Striving for new solar fuels, the water oxidation reaction currently is considered to be a bottleneck, hampering progress in the development of applicable technologies for the conversion of light into storable fuels. This review compares and unifies viewpoints on water oxidation from various fields of catalysis research. The first part deals with the thermodynamic efficiency and mechanisms of electrochemical water splitting by metal oxides on electrode surfaces, explaining the recent concept of the potential-determining step. Subsequently, novel cobalt oxide-based catalysts for heterogeneous (electro)catalysis are discussed. These may share structural and functional properties with surface oxides, multinuclear molecular catalysts and the catalytic manganese–calcium complex of photosynthetic water oxidation. Recent developments in homogeneous water-oxidation catalysis are outlined with a focus on the discovery of mononuclear ruthenium (and non-ruthenium) complexes that efficiently mediate O2 evolution from water. Water oxidation in photosynthesis is the subject of a concise presentation of structure and function of the natural paragon—the manganese–calcium complex in photosystem II—for which ideas concerning redox-potential leveling, proton removal, and OO bond formation mechanisms are discussed. The last part highlights common themes and unifying concepts.

The Mechanism of Water Oxidation: From Electrolysis via Homogeneous to Biological Catalysis

Life on earth is almost entirely solar-powered. We can get some idea of the enormous quantity of energy received from the sun by noting that during daylight hours, the sun provides several thousand times more power to the surface of the U.S.A. than is produced by all of the nation’s electrical power stations. 1,2 Around 50% of the radiation that reaches the earth’s surface, roughly the visible region, is of a frequency useful to photosynthetic organisms. Oxygenic photosynthetic organisms convert this radiation into chemical energy, in the form of carbohydrate and dioxygen, at an optimal efficiency of something like 25%. 3 These products together sustain the rest of aerobic life, with carbohydrate acting as a source of high-energy electrons and dioxygen providing a lower-energy destination for these electrons. The overall equation of oxygenic photosynthesis is given in eq 1, where (CH2O) represents carbohydrate:

Water-splitting chemistry of photosystem II.

The manganese and calcium ions of photosynthetic oxygen evolution.

The challenge of cyclic and acyclic schiff bases and related derivatives

This self-contained, comprehensive book describes the fundamental properties of soft x-rays and extreme ultraviolet (EUV) radiation and discusses their applications in a wide variety of fields, including EUV lithography for semiconductor chip manufacture and soft x-ray biomicroscopy. The author begins by presenting the relevant basic principles such as radiation and scattering, wave propagation, diffraction, and coherence. He then goes on to examine a broad range of phenomena and applications. The topics covered include EUV lithography, biomicroscopy, spectromicroscopy, EUV astronomy, synchrotron radiation, and soft x-ray lasers. He also provides a great deal of useful reference material such as electron binding energies, characteristic emission lines and photo-absorption cross-sections. The book will be of great interest to graduate students and researchers in engineering, physics, chemistry, and the life sciences. It will also appeal to practicing engineers involved in semiconductor fabrication and materials science.

X-Rays and Extreme Ultraviolet Radiation: Principles and Applications

State of manganese in the photosynthetic apparatus. 1. Extended x-ray absorption fine structure studies on chloroplasts and di-.mu.-oxo-bridged dimanganese model compounds

The risks and costs of the present method of visualizing the coronary arteries have limited the use of coronary angiography in long-term serial studies needed to establish the natural history of coronary atherosclerosis and its response to interventions. A less invasive method, in which the contrast agent is administered intravenously, has been developed using synchrotron radiation as the illuminating source. The present report describes the initial results in human subjects. The findings indicate that transvenous coronary angiograms can be acquired in this manner. Further refinements in the x-ray imaging system are expected to result in increased x-ray fluence and improved image quality.

https://www.pnas.org/content/pnas/83/24/9724.full.pdf

Transvenous coronary angiography in humans using synchrotron radiation.

Multilayer reflectors for the X-ray region have now progressed beyond the experimental stage to the point where they can be relied upon as optics for experimental systems, in synchrotron radiation research as well as in other fields. This paper reviews the design considerations for an X-ray microprobe, and summarizes experience with prototypes tested at both SSRL and NSLS. The optical systems described employ multilayer-coated spherical mirrors arranged in the Kirkpatrick-Baez configuration to demagnify the X-ray source by a factor of several hundred. By this means a spot of X-rays less than 10 μm square can be produced. The optical aberrations and other factors that limit the performance are detailed, and possible ways to improve the performance are discussed. In the prototypes the spot is directed on the specimen which is carried on a stage that can be translated horizontally and vertically. The characteristic fluorescent X-rays excited by the focused 10 keV photons are analysed by an energy-dispersive Si(Li) detector, so that by scanning the stage an elemental concentration map of the specimen is built up. In a companion paper [A.C. Thompson, J.H. Underwood, Y. Wu, R.D. Giauque, K.W. Jones and M.L. Rivers, these Proceedings, p. 318] some experimental programs are described, and estimates of the elemental sensitivity are provided.

X-ray microprobe using multilayer mirrors

Extended X-ray Absorption Fine Structure (EXAFS) studies on the manganese contained in spinach chloroplasts and on certain di-u-oxo bridged manganese dimers of the form (X{sub 2}Mn)O{sub 2}(MnX{sub 2} (X=2,2'-bypyridine and 1,10-phenanthroline) are reported. From these studies, the manganese associated with photosynthetic oxygen evolution is suggested to occur as a bridged transition metal dimer with most likely another manganese. Extensive details on the analysis are included.

/pdf/the-state-of-manganese-in-the-photosynthetic-apparatus-i-2uferq19ei.pdf

THE STATE OF MANGANESE IN THE PHOTOSYNTHETIC APPARATUS. I. EXAFS STUDIES ON CHLOROPLASTS AND di-u-oxo BRIDGED di-MANGANESE MODEL COMPOUNDS

https://escholarship.org/content/qt2cz0f6z5/qt2cz0f6z5.pdf?t=p0wt9d

A.C. Thompson

Papers

State of manganese in the photosynthetic apparatus. 1. Extended x-ray absorption fine structure studies on chloroplasts and di-.mu.-oxo-bridged dimanganese model compounds

Transvenous coronary angiography in humans using synchrotron radiation.

X-ray microprobe using multilayer mirrors

THE STATE OF MANGANESE IN THE PHOTOSYNTHETIC APPARATUS. I. EXAFS STUDIES ON CHLOROPLASTS AND di-u-oxo BRIDGED di-MANGANESE MODEL COMPOUNDS

Computed tomography using synchrotron radiation