Computational Design of Catalysts: The Control of Chemical Transformation to Minimize the Environmental Impact of Chemical Processes
EMSL Project ID
34000
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; mixed homogeneous/heterogeneous catalysts; transition metal oxides; ligand design for C-C coupling reactions; water-gas-shift (WGS) and preferential oxidation (PROX) of CO in the presence of H2 with metals and metal oxides; catalytic partial oxidation of methane over metal nanoparticles; structure function relationships for zeolite acid catalysis; C-H bond activation over promoted metal sulfides; metal particle sintering on alumina; effect of the metal-support interaction on catalytic conversion of CO2; O2 dissociation at a (111) FCC metal surface; acid properties of polyoxometallate clusters; formation of C-C bonds from C1 species, specifically during the formation of hydrocarbons and alcohols from mixtures of H2 and CO on Fe, Co, and Rh; reactivity of small molecules gamma-Al2O3 supported catalysts; and quantitative prediction of reaction intermediates for homogeneous electrocatalysis.
Project Details
Project type
Capability Research
Start Date
2009-10-01
End Date
2012-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Akpa BS, C DAgostino, LF Gladden, K Hindle, H Manyar, J McGregor, M Neurock, N Sinha, EH Stitt, D Weber, JA Zeitler, and DW Rooney. 2012. "Solvent Effects in the Hydrogenation of 2-Butanone." Journal of Catalysis 289:30-41. doi:10.1016/j.jcat.2012.01.011
Allian AD, K Takanabe, KL Fujdala, X Hao, TJ Truex, J Cai, C Buda, M Neurock, and E Iglesia. 2011. "Chemisorption of CO and Mechanism of CO Oxidation on Supported Platinum Nanoclusters." Journal of the American Chemical Society 133(12):4498-4517. doi:10.1021/ja110073u
Carrasquillo-Flores R, JMR Gallo, K Hahn, JA Dumesic, and M Mavrikakis. 2013. "Density Functional Theory and Reaction Kinetics Studies of the Water–Gas Shift Reaction on Pt–Re Catalysts." ChemCatChem 5(12):3690-3699. doi:10.1002/cctc.201300365
Chen M, JE Dyer, K Li, and DA Dixon. 2013. "Prediction of Structures and Atomization Energies of Small Silver Clusters, (Ag)n, n < 100." Journal of Physical Chemistry A 117(34):8298–8313. doi:10.1021/jp404493w
Chin YH, C Buda, M Neurock, and E Iglesia. 2011. "Reactivity of Chemisorbed Oxygen Atoms and Their Catalytic Reactivity of Chemisorbed Oxygen Atoms and Their Catalytic." Journal of the American Chemical Society 133(40):15958–15978. doi:10.1021/ja202411v
Chin YH, C Buda, M Neurock, and E Iglesia. 2011. "Selectivity of Chemisorbed Oxygen in C–H Bond Activation and CO Oxidation and Kinetic Consequences for CH?–O? Catalysis on Pt and Rh Clusters." Journal of Catalysis 283(1):10-24. doi:10.1016/j.jcat.2011.06.011
Craciun R, AJ Vincent, KH Shaughnessy, and DA Dixon. 2010. "Prediction of Reliable Metal-PH? Bond Energies for Ni, Pd, and Pt in the 0 and +2 Oxidation States." Inorganic Chemistry 49(12):5546-5553. doi:10.1021/ic1004853
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
Craciun R, RT Long, and DA Dixon. 2010. "Electron Affinities, Fluoride Affinities, and Heats of Formation of the Second Row Transition Metal Hexafluorides: MF6 (M ) Mo, Tc, Ru, Rh, Pd, Ag)." Journal of Physical Chemistry A 114(28):7571-7582. doi:10.1021/jp1022949
Deskins NA, D Mei, and M Dupuis. 2009. "Adsorption and diffusion of a single Pt atom on gamma-Al2O3 surfaces." Surface Science 603(17):2793-2807.
