The integration of photovoltaics and catalysts into a useful system for solar energy conversion will require a number of advances, including discovery of inexpensive electrocatalysts for the half-reactions of interest. For schemes based on water oxidation, it is possible to envision catalysts derived from molecular transition metal complexes, or from inorganic solid-state materials. Molecular catalysts for water oxidation are somewhat controversial, since ligands in the catalytic species may readily undergo degradation under highly oxidizing conditions. Also, it is difficult to confidently associate catalytic activity with a particular molecular species, since these may oxidatively decompose to catalytic metal oxide materials under the conditions of electro- or photo-catalysis. However, molecularly derived catalysts offer a number of potential advantages, including the synthetic tunability of structure-activity relationships and chemical properties. The study of model, high-valent molecular species can provide key insights into the mechanism of water oxidation, and thereby help bridge the gap between heterogeneous and homogeneous systems to allow for more rational design of catalysts. This presentation will describe high-valent metal complexes and clusters, and key mechanistic insight into how such species mediate the evolution of oxygen <i>via</i> water oxidation.

Highly oxidized metal centers and metal-metal cooperativity in oxo clusters for water splitting

2019 Spring National Meeting

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