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Water oxidation by a dye-catalyst diad in natural sunlight: timing and coordination of excitations and reactions across timescales of picoseconds to hours

The mechanisms of how dyes and catalysts for solar-driven transformations such as water oxidation to form O(2) work have been intensively investigated, however little is known about how their independent photophysical and chemical processes work together. The level of coordination between the dye an...

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Detalles Bibliográficos
Autores principales: Massad, Ramzi N., Cheshire, Thomas P., Fan, Chenqi, Houle, Frances A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9945043/
https://www.ncbi.nlm.nih.gov/pubmed/36845923
http://dx.doi.org/10.1039/d2sc06966k
Descripción
Sumario:The mechanisms of how dyes and catalysts for solar-driven transformations such as water oxidation to form O(2) work have been intensively investigated, however little is known about how their independent photophysical and chemical processes work together. The level of coordination between the dye and the catalyst in time determines the overall water oxidation system's efficiency. In this computational stochastic kinetics study, we have examined coordination and timing for a Ru-based dye-catalyst diad, [P2Ru(4-mebpy-4′-bimpy)Ru(tpy)(OH(2))](4+), where P2 is 4,4′-bisphosphonato-2,2′-bipyridine, 4-mebpy-4′-bimpy is 4-(methylbipyridin-4′-yl)-N-benzimid-N′-pyridine, a bridging ligand, and tpy is (2,2′:6′,2′′-terpyridine), taking advantage of the extensive data available for both dye and catalyst, and direct studies of the diads bound to a semiconductor surface. The simulation results for both ensembles of diads and single diads show that progress through the generally accepted water oxidation catalytic cycle is not controlled by the relatively low flux of solar irradiation or by charge or excitation losses, rather is gated by buildup of intermediates whose chemical reactions are not accelerated by photoexcitations. The stochastics of these thermal reactions govern the level of coordination between the dye and the catalyst. This suggests that catalytic efficiency can be improved in these multiphoton catalytic cycles by providing a means for photostimulation of all intermediates so that the catalytic rate is governed by charge injection under solar illumination alone.