Fang Z, and DA Dixon. 2013. "Hydrolysis of ZrCl4 and HfCl4: The Initial Steps in the High-Temperature Oxidation of Metal Chlorides to Produce ZrO2 and HfO2." Journal of Physical Chemistry C. doi:10.1021/jp400228d
Ferrin PA, and M Mavrikakis. 2009. "Structure Sensitivity of Methanol Electrooxidation on Transition Metals." Journal of the American Chemical Society 131(40):14381-14389. doi:10.1021/ja904010u
Ferrin PA, DA Simonetti, S Kandoi, EL Kunkes, JA Dumesic, JK Norskov, and E Mavrikakis. 2009. "Modeling Ethanol Decomposition on Transition Metals: A Combined Application of Scaling and Brønsted-Evans-Polanyi Relations." Journal of the American Chemical Society 131:5809-5815. doi:10.1021/ja8099322
Ferrin PA, S Kandoi, AU Nilekar, and M Mavrikakis. 2012. "Hydrogen Adsorption, Absorption and Diffusion on and in Transition Metal Surfaces: A DFT Study." Surface Science 606:679-689. doi:10.1016/j.susc.2011.12.017
Ge Q ,Gutowski M S 2015. "A Comparative Study of Methanol Adsorption and Dissociation over WO3(001) and ReO3(001)" Topics in Catalysis 58(10):655–664. 10.1007/s11244-015-0402-0
Gounder RP, AJ Jones, RT Carr, and E Iglesia. 2012. "Solvation and Acid Strength Effects on Catalysis by Faujasite Zeolites." Journal of Catalysis 286: 214–223. doi:10.1016/j.jcat.2011.11.002
Grabow LC, and M Mavrikakis. 2011. "Mechanism of Methanol Synthesis on Cu through CO2 and CO Hydrogenation." ACS Catalysis 1(4):365–384. doi:10.1021/cs200055d
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
Hahn K, and M Mavrikakis. 2014. "Atomic and Molecular Adsorption on Re(0001)." Topics in Catalysis. doi:10.1007/s11244-013-0162-7
Haranczyk M, and MS Gutowski. 2010. "Combinatorial–Computational–Chemoinformatics (C³) Approach to Finding and Analyzing Low-Energy Tautomers." Journal of Computer-Aided Molecular Design 24(6-7):627-638. doi:10.1007/s10822-010-9344-6
Herron JA, and M Mavrikakis. 2014. "On the Composition of Bimetallic Near Surface Alloys in the Presence of Oxygen and Carbon Monoxide." Catalysis Communications 52:65-71. doi:10.1016/j.catcom.2013.10.021
Herron JA, S Tonelli, and M Mavrikakis. 2012. "Atomic and Molecular Adsorption on Pd(111)." Surface Science 606(21-22):1670-1679. doi:10.1016/j.susc.2012.07.003
Herron JA, S Tonelli, and M Mavrikakis. 2013. "Atomic and Molecular Adsorption on Ru(0001)." Surface Science 614:64-74. doi:10.1016/j.susc.2013.04.002
Ide MS, M Neurock, and RJ Davis. 2012. "Mechanistic Insights on the Hydrogenation of ?,?-Unsaturated Ketones and Aldehydes to Unsaturated Alcohols over Metal Catalysts." ACS Catalysis 2(4):671-683. doi:10.1021/cs200567z
Jackson VE, KE Gutowski, and DA Dixon. 2013. "Density Functional Theory Study of the Complexation of the Uranyl Dication with Anionic Phosphate Ligands with and without Water Molecules ." Journal of Physical Chemistry A 117(36):8939–8957. doi:10.1021/jp405470k
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Kandoi S, JP Greeley, DA Simonetti, J Shabaker, JA Dumesic, and M Mavrikakis. 2010. "Reaction Kinetics of Ethylene Glycol Reforming over Platinum in the Vapor versus Aqueous Phases." Journal of Physical Chemistry C 115(4):961–971. doi:10.1021/jp104136s
Kandoi S, PA Ferrin, and E Mavrikakis. 2010. "Hydrogen on and in Selected Overlayer Near-Surface Alloys and the Effect of Subsurface Hydrogen on the Reactivity of Alloy Surfaces." Topics in Catalysis 53(5-6):384-392. doi:10.1007/s11244-010-9444-5
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Kulkarni A, M Bedolla-Pantoja, S Singh, RF Lobo, M Mavrikakis, and MA Barteau. 2012. "Reactions of Propylene Oxide on Supported Silver Catalysts: Insights into Pathways Limiting Epoxidation Selectivity." Topics in Catalysis 55(1-2):3-12. doi:10.1007/s11244-012-9773-7
Ling S, and MS Gutowski. 2011. "SSC: A Tool for Constructing Libraries for Systematic Screening of Conformers." Journal of Computational Chemistry 32(9):2047-2054. doi:10.1002/jcc.21774
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
Li S, C Guenther, MS Kelley, and DA Dixon. 2011. "Molecular Structures, Acid?Base Properties, and Formation of Group 6 Transition Metal Hydroxides." Journal of Physical Chemistry C 115(16):8072-8103. doi:10.1021/jp111031x
Mei D, and Q Ge. 2012. "A DFT+U study of structure and reducibility of CenO2n-x (n?4, 0?x?n) nanoclusters." Computational and Theoretical Chemistry 987:25-31. doi:10.1016/j.comptc.2011.11.009
