Thursday, January 22, 2009

Chem. Soc. Rev. - Chemical Society Reviews (RSC) - up to Jan. 21, 2009

Chemical Society Reviews (RSC) - up to Jan. 21, 2009

Some interesting Chem. Soc. Rev. articles that might be of interest to the group
(no NMR here, but some interesting topics)

Critical Review

Chem. Soc. Rev., 2009, 38, 185 - 196, DOI: 10.1039/b802262n
Photosynthetic energy conversion: natural and artificial

James Barber
Photosystem II (PSII) is the water splitting enzyme of photosynthesis. Its appearance during evolution dramatically changed the chemical composition of our planet and set in motion an unprecedented explosion in biological activity. Powered by sunlight, PSII supplies biology with the hydrogen needed to convert carbon dioxide into organic molecules. The questions now are can we continue to exploit this photosynthetic process through increased use of biomass as an energy source and, more importantly, can we address the energy/CO2 problem by developing new photochemical technologies which mimic the natural system? (Critical review, 82 references)

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Tutorial Review

Chem. Soc. Rev., 2009, 38, 25 - 35, DOI: 10.1039/b800582f
Biology and technology for photochemical fuel production

Michael Hambourger, Gary F. Moore, David M. Kramer, Devens Gust, Ana L. Moore and Thomas A. Moore
Sunlight is the ultimate energy source for the vast majority of life on Earth, and organisms have evolved elegant machinery for energy capture and utilization. Solar energy, whether converted to wind, rain, biomass or fossil fuels, is also the primary energy source for human-engineered energy transduction systems. This tutorial review draws parallels between biological and technological energy systems. Aspects of biology that might be advantageously incorporated into emerging technologies are highlighted, as well as ways in which technology might improve upon the principles found in biological systems. Emphasis is placed upon artificial photosynthesis, as well as the use of protonmotive force in biology.

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Tutorial Review

Chem. Soc. Rev., 2009, 38, 73 - 82, DOI: 10.1039/b718842k
New approaches to hydrogen storage

Jason Graetz
The emergence of a Hydrogen Economy will require the development of new media capable of safely storing hydrogen in a compact and light weight package. Metal hydrides and complex hydrides, where hydrogen is chemically bonded to the metal atoms in the bulk, offer some hope of overcoming the challenges associated with hydrogen storage. The objective is to find a material with a high volumetric and gravimetric hydrogen density that can also meet the unique demands of a low temperature automotive fuel cell. Currently, there is considerable effort to develop new materials with tunable thermodynamic and kinetic properties. This tutorial review provides an overview of the different types of metal hydrides and complex hydrides being investigated for on-board (reversible) and off-board (non-reversible) hydrogen storage along with a few new approaches to improving the hydrogenation–dehydrogenation properties.

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Tutorial Review

Chem. Soc. Rev., 2008, 37, 2383 - 2392, DOI: 10.1039/b710347f
Current state for the development of metallopharmaceutics and anti-diabetic metal complexes

Hiromu Sakurai, Yutaka Yoshikawa and Hiroyuki Yasui
This tutorial review introduces the current state of metallopharmaceutics development by focusing on the topics of anti-diabetic vanadium and zinc complexes. Over thousands of years, people have produced many types of inorganic compounds, and the modern concept of chemotherapy was achieved by Ehrlich, who used an arsenic-containing compound to treat syphilis. Since then, many metallopharmaceutics have been developed worldwide. This review will be helpful to researchers who are interested in the current states of not only metallopharmaceutics but also anti-diabetic metal complexes.

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Critical Review

Chem. Soc. Rev., 2008, 37, 2274 - 2309, DOI: 10.1039/b719149a
In-silico investigations in heterogeneous catalysis—combustion and synthesis of small alkanes

Oliver R. Inderwildi and Stephen J. Jenkins
In this critical review, we cover first-principles density functional calculations relevant to alkane oxidation and synthesis over transition metal catalysts. For oxidation, we focus upon Pt, Rh, Pd and Ni surfaces, while for synthesis we consider Co, Ru, Fe and Ni. Throughout, we emphasise the insight to be gained by thinking of each kind of reaction as the inverse of the other, with the directionality determined simply by the choice of metal catalyst and the reaction conditions. We highlight particularly the role of low-coordination sites (steps, kinks, etc.) and the emerging consensus over the importance of the formyl intermediate in facilitating the rate-determining step (249 references).

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Editorial

Chem. Soc. Rev., 2008, 37, 2153 - 2154, DOI: 10.1039/b814437k
Chemistry at surfaces

Hans-Peter Steinrück, Jörg Libuda and Sir David A. King

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Tutorial Review

Chem. Soc. Rev., 2008, 37, 2204 - 2211, DOI: 10.1039/b719206c
Automotive catalysis studied by surface science

Michael Bowker
In this tutorial review I discuss the significant impact that surface science has had on our understanding of the catalytic phenomena associated with automobile exhaust depollution catalysis. For oxidation reactions it has generally been found that reactions are self-poisoned at low temperatures by the presence of strongly adsorbed reactants (such as molecular CO and NO), and that the rapid acceleration in rate at elevated temperatures (often called light-off) is due to the desorption of such adsorbates, which then frees up sites for dissociation and hence for oxidation reactions. In some circumstances such autocatalytic phenomena can then manifest themselves as oscillatory reactions which can vary in rate in both space and time. For NO reduction, the efficiency of depollution (by production of molecular nitrogen) is strongly affected by the nature of the metal used. Rh is extremely effective because it can dissociate NO much more readily than metals such as Pd and Pt, enabling oxygen removal (by reaction with CO to CO2) even at room temperature. Rh is also very selective in producing predominantly N2, rather than N2O. NOx storage and reduction (NSR) is an important recent development for removal of NOx under the highly oxidising conditions of a lean-burn engine exhaust, and the strategy involves storing NOx on BaO under oxidising conditions followed by the creation of reducing conditions to de-store and reduce it to nitrogen. By the use of STM it has been shown that this storage process is extremely facile, occurring fast even under UHV conditions, and that the storage occurs on BaO in the vicinity of Pt, with most of the oxide being converted to nitrate.
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Critical Review
Chem. Soc. Rev., 2008, 37, 2224 - 2242, DOI: 10.1039/b718768h
Oxide ultra-thin films on metals: new materials for the design of supported metal catalysts

Hans-Joachim Freund and Gianfranco Pacchioni
Ultrathin oxide films on metals offer new opportunities for the design of supported nanoclusters with potential use in catalysis. This requires a characterization at the atomistic level of the structure and composition of the thin film, of its morphology and defect structure. A proper selection of metal/oxide interface, film thickness, lattice mismatch, etc. makes it possible to prepare collections of supported metal particles with novel properties. This critical review describes some illustrative examples, emphasizes the role of the interplay between theory and experiment, and relates some recent findings related to the possibility to control the charge state of a supported nanoparticle on an ultrathin oxide film (211 references).

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