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
Kinetically Relevant Steps and H2/D2 Isotope Effects in Fischer−Tropsch Synthesis on Fe and Co Catalysts
Ojeda M, A Li, RP Nabar, AU Nilekar, M Mavrikakis, and E Iglesia. 2010. "Kinetically Relevant Steps and H2/D2 Isotope Effects in Fischer-Tropsch Synthesis on Fe and Co Catalysts." Journal of Physical Chemistry C 114(46):19761-19770. doi:10.1021/jp1073076
First-Principles Analysis of NOx Adsorption on Anhydrous γ-Al2O3 Surfaces
Mei D, Q Ge, J Szanyi, and CHF Peden. 2009. "First-principles Analysis of NOx Adsorption on Anhydrous ?-Al2O3 Surfaces." Journal of Physical Chemistry C 113(18):7779-7789. doi:10.1021/jp8103563
Coverage Effects on the Palladium-Catalyzed Synthesis of Vinyl Acetate: Comparison between Theory and Experiment
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
Third Row Transition Metal Hexafluorides, Extraordinary Oxidizers, and Lewis Acids: Electron Affinities, Fluoride Affinities, and Heats of Formation of WF6, ReF6, OsF6, IrF6, PtF6, and AuF6
Craciun R, D Picone, RT Long, S Li, DA Dixon, KA Peterson, and KO Christe. 2010. "Third Row Transition Metal Hexafluorides, Extraordinary Oxidizers, and Lewis Acids: Electron Affinities, Fluoride Affinities, and Heats of Formation of WF?, ReF?, OsF?, IrF?, PtF?, and AuF?." Inorganic Chemistry 49(3):1056-1070. doi:10.1021/ic901967h
Heats of Formation of XeF3+, XeF3−, XeF5+, XeF7+, XeF7−, and XeF8 from High Level Electronic Structure Calculations
Grant DJ, TH Wang, and DA Dixon. 2010. "Heats of Formation of XeF??, XeF??, XeF??, XeF??, and XeF? from High Level Electronic Structure Calculations." Inorganic Chemistry 49(1):261-270. doi:10.1021/ic901956g
Molecular Structures and Energetics of the (ZrO2)n and (HfO2)n (n = 1−4) Clusters and Their Anions
Li S, and DA Dixon. 2010. "Molecular Structures and Energetics of the (ZrO?)n and (HfO?)n (n = 1-4) Clusters and Their Anions." Journal of Physical Chemistry A 114(7):2665-2683. doi:10.1021/jp910310j
Structural and Electronic Properties of Reduced Transition Metal Oxide Clusters, M3O8 and M3O8− (M = Cr, W), from Photoelectron Spectroscopy and Quantum Chemical Calculations
Li S, HJ Zhai, LS Wang, and DA Dixon. 2010. "Structural and Electronic Properties of Reduced Transition Metal Oxide Clusters, M?O? and M?O?? (M = Cr, W), from Photoelectron Spectroscopy and Quantum Chemical Calculations." Journal of Physical Chemistry A 113(42):11273-11288. doi:10.1021/jp9082008
Correlating Acid Properties and Catalytic Function: A First-Principles Analysis of Alcohol Dehydration Pathways on Polyoxometalates
Janik MJ, J Macht, E Iglesia, and M Neurock. 2009. "Correlating Acid Properties and Catalytic Function: A First-Principles Analysis of Alcohol Dehydration Pathways on Polyoxometalates." Journal of Physical Chemistry C 113(5):1872-1885. doi:10.1021/jp8078748
First-Principles Prediction of Equilibrium Potentials for Water Activation by a Series of Metals
Taylor CD, RG Kelly, and M Neurock. 2007. "First-Principles Prediction of Equilibrium Potentials for Water Activation by a Series of Metals." Journal of the Electrochemical Society 154(12):F217-221. doi:10.1149/1.2783780
On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper
Gokhale AA, JA Dumesic, and M Mavrikakis. 2008. "On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper." Journal of the American Chemical Society 130(4):1402-1414. doi:10.1021/ja0768237
Step Effects on the Dissociation of NO on Close-Packed Rhodium Surfaces
Rempel J, JP Greeley, LB Hansen, OH Nielsen, JK Norskov, and M Mavrikakis. 2009. "Step Effects on the Dissociation of NO on Close-Packed Rhodium Surfaces." Journal of Physical Chemistry C 113(48):20623-20631. doi:10.1021/jp904108c
Weak molecular chemisorption of N2/Pt(111)
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
Molecular and Atomic Hydrogen Interactions with Au−Ir Near-Surface Alloys
Ferrin PA, S Kandoi, J Zhang, RR Adzic, and M Mavrikakis. 2009. "Molecular and Atomic Hydrogen Interactions with Au-Ir Near-Surface Alloys." Journal of Physical Chemistry C 113:1411-1417. doi:10.1021/jp804758y
Reactivity descriptors for direct methanol fuel cell anode catalysts
Ferrin P, AU Nilekar, JP Greeley, M Mavrikakis, and J Rossmeisl. 2008. "Reactivity Descriptors for Direct Methanol Fuel Cell Anode Catalysts." Surface Science 602(21):3424-3431. doi:10.1016/j.susc.2008.08.011
Surface segregation energies in low-index open surfaces of bimetallic transition metal alloys
Nilekar AU, AV Ruban, and M Mavrikakis. 2008. "Surface Segregation Energies in Low-Index Open Surfaces of Bimetallic Transition Metal Alloys." Surface Science 603(1):91-96. doi:10.1016/j.susc.2008.10.029
Correlating STM contrast and atomic-scale structure by chemical modification: Vacancy dislocation loops on FeO/Pt(111)
