1. Setting the Scope of the Challenge 6474 1.1. The Need for Solar Energy Supply and Storage 6474 1.2. An Imperative for Discovery Research 6477 1.3. Scope of Review 6478 2. Large-Scale Centralized Energy Storage 6478 2.1. Pumped Hydroelectric Energy Storage (PHES) 6479 2.2. Compressed Air Energy Storage (CAES) 6480 3. Smaller Scale Grid and Distributed Energy Storage 6481 3.1. Flywheel Energy Storage (FES) 6481 3.2. Superconducting Magnetic Energy Storage 6482 4. Chemical Energy Storage: Electrochemical 6482 4.1. Batteries 6482 4.1.1. Lead-Acid Batteries 6483 4.1.2. Alkaline Batteries 6484 4.1.3. Lithium-Ion Batteries 6484 4.1.4. High-Temperature Sodium Batteries 6484 4.1.5. Liquid Flow Batteries 6485 4.1.6. Metal-Air Batteries 6485 4.2. Capacitors 6485 5. Chemical Energy Storage: Solar Fuels 6486 5.1. Solar Fuels in Nature 6486 5.2. Artificial Photosynthesis and General Considerations of Water Splitting 6486

Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds

Protein Radicals in Enzyme Catalysis.

Claisen rearrangement over the past nine decades.

This review focuses primarily on homogeneous catalysts for the oxidation of water, but does include selected heterogeneous systems. It does not attempt to summarize all chemistry related to systems that are capable of oxidizing water. In particular, heterogeneous catalysts that have no direct relevance to understanding the WOC [water-oxidizing complex] are not discussed in detail. Neither are nonbiomimetic systems for artificial photosynthesis or water-splitting in its elements discussed. However, a list of some of the recent references in these areas can be found in section X (Nonbiomimetic Water Oxidation Catalysts). The authors will first give a brief summary of the current view of the photosynthetic WOC and its functionality, followed by analysis of the thermodynamic and kinetic constraints for water-oxidation that have to be overcome by any catalyst. Since manganese is the metal that performs this reaction in the WOC, manganese catalysts will be discussed first, followed by other transition metals, particularly ruthenium. In the final section the authors summarize the principles of reactivity learned from theory and existing models that will guide one toward synthesis of better catalysts in the future. This review does not attempt to summarize manganese chemistry relevant to nonfunctional (structural) models of the WOC, whichmore » has been reviewed recently. Water-oxidation catalysts are intrinsically important in their own right, independent of possible biological relevance. They have direct applications as catalysts in artificial photosynthetic systems for the splitting of water that could be used in future fuel cells for the generation of electricity. 133 refs.« less

Synthetic Water-Oxidation Catalysts for Artificial Photosynthetic Water Oxidation.

A series of bis-phenylpyridine, bis-aquo iridium(III) complexes is herein shown to robustly and efficiently catalyze the oxidation of water to dioxygen in the presence of a sacrificial oxidant. Through substitution on the cyclometalating ligands of these complexes, it is shown that a broad range of oxidation potentials can be achieved within this class of catalyst. Parallel, dynamic monitoring of oxygen evolution, made possible by equipping reaction vessels with pressure-voltage transducers, facilitates correlation of these complexes' ionization potentials with their respective activity toward water oxidation. The importance of these catalysts lies in (A) their ability to oxidize water in a purely aqueous medium, (B) their simplicity of design, (C) their durability, and (D) the ease with which they can be tuned to accommodate the electrochemical needs of photosensitizers in hypothetical photochemical water oxidation and full artificial photosynthetic schemes.

Cyclometalated iridium(III) Aquo complexes: efficient and tunable catalysts for the homogeneous oxidation of water.

Studies on tumor promoters .8. the synthesis of phorbol

Alicyclic Claisen rearrangement. A general carbocycle synthesis based on four-atom-ring contractions of lactones

Claisen-rearrangement-mediated ring contraction of macrocyclic lactones : A new approach to carbocycles and heterocycles

A new approach to heterocycles: synthesis of (.+-.)-N-benzoylmeroquinene methyl ester

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Papers

Studies on tumor promoters .8. the synthesis of phorbol

Alicyclic Claisen rearrangement. A general carbocycle synthesis based on four-atom-ring contractions of lactones

Claisen-rearrangement-mediated ring contraction of macrocyclic lactones : A new approach to carbocycles and heterocycles

Alicyclic Claisen rearrangement. A general carbocycle synthesis based on four-atom-ring contractions of lactones

A new approach to heterocycles: synthesis of (.+-.)-N-benzoylmeroquinene methyl ester