Jump to main content
Jump to site search

Issue 42, 2011
Previous Article Next Article

A comparison between artificial and natural water oxidation

Author affiliations


Two artificial water oxidation catalysts, the blue dimer and the Llobet catalyst, have been studied using hybrid DFT methods. The results are compared to those for water oxidation in the natural photosystem II enzyme. Studies on the latter system have now reached a high level of understanding, at present much higher than the one for the artificial systems. A recent high resolution X-ray structural investigation of PSII has confirmed the main features of the structure of the oxygen evolving complex (OEC) suggested by previous DFT cluster studies. The O–O bond formation mechanism suggested is of direct coupling (DC) type between an oxygen radical and a bridging oxo ligand. A similar DC mechanism is found for the Llobet catalyst, while an acid–base (AB) mechanism is preferred for the blue dimer. All of them require at least one oxygen radical. Full energy diagrams, including both redox and chemical steps, have been constructed illustrating similarities and differences to the natural system. Unlike previous DFT studies, the results of the present study suggest that the blue dimer is rate-limited by the initial redox steps, and the Llobet catalyst by O2 release. The results could be useful for further improvement of the artificial systems.

Graphical abstract: A comparison between artificial and natural water oxidation

Back to tab navigation

Supplementary files

Publication details

The article was received on 12 Jul 2011, accepted on 19 Sep 2011 and first published on 30 Sep 2011

Article type: Paper
DOI: 10.1039/C1DT11323B
Citation: Dalton Trans., 2011,40, 11296-11307
  •   Request permissions

    A comparison between artificial and natural water oxidation

    X. Li, G. Chen, S. Schinzel and P. E. M. Siegbahn, Dalton Trans., 2011, 40, 11296
    DOI: 10.1039/C1DT11323B

Search articles by author