Distinguishing homogeneous and heterogeneous water oxidation catalysis when beginning with cobalt polyoxometalates

2013 Fall.Includes bibliographical references.Development of energy storage technologies is required prior to broad implementation of renewable energy sources such as wind or solar power. One of the leading proposals is to store this energy by splitting water into hydrogen and oxygen--that is, to store energy in chemical bonds. A major obstacle en route to this overall goal is the development of efficient, cost-effective water oxidation catalysts (WOCs). Due to the highly oxidizing environment needed to drive this reaction, one question which has arisen when dealing with homogeneous precatalysts is whether these precursors remain as intact, homogeneous WOCs, or whether they are transformed into heterogeneous metal-oxide catalysts. This problem, reviewed in Chapter II, addresses the methods and literature studies related to distinguishing homogeneous and heterogeneous water oxidation catalysts. Chapters III through V further develop the methodology for distinguishing homogeneous and heterogeneous water oxidation catalysis when beginning with the cobalt polyoxometalate [Co4(H2O)2(PW9O34)2]10- (Co4POM). In Chapter III, the investigation of Co4POM using electrochemical oxidation at a glassy carbon electrode reveals that under the conditions therein, an in-situ formed, heterogeneous cobalt-oxo-hydroxo (CoOx) material is the dominant catalyst and is formed from Co2+ leached from the Co4POM. In Chapter IV, investigation of whether the intact Co4POM could be a catalyst under other, more forcing conditions of higher electrochemical potentials and lower Co4POM concentrations is reported. Although the Co4POM shows different electrochemical properties relative to CoOx controls, the possibility that the Co4POM is being transformed into a meta-stable heterogeneous catalyst cannot be ruled out since the Co4POM degrades during the experiment. Lastly, Chapter V presents a kinetic and mechanistic study of the Co4POM when using a ruthenium(III)tris(2,2'-bipyridine) (Ru(III)(bpy)33+) chemical oxidant to drive the water oxidation reaction (i.e., rather than electrochemically driven oxidation). In this study, it was found that Co4POM catalyzes the oxidation of water as well as oxidation of the 2,2'-bipyridine ligand. In contrast, controls with in-situ formed CoOx catalysts more selectively promote the catalytic oxidation of water. The difference in reactivity and kinetics between the Co4POM and CoOx systems indicates that the active catalysts are fundamentally different when a chemical oxidant is employed. Overall, these studies demonstrate the need for careful experimental controls and highlight the importance which reaction conditions--in particular the source and electrochemical potential of the oxidant--can play in determining the active oxidation catalyst in water oxidation reactions