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В Научном совете по катализу РАН

Е.З. Голосман. Будут ли катализаторы в России?

Решение конференции "Научные основы приготовления и технологии катализаторов"

Катализ: взгляд сквозь годы (продолжение).
М.г. Слинько. Краткая история промышленного катализав России до 60-х годов XX столетия

Стефен Дж. Липпард. Тихая революция в химии

Премии по химии

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Будут ли катализаторы в России?

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Решение конференции "Научные основы приготовления и технологии катализаторов"

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Стефен Дж. Липпард. Тихая революция в химии

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Премии по химии

THE WOLF FOUNDATION 2001 PRIZE IN CHEMISTRY

The Prize Committee for Chemistry has unanimously decided that the Prize for 2001 be jointly awarded to

Henri B. KaganRyoji Noyori    K. Barry Sharpless
University of Paris-South Nagoya University     Scripps Research Institute
Paris, France Nagoya, Japan     La Jolla, California, USA

for their pioneering, creative and crucial work in developing asymmetric catalysis for the synthesis of chiral molecules, greatly increasing mankind's ability to create new products of fundamental and practical importance.

H. B. Kagan (born 1930, France) , R. Noyori (born 1938, Japan) and K. B. Sharpless (born 1941, USA), have independently made great advances in developing the ability to synthesize chiral molecules. They pioneered the use of chiral molecular metal complexes as catalysts in asymmetric synthesis. Minute amounts of such catalysts can enable the production of large amounts of desired products of controlled handedness. These catalysts can perform various molecular transformations in an asymmetric fashion, such as reduction, oxidation and isomerization, leading to a variety of useful chiral products.

The chiral synthetic advances made by these three scientists, working on three different continents but pursuing the same significant goals, are critical to pharmaceutical manufacturing and the preparation of a very large number of molecules of controlled handedness. Their pioneering work has revolutionized our understanding of asymmetric catalysis and provided the means for efficient industrial and laboratory preparations of important pharmaceutical products and fine chemicals needed for daily life.

* * * * *

The first example of asymmetric catalysis (cyclopropanation) by a well-defined metal (copper) complex was reported by Noyori in 1966. Although only a low enantiomeric excess was obtained, the result stimulated further research. In 1971, Kagan reported a breakthrough in catalytic enantioselectivity. Using a C2-symmetric ligand (DIOP) for the first time, he obtained a very high enantiomeric excess in alkene hydrogenation, catalyzed by a rhodium complex. Kagan's work had a strong influence on the course of research in the field of asymmetric catalysis, leading to the development of a variety of C2-symmetric ligands and stimulating the study of several important reactions, such as asymmetric hydrogenation, hydroformylation, hydrosilylation and allylic alkylation. In 1980, Noyori reported asymmetric catalysis, by complexes of a new diphosphine ligand, BINAP. Catalysis by ruthenium and rhodium complexes of this ligand, resulted in spectacular laboratory and commercial applications, in asymmetric hydrogenation and isomerization. In the same year, Sharpless reported a breakthrough in the important field of asymmetric oxidation. His general method for the highly enantioselective epoxidation of allylic alcohols catalyzed by a titanium complex, is of broad scope and is used routinely in synthesis. More recently, Sharpless developed another highly useful synthetic methodology, the asymmetric dihydroxylation of alkenes, catalyzed by an osmium complex.

January 2001

Professor Francisco Zaera is selected as the recipient of the 2001 American Chemical Society/ George A. Olah Award in Hydrocarbon or Petroleum Chemistry. This award recognizes Professor Zaera's many contributions to understanding the kinetics and mechanisms of surface chemical reactions that involve hydrocarbon and related transformations. This award was established in 1948 and has a long list of distinguished recipients, including John Bercaw, Bruce Gates, Edward Arnett, Cheves Walling, Robert Burwell, William Pryor, Paul Gassman, Andrew Streitwieser, George Olah, George Hammond, Robert Taft, George Pimentel, and Kenneth Pitzer. The criteria for the award include: "Special consideration shall be given to the independence of thought and the originality shown."

GABOR SOMORJAI NAMED
2000 PAULING AWARD MEDALIST

The American Chemical Society's Oregon, Portland, and Puget Sound Sections have named Gabor A. Somorjai the recipient of the 2000 Pauling Award. The award, which honors Linus Pauling, the 1954 Nobel Laureate in Chemistry and a native of the Pacific North-West, consists of a gold medal. Recipients are recognized for contributions to chemistry of national and international significance. Somorjai, a professor of chemistry at the University of California, Berkeley, will receive the award following a symposium entitled "Surface Science and Catalysis at the Frontiers of Chemistry", which will be held on Oct. 21 at Western Washington University, Bellingham.

Somorjai is known for his work in developing the molecular foundations of surface science, with particular emphasis on heterogeneous catalysis. In the mid-1960s, Somorjai used low-energy electron diffraction (LEED) to make the important discovery that clean Pt (100) surfaces reconstruct. In surface reconstruction, atoms at a surface assume positions different from what one would expect if the bulk structure of the material were abruptly terminated. Somorjai's proposal of clean-surface reconstruction for the Pt(100) single-crystal surface was controversial at the time, but since then many other surfaces have been observed to exhibit reconstruction and the phenomenon is no longer considered surprising.

