Electrochemical and Spectroscopic Study of Mononuclear Ruthenium Water Oxidation Catalysts: A Combined Experimental and Theoretical Investigation

J. M. de Ruiter, R. L. Purchase, A. Monti, C. J. M. van der Ham, M. P. Gullo, Khurram Saleem Joya, M. D'Angelantonio, A. Barbieri, D. G. H. Hetterscheid, H. J. M. de Groot, F. Buda

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11 Scopus citations

Abstract

One of the key challenges in designing light-driven artificial photosynthesis devices is the optimization of the catalytic water oxidation process. For this optimization it is crucial to establish the catalytic mechanism and the intermediates of the catalytic cycle, yet a full description is often difficult to obtain using only experimental data. Here we consider a series of mononuclear ruthenium water oxidation catalysts of the form [Ru(cy)(L)(H2O)](2+) (cy = p-cymene, L = 2,2'-bipyridine and its derivatives). The proposed catalytic cycle and intermediates are examined using density functional theory (DFT), radiation chemistry, spectroscopic techniques, and electrochemistry to establish the water oxidation mechanism. The stability of the catalyst is investigated using online electrochemical mass spectrometry (OLEMS). The comparison between the calculated absorption spectra of the proposed intermediates with experimental spectra, as well as free energy calculations with electrochemical data, provides strong evidence for the proposed pathway: a water oxidation catalytic cycle involving four proton-coupled electron transfer (PCET) steps. The thermodynamic bottleneck is identified as the third PCET step, which involves O-O bond formation. The good agreement between the optical and thermodynamic data and DFT predictions further confirms the general applicability of this methodology as a powerful tool in the characterization of water oxidation catalysts and for the interpretation of experimental observables.
Original languageEnglish (US)
Pages (from-to)7340-7349
Number of pages10
JournalACS Catalysis
Volume6
Issue number11
DOIs
StatePublished - Oct 3 2016

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