liao, Rong‐Zhen; Laine, Tanja M.; Arafa, Wael A. A.; Siegbahn, Per E. M.; Kärkäs, Markus D.; Johnston, Eric V.

doi:10.1002/cssc.201601171

Cited by 14 publications

(6 citation statements)

References 101 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Therefore, it was important to substantiate the catalytic performance of Mn 19 Br under light-driven OER conditions. A well-established literature protocol, 63 involving a three-component system consisting of a colloidal suspension of Mn 19 Br, [Ru-(bpy) 2 (deeb)](PF 6 ) 2 as photosensitizer, and Na 2 S 2 O 8 as sacrificial electron acceptor was applied. Further, control experiments in which one of each of the three photocatalytic components were removed resulted in negligible O 2 evolution, demonstrating that all three components are integral for overall OER activity (Table S2).…”

Section: Structure Ofsupporting

confidence: 85%

Bioinspired Water Oxidation Using a Mn-Oxo Cluster Stabilized by Non-Innocent Organic Tyrosine Y161 and Plastoquinone Mimics

Soriano-López

Elliott

Kathalikkattil

et al. 2020

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

The complexity and energy demand of the H 2 O oxidation half-reaction represents the bottleneck for the development of sustainable, environmentally friendly H 2 economies using H 2 O as energy feedstock. In Nature, photosynthetic H 2 O oxidation processes occur in photosystem-II (PS-II) and are facilitated by the oxygen evolving complex (OEC), a manganese-oxo cluster {Mn 4 CaO 5 } with cubane-like topology. In recent years, the use of manganese-based H 2 O oxidation catalysts has attracted significant scientific attention, not only to mimic and understand naturally occurring processes, but also due to the low toxicity and high abundancy of Mn in the Earth's crust. Here we report the catalytic H 2 O oxidation activity at pH 7.2 of a high-nuclearity manganese-oxo cluster. The species, which contains multiple cubane motifs and which is stabilized by redox-active aromatic organic ligands, gives rise to an onset overpotential as low as 255 mV when dispersed in a carbon paste matrix, achieving high current densities of 10 mA cm −2 and even 100 mA cm −2 at η = 482 and 654 mV, respectively. The electrodes show good stability under turnover conditions for 7 h. Additionally, direct light-induced O 2 evolution measurements confirm a reaction rate of 0.72 s −1 and turnover number (TON) of up to 55. The outlined experimental concept demonstrates how a synergistic effect between non-innocent, redoxactive organic ligands and bioinspired Mn oxo-clusters resembling the natural {Mn 4 CaO 5 } unit, which are dispersed in a conductive carbon matrix and protected by a Nafion membrane, can facilitate remarkably high catalytic activity under neutral, environmentally friendly pH conditions.

show abstract

Section: Structure Ofsupporting

confidence: 85%

Bioinspired Water Oxidation Using a Mn-Oxo Cluster Stabilized by Non-Innocent Organic Tyrosine Y161 and Plastoquinone Mimics

Soriano-López

Elliott

Kathalikkattil

et al. 2020

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

show abstract

“…For a conceptional similar system it has been shown that changing the functional group coordinating to the metal center significantly alters the reduction potentials and thereby potentially the catalytic activity. 49 We further compared the thermodynamics of the whole catalytic cycle with an thermodynamically ideal catalyst as has been done in previous work. 47,48,50 Here, 'ideal' is meant in the sense that the Gibbs free energy associated with water oxidation (see Equation 1) is equally distributed among four PCETs, thereby minimizing the theoretical overpotential of the reaction.…”

Section: Py5ome Variant: Para-omementioning

confidence: 99%

Towards the rational design of the Py5-ligand framework for ruthenium-based water oxidation catalysts

2018

View full text Add to dashboard Cite

In order to rationally design water oxidation catalysts (WOCs), an in-depth understanding of the reaction mechanism is essential. In this study we showcase the complexity of catalytic water oxidation, by elucidating how modifications of the pentapyridyl (Py5) ligand-framework influence the thermodynamics and kinetics of the process. In the reaction mechanism the pyridine-water exchange was identified as a key reaction which appears to determine the reactivity of the Py5-WOCs. Exploring the capabilities of in silico design we show which modifications of the ligand framework appear promising when attempting to improve the catalytic performance of WOCs derived from Py5.

show abstract

“…The UV–vis absorption spectra of Ru III complexes ( 4a–g ) in CH 3 CN at neutral pH displayed three bands, at about 250, 330 and 420 nm (See Supporting Information). The first intense band was ascribed to π–π* transitions within the ancillary ligands while the latter two broad absorption bands were assigned to metal‐to‐ligand charge transfer (MLCT) transitions as expected for a Ru III complex …”

Section: Resultsmentioning

confidence: 92%

Water as a solvent for Ru‐catalyzed click reaction: Highly efficient recyclable catalytic system for triazolocoumarins synthesis

Arafa

Nayl

2019

Applied Organom Chemis

View full text Add to dashboard Cite

A new family of Ru (III) complexes has been synthesized, characterized and their catalytic performance has been tested for alkyne–azide cycloaddition (AAC) in water under ultrasonic irradiation conditions. These complexes are found to be effective heterogeneous catalysts for the regioselective synthesis of 1,4‐disubstituted‐1,2,3‐triazoles giving access to these products in excellent yields. The catalyst system is equally active for one‐pot multi‐component protocol of the AAC reactions. Also, successive sequencing of Huisgen reaction with Knoevenagel condensation reaction results in the effective assembly of a diversified hitherto unreported 1,2,3‐triazolyl coumarin frameworks. In present strategy, the catalyst could be easily isolated by simple filtration and reused up to eight consecutive cycles without significant drop in the reaction yields. During the leaching experiment, there is no leaching amount of the catalyst was detected, suggesting true heterogeneity in the catalytic system. The results of gram‐scale reaction and green metrics calculations also confirmed the sustainability and industrial applicability of the current catalytic protocol.

show abstract

Chemical and Photochemical Water Oxidation Mediated by an Efficient Single‐Site Ruthenium Catalyst

Cited by 14 publications

References 101 publications

Bioinspired Water Oxidation Using a Mn-Oxo Cluster Stabilized by Non-Innocent Organic Tyrosine Y161 and Plastoquinone Mimics

Bioinspired Water Oxidation Using a Mn-Oxo Cluster Stabilized by Non-Innocent Organic Tyrosine Y161 and Plastoquinone Mimics

Towards the rational design of the Py5-ligand framework for ruthenium-based water oxidation catalysts

Water as a solvent for Ru‐catalyzed click reaction: Highly efficient recyclable catalytic system for triazolocoumarins synthesis

Contact Info

Product

Resources

About