Subsequent to the Pt (100) work, Somorjai used a variety of surface structural techniques to probe increasingly complex surfaces. Research in his laboratory included the first studies of adsorption on stepped surfaces, the first investigation of surface melting and freezing using LEED, the first surface structural studies of molecular crystals, and the first structural characterization of an adsorbed organic molecule using LEED.

In addition to his groundbreaking studies of surface structure, Somorjai developed the field in which model systems are used to probe heterogeneous catalysis reactions. Using molecular beam scattering methods, he directly showed that steps on platinum surfaces are essential for dissociation of hydrogen, a key process in many surface-catalyzed reactions. Somorjai also pioneered the use of single-crystal metal surfaces as model catalysts to investigate the kinetics and mechanisms of heterogeneous catalysis reactions.

His development of a high-pressure catalytic reactor that could be isolated from an ultrahigh vacuum allowed the use of electron spectroscopic techniques for characterizing single-crystal catalyst surfaces immediately before and after high-pressure experiments. This approach enables the correlation of the high-pressure kinetics of a catalytic reaction with the structural and compositional characterization of the single-crystal catalyst. Most recently, Somorjai has incorporated scanning tunneling microscopy and sum frequency generation into the wide array of techniques used in his laboratory to investigate surface.

Somorjai studied chemical engineering at Technical University, Budapest, receiving a BS degree in 1956. He then left Hungary to emigrate to the US, where he received a Ph.D. degree from UC Berkeley in 1959. Following that, he took a position with the solid-state materials group at IBM Research. In 1964, Somorjai accepted a faculty position in chemistry at Berkeley, where has been ever since. He has also been a principal investigator at Lawrence Berkeley National Laboratory since that time.

Somorjai has published more than 750 articles and has authored three textbooks. He serves on the editorial boards of 14 journals and is co-editor-in-chief of Catalysis Letters.

His extensive list of awards includes the Wolf Prize in Chemistry, the Von Hippel Award of the Materials Research Society, as well as ACS's Adamson, Debye, and Colloid & Surface Chemistry Awards and Award for Creative Research in Catalysis. Somorjai is a member of the National Academy of Sciences, a fellow of the American Association for the Advancement of Science, and an honorary member of the Hungarian Academy of Sciences.

August 21, 2000 C & EN

ACS Award for Creative Research in Homogeneous or Heterogeneous Catalysis

Sponsored by Shell Oil Foundation

Chemical engineering professor ALEXIS T. BELL of the University of California, Berkeley, is being honored for his research on relations between structures of catalysts and catalyst performance. He has advanced the understanding of how to design catalysts of high efficiency and selectivity.

A vice president of research and development at one chemical company says of him: "Alex is one of the few catalyst researchers in the world whose work successfully encompasses the whole range of techniques and considerations from molecular-level theory through surface science to kinetics, transport-coupled kinetics, and reactor-level performance, including transient catalytic behavior. His accomplishments toward the development of fundamental understanding and methodology toward the rational design of heterogeneous catalysts are unique and of major importance. In fact, Alex is perhaps one of the three leading researchers in heterogeneous catalysis today.

Bell's achievements are in the four areas of elucidation of reaction mechanisms, determination of structure-property relationships, mechanistic studies of zeolite synthesis, and development of theoretical techniques. In carrying out these studies, he has been a pioneer in the use of in situ infrared and Raman spectrophotometry and nuclear magnetic resonance.

In particular, in analyzing reaction mechanisms, he learned that zirconium oxide greatly improves the catalytic activity of copper supported on silica in the hy-drogenation of carbon monoxide or dioxide to methanol. The hydrogenation takes place on the surface of the zirconium oxide and not on the surface of silicon. Carbon monoxide is adsorbed onto zirconium oxide as a formate and carbon dioxide as a bicarbonate. Copper mediates dissociation of hydrogen to atoms, which perform the reduction. The product methoxide cleaves from the zirconium oxide by reductive elimination or hydrolysis.

Working with chemical engineering professor Enrique Iglesia of UC Berkeley on structure-property relationships, Bell found that vanadium oxide catalyzes dehydrogenation of propane by oxygen to propylene. Such a process would be greatly superior to steam cracking of paraffins as is done now. In this work, they get the optimum dispersion of vanadium oxide by supporting it on basic zirconium oxide rather than acidic silica. But zirconium oxide forms zirconium vanadate at high temperatures, which catalyzes combustion of propane and propylene. Their ongoing work is aimed at suppressing the combustion reaction.

In theoretical work with chemical engineering professors Doros Theodorou, now at the University of Petras in Greece, and Arup Chakraborty of UC Berkeley, Bell has derived what he calls a coarsegrained theory to predict diffusivity of long-chain hydrocarbons in zeolite. This treatment is superior to molecular dynamics simulations in predicting the dependence of diffusivity on the molecular weight of the hydrocarbon. The treatment successfully models the diffusivity as a function of the loading of the hydrocarbon and the strength and concentration of adsorption centers in the zeolite. Elsewhere, the collaborators have used quantum calculations to model the binding of protons and copper(I) and (II) ions to zeolite.

Bell was born in New York City in 1942. He received a bachelor's degree in chemical engineering from Massachusetts Institute of Technology in 1964 and a doctor of science degree in chemical engineering there in 1967. He joined the chemical engineering faculty of Berkeley in 1967 and has stayed there since. He served as chairman of the department of chemical engineering from 1981 to 1991 and as dean of the College of Chemistry from 1994 to 1999.

JANUARY 1, 2001 C&EN


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