Computational Design of Catalysts: The Control of Chemical Transformation to Minimize the Environmental Impact of Chemical Processes
EMSL Project ID
20691
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.
Project Details
Project type
Capability Research
Start Date
2006-10-01
End Date
2009-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
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Alayoglu S, AU Nilekar, E Mavrikakis, and BW Eichhorn. 2008. "Ru–Pt core–shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen." Nature Materials 7:333-338. doi:10.1038/nmat2156
Alayoglu S, AU Nilekar, E Mavrikakis, and BW Eichhorn. 2008. "Ru–Pt core–shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen." Nature Materials 7(4):333-338. doi:10.1038/nmat2156
Barteau MA. 2006. "Surface science and the advancement of direct olefin epoxidation A perspective on the article, ‘‘Partial oxidation of higher olefins on Ag(111) and Ag(110): Conversion of styrene to styrene oxide, benzene, and benzoic acid’’, by Andreas Klust and Robert J. Madix." Surface Science 600(23):5021-5023.
Bruch LW, RP Nabar, and M Mavrikakis. 2009. "Weak Molecular Chemisorption of N2/Pt(111)." Journal of Physics: Condensed Matter 21(26):264009-264016. doi:10.1088/0953-8984/21/26/264009
Calaza F, D Stacchiola, M Neurock, and WT Tysoe. 2010. "Coverage Effects on the Palladium-Catalyzed Synthesis of Vinyl Acetate: Comparison between Theory and Experiment." Journal of the American Chemical Society 132(7):2202-2207. doi:10.1021/ja907061m
Cheng L, and Q Ge. 2007. "Effect of γ-Al₂O₃ substrate on NO₂ interaction with supported BaO clusters." Surface Science 601(12):L65-L68.
Cheng L, and Q Ge. 2008. "Effect of BaO Morphology on NOx Abatement: NO? Interaction with Unsupported and ?-Al?O?-Supported BaO." Journal of Physical Chemistry C 112(43):16924–16931. doi:10.1021/jp806884c
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Grabow LC, AA Gokhale, ST Evans, JA Dumesic, and E Mavrikakis. 2008. "Mechanism of the Water Gas Shift Reaction on Pt: First Principles, Experiments, and Microkinetic Modeling." Journal of Physical Chemistry C 112(12):4608-4617. doi:10.1021/jp7099702
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Janik MJ, CD Taylor, and M Neurock. 2007. "First Principles Analysis of the Electrocatalytic Oxidation of Methanol and Carbon Monoxide." Topics in Catalysis 46(3-4):306-319. doi:10.1007/s11244-007-9004-9
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Mei D, NA Deskins, M Dupuis, and Q Ge. 2008. "Density Functional Theory Study of Methanol Decomposition on the CeO2(110) Surface ." Journal of Physical Chemistry C 112(11):4257-4266.
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Yang Y, CA Mims, RS Disselkamp, D Mei, JH Kwak, J Szanyi, CHF Peden, and CT Campbell. 2008. "Isotope effects in methanol synthesis and the reactivity of copper formates on a Cu/SiO2 catalyst." Catalysis Letters 125(3-4):201-208. doi:10.1007/s10562-008-9592-4
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