We describe here a direct comparison of electrochemical and spectrochemical experiments to determine rates and selectivity of oxygen reduction catalyzed by iron 5,10,15,20-meso-tetraphenylporphyrin chloride. Strong agreement was found between the two methods suggesting the same mechanism is occurring under both conditions, with the same overall third order rate constant kcat = (1.1 ± 0.1) × 106 M-2 s-1. This report provides a rare example of characterization of a redox catalytic process by two common but very different methods. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.
Revised: June 26, 2015 |
Published: September 10, 2014
Citation
Wasylenko D.J., C. Rodriguez, M.L. Pegis, and J.M. Mayer. 2014.Direct Comparison of Electrochemical and Spectrochemical Kinetics for Catalytic Oxygen Reduction.Journal of the American Chemical Society 136, no. 36:12544-12547.PNNL-SA-102821.doi:10.1021/ja505667t