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Версия для печати | Главная > Институт > Научные советы > Научный совет по катализу > ... > 2001 год > № 20

№ 20

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Поздравления В.Пармона "С наступающим Новым 2002 Годом!"

Профессор А. Белл - Почетный профессор Сибирского отделения РАН

О премии им. В.А. Коптюга

Нобелевские лауреаты в области химии 2001 года

За рубежом

Р.А. Буянов. "Катализ: взгляд сквозь годы"

IX Международный симпозиум
"Магнитный резонанс в коллоидах и на поверхности"

А.С. Носков. Букварь для специалистов по катализу

Г.Е. Голосман
"Отечественные разработчики и производители катализаторов.
Новомосковский институт азотной промышленности"

Г.С. Яблонский "Четвертый критерий"




С наступающим Новым 2002 Годом

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Профессор А. Белл - Почетный профессор Сибирского отделения РАН

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О премии им. В.А. Коптюга

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Нобелевские лауреаты в области химии 2001 года

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Nitrogen Helps Catalytic TiO2 See the Light

Sunlight-driven TiO2 catalysis of reactions that oxidize organic pollutants in water or air has been a goal of chemists for several years. TiO2 normally absorbs sunlight in the UV region below about 390 nm, leading to an excited electronic state that helps to form oxygen and hydroxyl radicals that have been shown to degrade aldehydes, NOx gases, and organic solvents. Researchers have been anxious to broaden TiO2's absorption range into the visible region to beyond the maximum in the solar spectrum's intensity at 460 nm, which would make degradation reactions proceed more efficiently. Several research groups have been looking at doping TiO2 to accomplish that goal. Now, a research team led by Ryoji Asahi at Toyota Central R&D Laboratories in Japan has succeeded by doping TiO2 with nitrogen using a sputtering technique to prepare crystalline films of TiO2-xNx [Science, 293, 269, 2001]. The team evaluated the photocatalytic activity of TiO2-xNx by measuring the decomposition rates of methylene blue and gaseous acetaldehyde under various conditions. The new material outperforms TiO2 over the range of 350 to 520 nm, they find.

C&EN/July 16, 2001

Metal Catalyst Promotes [2+2] Cycloaddition

Alkene [2+2] cycloadditions are typically photochemically induced and generally exhibit poor stereoselectivity. Now, a catalyst has been developed that can extend [2+2] cycloaddition methodology to photochemically fragile substrates, enabling a new technique for the synthesis of fused cyclobutane-containing natural products. Michael J. Krische and colleagues at the University of Texas, Austin, have developed a highly stereoselective cobalt catalyst for the intramolecular [2+2] cycloaddition of bis-enones to form substituted bicyclo[3.2.0] ring systems [J. Am. Chem. Soc., 123, 6716, 2001]. The reaction is viable for a variety of substituted bis-enones, but it requires at least one aromatic enone partner. In each case, independent of the alkene geometry of the starting bis-enone, [2+2] cycloadducts are formed as single stereoisomers.

C&EN/July 16, 2001

Enantioselective Oxidations of Secondary Alcohols with Oxygen

Two research groups have developed methods for catalytic, enantioselective oxidations of secondary alcohols using molecular oxygen as the terminal oxidant. These methods can be used to resolve racemic mixtures of secondary alcohols and to break the symmetry of meso-diols. Assistant chemistry professors Brian M. Stoltz at Caltech and Matthew S. Sigman at the University of Utah and their co-workers have accomplished the feat independently and at about the same time [J. Am. Chem. Soc., 123, 7475 and 7725, 2001; manuscripts were received a week apart]. Both groups use palladium(II) catalytic systems with the chiral diamine(-)-sparteine as a ligand. After two cycles, a preparative-scale oxidative resolution of racemic a -methyl-2-naphthalenemethanol (shown) by the Caltech group resulted in 68% yield of the optically enriched product in 99% enantiomeric excess. Both groups demonstrate de-symmetrization of meso-diols in comparable yields but slightly lower enantiomeric excesses.

C&EN/July 30, 2001

Catalysts for Producing Chemicals from Renewable Feedstocks

The US Department of Energy's Brookhaven National Laboratory and DuPont Company have developed a new class of catalysts, homogeneous hydrido complexes that could someday convert plant-derived feedstocks into industrially useful materials, such as chemicals and synthetic fibers. This research is described in the October 12 issue of the German journal Angewandte Chemie. "This is an early step in a long-term goal to develop new ways to make chemicals and fibers", said Morris Bullock, Brookhaven's principal researcher in the project.

The Brookhaven/DuPont collaboration used a ruthenium-based catalyst to accelerate the removal of oxygen from diols commonly found in plants. Selective removal of oxygen converts diols into alcohols, which are used for making industrial materials. The researchers hope to extend this deoxygenation method to more complex compounds such as diols and polyols (e.g. glucose) for converting organic plant material into chemicals for application in large-scale industrial processes.

DuPont's goal is to derive 25% of its revenues in 2010 from renewable raw materials, like carbohydrates. Paul Fagan, principal researcher on the project at DuPont, said, "This research is a starting point to develop improved industrially important catalysts for key transformations of biomolecules. We realize there is much more work to be done on these catalysts, but this is the kind of chemistry that will help DuPont meet its goal". Research is continuing to improve the activity of the new catalysts so that they become attractive for industrial use. Two patent applications have been filed on the catalysts.

Making progress on this goal, DuPont and Partners Tate&Lyle have already successfully manufactured a critical raw material,
1,3-propanediol, for its newest fabric polymer SoronaTM, using a fermentation process based on corn sugar, a renewable resource. The chemical was produced by DuPont scientists at a pilot plant located at Tate&Lyle's Decatur, Illinois, facility. Tate&Lyle, a major corn-based products company with expertise in fermentation processes, is one of DuPont's development partners in the effort. The other is Genencor, which is developing the biocatalyst for this process. The 1,3-propanediol is then reacted with petroleum-derived terephthalic acid to produce the Sonora polymer.

Reference: Marcel Schlaf, Prasenjit Ghosh, Paul J. Fagan, et al., Metal-Catalyzed Selective Deoxygenation of Diols to Alcohols. Angew. Chem. Intern. Ed., 40(20), 3887-3890, 2001.

John K. Borchardt . The Alchemist The Chem. Web Magazine


Р.А. Буянов. "Катализ: взгляд сквозь годы"

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IX Международный симпозиум "Магнитный резонанс в коллоидах и на поверхности"

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А.С. Носков. Букварь для специалистов по катализу

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Г.Е. Голосман

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Г.С. Яблонский "Четвертый критерий"

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