John R. Shapley
Emeritus Professor of Chemistry
Professor Shapley received B.S. and Ph.D. degrees from Kansas and Harvard, respectively, and joined the faculty in 1972 after a postdoctoral year at Stanford. The research in his group involves synthesis of inorganic and organometallic compounds and examination of their properties in relation to catalytic solutions for environmental problems.
Research
We are interested in inorganic and organo-metallic chemistry that relates to catalytic solutions for environmental problems. Current examples include: 1) natural gas conversion to hydrocarbons for sulfur-free fuels; 2) oxidation of hydrogen, methanol, or other fuels in fuel cells; and 3) selective nitrate reduction in drinking water.
- The conversion of natural gas (largely methane) to liquid fuels and chemicals now occurs in two steps: first, partial oxidation to synthesis gas (CO+H2); and, second, reductive polymerization (Fischer-Tropsch) to hydrocarbons. The first stage is very energy intensive and the second is highly non-selective. Significant aspects of the mechanisms for these processes remain undetermined, hindering the rational design of new catalysts with improved properties. There also is interest in a one-step process. Organometallic clusters provide the best models for intermediates in catalytic transformations of various hydrocarbon groups on metal surfaces.
- Fuel cells represent an increasingly attractive 'green' alternative to traditional power sources based on combustion. Fuel cells are thermodynamically more efficient, and they generate no noxious byproducts, but there are interesting catalytic challenges. Our specific focus is on producing bimetallic nano-particles to function directly as oxidation catalysts on the fuel cell anodes or indirectly to convert liquid fuels into hydrogen. We are synthesizing mixed-metal clusters that incorporate catalytically active metals and studying their interaction with models for carbon (fullerenes) or oxide (silsesquioxanes) supports.
- Supplies of drinking water are at risk from nitrate ion contamination, which can lead to methemoglobinemia ('blue baby' syndrome) as well as other deleterious health effects. One approach to keeping the nitrate ion concentration below mandated levels is the selective catalytic reduction of nitrate with hydrogen into nitrogen gas and water. This is the only method that can completely convert the nitrate to innocuous products. However, the catalysts currently available are not sufficiently selective to nitrogen alone, as the net release of ammonia is also significantly higher than permitted levels. We are examining the properties of colloidal, nanoscale Pd/Cu particles to maximize the catalytic efficiency of nitrate reduction and probing other bimetallic combinations to discover catalysts with improved selectivity.
Publications
"Preparation and Properties of Triosmium Propyl and Propylidene Complexes," M. E. Cree and J. R. Shapley, Inorg. Chimica Acta, 345, 345-352 (2003).
"Formation of Cs-Ir3(CO)3(
5-C9H7)3 Interconversion of Cs and C-3v Isomers," M. C. Comstock and J. R. Shapley, Organometallics, 21, 5983-5986 (2002).
"Dinuclear Tungsten, Molybdenum, and Ruthenium Complexes Derived from 1,2-Bis(3-Indenyl)Ethane," R. Khayatpoor and J. R. Shapley, Organometallics, 21, 4794-4798 (2002).
"Electrochemistry of Carbidopentaruthenium C60 Complexes and Related Clusters," A. J. Babcock, J. H. Li, K. Lee, and J. R. Shapley, Organometallics, 21, 3940-3946, (2002).
"Carbidoheptarhenate Cluster Complexes of Cadmium and Zinc Units: The Structure of [PPh4]2[Re7C(CO)21(µ3-ZnCl)]," C. A. Wright, J. R. Shapley, Inorganic Chemistry, 40, 6338 (2001).
