A dyad complex has been constructed as a soluble molecular model of a heterogeneous cobalt-based oxygen-evolving catalyst (Co-OEC). To this end, the Co(4)O(4) core of a cobalt-oxo cubane was covalently appended to Re(I) photosensitisers. The resulting adduct was characterised both in the solid state (by X-ray diffraction) and in solution using a variety of techniques. In particular, the covalent attachment of the Re(I) moieties to the Co(4)O(4) core promotes emission quenching of the Re(I) photocentres, with implications for the energy and electron transduction process of Co-OEC-like catalysts.
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http://dx.doi.org/10.1002/cssc.201200682 | DOI Listing |
J Biol Inorg Chem
December 2024
Division of Chemistry and Chemical Engineering, Howard Hughes Medical Institute, California Institute of Technology, 147-75, Pasadena, CA, 91125, USA.
Dangler sites protruding from a core metallocluster were introduced into the bioinorganic lexicon in 2000 by R.D. Britt and co-workers in an analysis of the tetramanganese oxygen-evolving cluster in photosystem II.
View Article and Find Full Text PDFBiochim Biophys Acta Bioenerg
December 2024
Laboratory of Computational Biology, National Heart, Lung and Blood Institute, National Institutes of Health, Bethesda, MD 20892, USA. Electronic address:
Photosystem II (PSII) is a unique natural catalyst that converts solar energy into chemical energy using earth abundant elements in water at physiological pH. Understanding the reaction mechanism will aid the design of biomimetic artificial catalysts for efficient solar energy conversion. The MnOCa cluster cycles through five increasingly oxidized intermediates before oxidizing two water molecules into O and releasing protons to the lumen and electrons to drive PSII reactions.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Southern Laboratories-208A, Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India.
Understanding the basic structure of the oxygen-evolving complex (OEC) in photosystem II (PS-II) and the water oxidation mechanism can aid in the discovery of more efficient and sustainable catalysts for water oxidation. In this context, we present evidence of the formation of a [(TPA)Mn(O)(μ-O)Ce(NO)] () complex (TPA = tris(pyridyl-2-methyl)amine) by adding aqueous ceric ammonium nitrate to an acetonitrile solution of the [(TPA)Mn] () complex. This unique intermediate () was analyzed by using various spectroscopic techniques and electrospray ionization mass spectrometry.
View Article and Find Full Text PDFDalton Trans
November 2024
Intelligent Polymer Research Institute and ARC Centre of Excellence in Electromaterials Science, University of Wollongong, Wollongong, NSW 2522, Australia.
The activity and stability of a heterogeneous water oxidation catalyst inspired by the Photosystem II - Oxygen Evolving Center (PSII-OEC) is reported. Ca-doped birnessite MnO supported on a liquid crystalline reduced graphene oxide (LCrGO) substrate exhibited unprecedented performance for an abiological catalyst at pH 7, including an exceedingly low onset overpotential of 0.52 V (.
View Article and Find Full Text PDFChemSusChem
September 2024
Department of Chemistry, Centre for Materials Science and Nanotechnology, University of Oslo, Gaustadalléen 21, NO-0349, Oslo, Norway.
Perovskite oxides have great flexibility in their elemental composition, which is accompanied by large adjustability in their electronic properties. Herein, we synthesized twelve perovskite oxide-based catalysts for the oxygen evolution reaction (OER) in alkaline media. The catalysts are based on the parent oxide perovskite BaGdLaCoO (BGLC587) and are synthesized through the sol-gel citrate synthesis route.
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