4.6 Article

Collecting meaningful early-time kinetic data in homogeneous catalytic water oxidation with a sacrificial oxidant

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PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 16, 期 24, 页码 11942-11949

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ROYAL SOC CHEMISTRY
DOI: 10.1039/c3cp55406f

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  1. U.S. Department of Energy, Office of Basic Energy Sciences
  2. Solar Photochemistry Program [DE-FG02-07ER-15906]

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As the field of water oxidation catalysis grows, so does the sophistication of the associated experimental apparatuses. However, problems persist in studying some of the most basic aspects of catalytic water oxidation including acquisition of satisfactory early-reaction-time kinetics and rapid quantification of O-2 concentration. We seek to remedy these problems and through better experimental design, elucidate mechanistic aspects of catalytic water oxidation with theory backed by experimental data. Two new methods for evaluating homogeneous water oxidation catalysts by reaction with a stoichiometric oxidant are presented which eliminate problems of incomplete fast mixing and O-2 measurement response time. These methods generate early-reaction-time kinetics that have previously been unavailable.

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