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 organometallic chemistry that relates to catalytic solutions for environmental problems. Much of our work is in close collaboration with faculty in Civil and Environmental Engineering at UIUC.
Reductive removal by hydrogenation with metallic catalysts has emerged in recent years as a promising prospect for the removal of contaminants in drinking water. One such contaminant is nitrate, which when reduced in vivo to nitrite, can lead to methemoglobinemia ('blue baby syndrome') as well as other deleterious health effects. However, the selective catalytic reduction of nitrate to dinitrogen is a demanding reaction that requires significant interaction between different types of metal reaction centers. A fundamental understanding of the structure and reactivity relationships in known catalysts (e.g., Pd-Cu/Al--2O3) is lacking, and this deficiency limits the possibilities for generating truly useful catalytic systems for nitrate removal from water. One goal of our research has been to develop basic scientific information regarding the operation of bimetallic catalysts at the nanoscale level through the designed synthesis of Pd/Cu colloidal nanoparticles, where control of particle size and composition is achievable. Mechanistic consideration of the nitrate reduction process as involving a key oxygen atom transfer (OAT) to the metal surface has led to a broader scope for the investigation to include the contaminant oxyanion perchlorate. Related reductive approaches are being applied to other oxidized contaminants, such as the disinfection byproduct N-nitrosodimethylamine (NDMA), which has mechanistic pathways that overlap those for nitrate.
Publications
K. D. Hurley, Y. Zhang, and J. R. Shapley, "Heterogeneous Catalytic Reduction of Perchlorate in Water with Re-Pd Catalysts Derived from an Oxorhenium(V) Molecular Precursor," Inorg. Chem., 2009, in press.
K. A. Guy, H. Xu, J. C. Yang, C. J. Werth and J. R. Shapley, "Catalytic Nitrate and Nitrite Reduction with Pd-Cu/PVP Colloids in Water: Composition, Structure, and Reactivity Correlations," J. Phys. Chem., C, 2009, in press.
A. J. Frierdich, J. R. Shapley, and T. J. Strathmann, "Rapid Reduction of N-Nitrosamine Disinfection Byproducts in Water with Hydrogen and Porous Nickel Catalysts," Environ. Sci. Technol., 2008, 42, 262-269.
B. P. Chaplin, J. R. Shapley, and C. J. Werth, "Regeneration of Sulfur-Fouled Bimetallic Pd-Based Catalysts," Environ. Sci. Technol., 2007, 41, 5491-5497.
K. D. Hurley and J. R. Shapley, "Efficient Heterogeneous Catalytic Reduction of Perchlorate in Water," Environ. Sci. Technol., 2007, 41, 2044-2049.
B. P. Chaplin, E. Roundy, K. A. Guy, J. R. Shapley, and C. J. Werth, "Effects of Natural Water Ions and Humic Acid on Catalytic Nitrate Reduction Kinetics Using an Alumina Supported Pd-Cu Catalyst," Environ. Sci. Technol., 2006, 40, 3075-3081.
