Catalytic Activity of an Iron-Based Water Oxidation Catalyst: Substrate Effects of Graphitic Electrodes

The synthesis, characterization, and electrochemical studies of the dinuclear complex [(MeOH)Fe(Hbbpya)-μ-O-(Hbbpya)Fe(MeOH)](OTf)₄ (1) (with Hbbpya = N,N-bis(2,2'-bipyrid-6-yl)amine) are described. With the help of online electrochemical mass spectrometry, the complex is demonstrated to be active as a water oxidation catalyst. Comparing the results obtained for different electrode materials shows a clear substrate influence of the electrode, as the complex shows a significantly lower catalytic overpotential on graphitic working electrodes in comparison to other electrode materials. Cyclic voltammetry experiments provide evidence that the structure of complex 1 undergoes reversible changes under high-potential conditions, regenerating the original structure of complex 1 upon returning to lower potentials. Results from electrochemical quartz crystal microbalance experiments rule out that catalysis proceeds via deposition of catalytically active material on the electrode surface.