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 O2 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)(OH2)]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.

Version notes

Several of the photoexcitation rate coefficients for the dye were found to have small errors. All calculations and analyses are now corrected and the figures and tables in the paper have been updated with the new values. The new simulation results are very close to or identical to the previous version's values, and there are no changes to the conclusions.


Thumbnail image of dye-catalyst couplings across timescales ChemRxiv rev2.pdf