Electrocatalytic Water Oxidation by a Water-Soluble Nickel Porphyrin Complex at Neutral pH with Low Overpotential

The water-soluble cationic nickel(II) complex meso-tetrackis(4-N-methylpyridyl)porphyrin (I) can electro-catalyze water oxidation to O-2 in neutral aqueons solution (pH 7.0) with the onset of the catalytic wave appearing at similar to 1.0 V (vs NHE):. The homogeneous catalysis with 1 was verified, Catalyst 1 exhibited water oxidation activity in a pH range 2.0-8.0 and had a strict linear dependence of catalytic:current on its concentration. After 10 h of constant potential electrolysis at 1.32 V (vs NHE), a negligible difference Of the Solution was observed by UV-vis. In addition, inspection of the working electrode by electrochemistry, scanning electron microscope (SEM), and energy dispersive X-ray spectroscopy (EDX) showed no sign of deposition of NiOx films. These results strongly argued that 1 is a real molecular electrocatalyst for water oxidation. The turnover frequency (TOP) for this process was 0.67 s(-1) at 20 degrees C. On the basis of results from the kinetic isotope effect (KIE) and inhibition experiments, electrochemical studies in various buffer solutions with different anions and pHs, and DFT calculations, a catalytic cycle of 1 for water,oxidation via a formally Ni(IV) species was proposed.