Merte LR, J Knudsen, LC Grabow, RT Vang, E Laegsgaard, M Mavrikakis, and F Besenbacher. 2008. "Correlating STM Contrast and Atomic-Scale Structure by Chemical Modification: Vacancy Dislocation Loops on FeO/Pt(111)." Surface Science 603(2):L15–L18. doi:10.1016/j.susc.2008.11.014
Interaction of carbon dioxide with Cu overlayers on Pt(111)
Schumacher N, KJ Andersson, LC Grabow, M Mavrikakis, J Nerlov, and I Chorkendorff. 2008. "Interaction of Carbon Dioxide with Cu Overlayers on Pt(111)." Surface Science 602(3):702-711. doi:10.1016/j.susc.2007.11.030
Adsorption and Formation of BaO Overlayers on γ-Al2O3 Surfaces
Mei D, Q Ge, JH Kwak, DH Kim, J Szanyi, and CHF Peden. 2008. "Adsorption and Formation of BaO Overlayers on Gamma-Al2O3 Surfaces ." Journal of Physical Chemistry C 112(46):18050–18060. doi:10.1021/jp806212z
Effect of BaO Morphology on NOx Abatement: NO2 Interaction with Unsupported and γ-Al2O3-Supported BaO
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
Mechanistic Consequences of Composition in Acid Catalysis by Polyoxometalate Keggin Clusters
Macht J, MJ Janik, M Neurock, and E Iglesia. 2008. "Mechanistic Consequences of Composition in Acid Catalysis by Polyoxometalate Keggin Clusters." Journal of the American Chemical Society 130(31):10369-10379. doi:10.1021/ja803114r
Ru–Pt core–shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen
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
Mechanism of the Water Gas Shift Reaction on Pt: First Principles, Experiments, and Microkinetic Modeling
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
Improved oxygen reduction reactivity of platinum monolayers on transition metal surfaces
Nilekar AU, and E Mavrikakis. 2008. "Improved oxygen reduction reactivity of platinum monolayers on transition metal surfaces." Surface Science 602(14):L89-94. doi:10.1016/j.susc.2008.05.036
Dimer saddle point searches to determine the reactivity of formate on Cu(111)
Mei D, L Xu, and GA Henkelman. 2008. "Dimer Saddle Point Searches to Determine the Reactivity of Formate on Cu(111)." Journal of Catalysis 258(1):44-51. doi:10.1016/j.jcat.2008.05.024
Molecular Structures and Energetics of the (TiO2)n (n = 1−4) Clusters and Their Anions
Li S, and DA Dixon. 2008. "Molecular Structures and Energetics of the (TiO?)n (n = 1-4) Clusters and Their Anions." Journal of Physical Chemistry A 112(29):6646-6666. doi:10.1021/jp800170q
Bond Dissociation Energies in Second-Row Compounds
Grant DJ, MH Matus, JR Switzer, DA Dixon, JS Francisco, and KO Christe. 2008. "Bond Dissociation Energies in Second-Row Compounds." Journal of Physical Chemistry A 112(14):3145-3156. doi:10.1021/jp710373e
Structure and Heats of Formation of Iodine Fluorides and the Respective Closed-Shell Ions from CCSD(T) Electronic Structure Calculations and Reliable Prediction of the Steric Activity of the Free-Valence Electron Pair in ClF6−, BrF6−, and IF6−
Dixon DA, DJ Grant, KO Christe, and KA Peterson. 2008. "Structure and Heats of Formation of Iodine Fluorides and the Respective Closed-Shell Ions from CCSD(T) Electronic Structure Calculations and Reliable Prediction of the Steric Activity of the Free-Valence Electron Pair in ClF??, BrF??, and IF??." Inorganic Chemistry 47(12):5485-5494. doi:10.1021/ic800021h
Benchmark Calculations on the Electron Detachment Energies of MO3- and M2O6- (M = Cr, Mo, W)
Li S, and DA Dixon. 2007. "Benchmark Calculations on the Electron Detachment Energies of MO?? and M?O?? (M = Cr, Mo, W)." Journal of Physical Chemistry A 111(46):11908-11921. doi:10.1021/jp074768i
Catalytic Consequences of Composition in Polyoxometalate Clusters with Keggin Structure
Macht J, MJ Janik, M Neurock, and E Iglesia. 2007. "Catalytic Consequences of Composition in Polyoxometalate Clusters with Keggin Structure." Angewandte Chemie International Edition 46(41):7864-7868. doi:10.1002/anie.200701292
Structural Requirements and Reaction Pathways in Dimethyl Ether Combustion Catalyzed by Supported Pt Clusters
Ishikawa A, M Neurock, and E Iglesia. 2007. "Structural Requirements and Reaction Pathways in Dimethyl Ether Combustion Catalyzed by Supported Pt Clusters." Journal of the American Chemical Society 129(43):13201-13212. doi:10.1021/ja073712z
First Principles Analysis of the Electrocatalytic Oxidation of Methanol and Carbon Monoxide
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
Platinum Monolayer Fuel Cell Electrocatalysts
Adzic RR, J Zhang, K Sasaki, MB Vukmirovic, M Shao, JX Wang, AU Nilekar, M Mavrikakis, JA Valerio, and F Uribe. 2007. "Platinum Monolayer Fuel Cell Electrocatalysts." Topics in Catalysis 46(3-4):249-262. doi:10.1007/s11244-007-9003-x
Bimetallic and Ternary Alloys for Improved Oxygen Reduction Catalysis
Nilekar AU, Y Xu, J Zhang, MB Vukmirovic, K Sasaki, RR Adzic, and M Mavrikakis. 2007. "Bimetallic and Ternary Alloys for Improved Oxygen Reduction Catalysis ." Topics in Catalysis 46(3-4):276-284. doi:10.1007/s11244-007-9001-z