Electrochemical and Spectroscopic Study of Mononuclear Ruthenium Water Oxidation Catalysts: A Combined Experimental and Theoretical Investigation
Authorsde Ruiter, J. M.
Purchase, R. L.
van der Ham, C. J. M.
Gullo, M. P.
Joya, K. S.
Hetterscheid, D. G. H.
de Groot, H. J. M.
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AbstractOne 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.
CitationDe Ruiter JM, Purchase RL, Monti A, van der Ham CJM, Gullo MP, et al. (2016) Electrochemical and Spectroscopic Study of Mononuclear Ruthenium Water Oxidation Catalysts: A Combined Experimental and Theoretical Investigation. ACS Catalysis 6: 7340–7349. Available: http://dx.doi.org/10.1021/acscatal.6b02345.
SponsorsThe use of supercomputer facilities was sponsored by NINO Physical Sciences, with financial support from The Netherlands Organization for Scientific Research (NINO). K.S.J. acknowledges the Higher Education Commission (HEC), Pakistan, for a research grant. This research was also financed by the NWO-ECHO project number 713.011.002, by the BioSolar Cells open innovation consortium, supported by the Dutch Ministry of Economic Affairs, Agriculture and Innovation (project C1.9), and by the Italian National Research Council (CNR,
PublisherAmerican Chemical Society (ACS)