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

Water oxidation is a fundamental step in artificial photosynthesis for solar fuels production. In this study, we report a single-site Ru-based water oxidation catalyst, housing a dicarboxylate-benzimidazole ligand, that mediates both chemical and light-driven oxidation of water efficiently under neutral conditions. The importance of the incorporation of the negatively charged ligand framework is manifested in the low redox potentials of the developed complex, which allows water oxidation to be driven by the mild one-electron oxidant [Ru(bpy)3 ]3+ (bpy=2,2'-bipyridine). Furthermore, combined experimental and DFT studies provide insight into the mechanistic details of the catalytic cycle.

Catalyst-solvent interactions in a dinuclear Ru-based water oxidation catalyst.

Photocatalytic water oxidation represents a key process in conversion of solar energy into fuels and can be facilitated by the use of molecular transition metal-based catalysts. A novel straightforward approach for covalent linking of the catalytic units to other moieties is demonstrated by preparation of a dinuclear complex containing two [Ru(pdc)(pic)3]-derived units (pdc = 2,6-pyridinedicarboxylate, pic = 4-picoline). The activity of this complex towards chemical and photochemical oxidation of water was evaluated and a detailed insight is given into the interactions between the catalyst and acetonitrile, a common co-solvent employed to increase solubility of water oxidation catalysts. The solvent-induced transformations were studied by electrochemical and spectroscopic techniques and the relevant quantitative parameters were extracted.

Water oxidation catalyzed by molecular di- and nonanuclear Fe complexes: importance of a proper ligand framework.

The synthesis of two molecular iron complexes, a dinuclear iron(iii,iii) complex and a nonanuclear iron complex, based on the dinucleating ligand 2,2'-(2-hydroxy-5-methyl-1,3-phenylene)bis(1H-benzo[d]imidazole-4-carboxylic acid) is described. The two iron complexes were found to drive the oxidation of water by the one-electron oxidant [Ru(bpy)3](3+).

An Oxofluoride Catalyst Comprised of Transition Metals and a Metalloid for Application in Water Oxidation.

The application of the recently discovered oxofluoride solid solution (Cox Ni1-x )3 Sb4 O6 F6 as a catalyst for water oxidation is demonstrated. The phase exhibits a cubic arrangement of the active metal that forms oxo bridges to the metalloid with possible catalytic participation. The Co3 Sb4 O6 F6 compound proved to be capable of catalyzing 2H2 O→O2 +4H(+) +4e(-) at 0.33 V electrochemical and ≤0.39 V chemical overpotential with a TOF of 4.4⋅10(-3) , whereas Ni3 Sb4 O6 F6 needs a higher overpotential. Relatively large crystal cubes (0.3-0.5 mm) are easily synthesized and readily handled as they demonstrate both chemical resistance to wear after repeated in situ tests under experimental conditions, and have a mechanical hardness of 270 V0.1 using Vickers indentation. The combined properties of this compound offer a potential technical advantage for incorporation to a catalytic interface in future sustainable fuel production.

A Dinuclear Ruthenium-Based Water Oxidation Catalyst: Use of Non-Innocent Ligand Frameworks for Promoting Multi-Electron Reactions.

Insight into how H2 O is oxidized to O2 is envisioned to facilitate the rational design of artificial water oxidation catalysts, which is a vital component in solar-to-fuel conversion schemes. Herein, we report on the mechanistic features associated with a dinuclear Ru-based water oxidation catalyst. The catalytic action of the designed Ru complex was studied by the combined use of high-resolution mass spectrometry, electrochemistry, and quantum chemical calculations. Based on the obtained results, it is suggested that the designed ligand scaffold in Ru complex 1 has a non-innocent behavior, in which metal-ligand cooperation is an important part during the four-electron oxidation of H2 O. This feature is vital for the observed catalytic efficiency and highlights that the preparation of catalysts housing non-innocent molecular frameworks could be a general strategy for accessing efficient catalysts for activation of H2 O.

Efficient photochemical water oxidation by a dinuclear molecular ruthenium complex.

Herein is described the preparation of a dinuclear molecular Ru catalyst for H2O oxidation. The prepared catalyst mediates the photochemical oxidation of H2O with an efficiency comparable to state-of-the-art catalysts.