Computationally Intensive Research Project
Computational Design of Catalysts: The Control of Chemical Transformation to Minimize the Environmental Impact of Chemical Processes
MSC News
Additional Information
David A. Dixon,1 Mark A. Barteau,2 Donald Camaioni,3 Qingfeng Ge,4 Maciej S. Gutowski,5 James F. Haw,6 Clark R. Landis,7 Jun Li,3 Donghai Mei,3 Keiji Morokuma,8 Matthew Neurock,9 Lai-sheng Wang,10 James Franz,3 Michel Dupuis,3 William F. Schneider,11 Emmanouil Mavrikakis,12 James M. Caruthers13
1University of Alabama, Tuscaloosa, 2University of Delaware, 3Pacific Northwest National Laboratory, 4Southern Illinois University, 5Heriot-Watt University, 6University of Southern California, 7University of Wisconsin-Madison, 8Emory University, 9University of Virginia, 10Washington State University Tri-Cities, 11University of Notre Dame, 12University of Wisconsin-Madison, 13Purdue
FY07 Allocation - 1,200,000
Abstract
Catalysis is governed by a delicate balance between a myriad of competing bond making and breaking processes including adsorption, reaction, desorption, and surface diffusion that occur at active catalytic centers. These processes are explicitly controlled by the intrinsic bonds that form between the reactants or intermediates and the active catalytic site as well as by the local nanoscale environment about the site. For example, the specific atomic structural configuration and chemical makeup of the ligands that surround an active organometallic center in homogeneous catalysis; and the pore size, local acidity, and specific atomic structure in zeolite control their activity and selectivity in ways that are similar to that found in enzymes. Similarly, supported metal particles and metal oxides are complicated by their complex and ill-defined structure. The catalytic behavior is governed by their size and shape, interaction with the support, composition and atomic configuration for metal alloys and mixed metal oxides, the influence of solution as well as the presence of electric fields or applied potentials. We propose to use advanced computational chemistry approaches implemented on massively parallel computers to develop a quantitative description of catalysts so as to develop new design criteria and to develop new understanding of the physical phenomena that occur at different spatial and temporal scales and that underlie catalytic behavior. Catalysis is about improving kinetics and catalyst design will require quantitative information about transition states for critical reaction processes. Currently information about transition states, especially geometric and spectral information, is only readily accessible by computational methods. Yet such information is critical if we are to develop a language that can describe the events at the atomic level that describe homogeneous, heterogeneous and bio-catalysis. Computational chemistry is an enabling tool for addressing challenges in the optimal design of processes for controlling and enabling chemical transformations leading to processes that have high selectivity, have minimal environmental impact, and are optimal in their use of energy. We will apply the techniques of computational chemistry to address a variety of problems in catalysis science including: oxidative dehydrogenation; organic oxidation chemistry and selectivity; hydrogenation of alkenes and isomerization of alkenes and alkanes; olefin epoxidation; single site olefin polymerization catalysts; mechanisms of charge transfer; charge trapping and energy redistribution for organic photooxidation reactions; the cleavage of C-S, H-S, O-C, N-H bonds activated by metal complexation; supported BaO as NOx storage and reduction catalysts for lean-burn engines; supported single site transition metal catalysts; bond enthalpies for transition metal complexes for metal-alkyls and -hydrides; metastable bimetallic surfaces as catalysts for low temperature fuel cells, water-gas-shift reaction for hydrogen production, and Fischer-Tropsch synthesis of liquid fuels from synthesis gas; Pd(0)- and Pt(0)-catalyzed element-element addition to unsaturated hydrocarbons; activation of the N?N bond and its transformations; and electrocatalytic processes.