Mei D, J Du, and M Neurock. 2010. "First-principles-based Kinetic Monte Carlo Simulation of Nitric Oxide Reduction over Platinum Nanoparticles under Lean-burn Conditions." Industrial and Engineering Chemistry Research 49(21):10364-10373. doi:10.1021/ie100999e
Mei D, JH Kwak, J Szanyi, Q Ge, and CHF Peden. 2010. "Catalyst Size and Morphological Effects on the Interaction of NO2 with BaO/?-Al2O3 Materials ." Catalysis Today 151(3-4):304-313. doi:10.1016/j.cattod.2010.01.005
Mei D, Q Ge, JH Kwak, DH Kim, CM Verrier, J Szanyi, and CHF Peden. 2009. "Characterization of Surface and Bulk Nitrates of ?-Al2O3-Supported Alkaline Earth Oxides using Density Functional Theory." Physical Chemistry Chemical Physics. PCCP 11(18):3380-3389. doi:10.1039/b819347a
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
Merte LR, G Peng, R Bechstein, F Rieboldt, CA Farberow, LC Grabow, W Kudernatsch, S Wendt, E Laegsgaard, M Mavrikakis, and F Besenbacher. 2012. "Water-Mediated Proton Hopping on an Iron Oxide Surface." Science 336(6083):889-893. doi:10.1126/science.1219468
Merte LR, J Knudsen, FM Eichhorn, S Porsgaard, H Zeuthen, LC Grabow, E Laegsgaard, H Bluhm, MB Salmeron, M Mavrikakis, and F Besenbacher. 2011. "CO-Induced Embedding of Pt Adatoms in a Partially Reduced FeOx Film on Pt(111)." Journal of the American Chemical Society 133(28):10692–10695. doi:10.1021/ja2015923
Merte LR, LC Grabow, G Peng, J Knudsen, H Zeuthen, W Kudernatsch, S Porsgaard, E Laegsgaard, M Mavrikakis, and F Besenbacher. 2011. "Tip-Dependent Scanning Tunneling Microscopy Imaging of Ultrathin FeO Films on Pt(111)." Journal of Physical Chemistry C 115(5): 2089–2099. doi:10.1021/jp109581a
Neurock M. 2010. "Engineering Molecular Transformations for Sustainable Energy Conversion." Industrial and Engineering Chemistry Research 49(21):10183-10199. doi:10.1021/ie101300c
Nilekar AU, K Sasaki, CA Farberow, RR Adzic, and M Mavrikakis. 2011. "Mixed-Metal Pt Monolayer Electrocatalysts with Improved CO Tolerance." Journal of the American Chemical Society 133(46):18574–18576. doi:10.1021/ja2072675
Nilekar AU, S Alayoglu, BW Eichhorn, and M Mavrikakis. 2010. "Preferential CO Oxidation in Hydrogen: Reactivity of Core-Shell Nanoparticles." Journal of the American Chemical Society 132(21):7418-7428. doi:10.1021/ja101108w
Norton JR, T Spataru, DM Camaioni, SJ Lee, G Li, J Choi, and JA Franz. 2014. "Kinetics and Mechanism of the Hydrogenation of CpCr(CO)3•/[CpCr(CO)3]2 Equilibrium to CpCr(CO)3H." Organometallics 33(10):2496-2502. doi:10.1021/om4012399
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
Ojeda M, RP Nabar, AU Nilekar, A Ishikawa, M Mavrikakis, and E Iglesia. 2010. "CO activation pathways and the mechanism of Fischer–Tropsch synthesis." Journal of Catalysis 272(2):287-297. doi:10.1016/j.jcat.2010.04.012
Pan Y, C Liu, D Mei, and Q Ge. 2010. "Effects of Hydration and Oxygen Vacancy on CO2 Adsorption and Activation on ?-Ga2O3(100)." Langmuir 26(8):5551-5558. doi:10.1021/la903836v
Pan Y, D Mei, C Liu, and Q Ge. 2011. "Hydrogen Adsorption on Ga2O3 Surface: A Combined Experimental and Computational Study." Journal of Physical Chemistry C 115(20):10140-10146. doi:10.1021/jp2014226
Peng G, SJ Sibener, GC Schatz, and M Mavrikakis. 2012. "CO2 Hydrogenation to Formic Acid on Ni(110)." Surface Science 606(13-14):1050-1055. doi:10.1016/j.susc.2012.02.027
Peng G, SJ Sibener, GC Schatz, ST Ceyer, and M Mavrikakis. 2012. "CO2 Hydrogenation to Formic Acid on Ni(111)." Journal of Physical Chemistry C 116(4):3001-3006. doi:10.1021/jp210408
Rempel J, JP Greeley, LB Hansen, OH Nielsen, JK Norskov, and E 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
Rossmeisl J, PA Ferrin, GA Tritsaris, AU Nilekar, S Koh, SE Bae, SR Brankovic, P Strasser, and M Mavrikakis. 2012. "Bifunctional Anode Catalysts for Direct Methanol Fuel Cells." Energy & Environmental Science 5(8):8335-8342. doi:10.1039/c2ee21455e
Shi H, OY Gutierrez, GL Haller, D Mei, RJ Rousseau, and JA Lercher. 2013. "Structure sensitivity of hydrogenolytic cleavage of endocyclic and exocyclic C-C bonds in methylcyclohexane over supported iridium particles." Journal of Catalysis 297:70-78. doi:10.1016/j.jcat.2012.09.018
Sinha N, and M Neurock. 2012. "A First Principles Analysis of the Hydrogenation of C1AC4 Aldehydes and Ketones Over Ru(0001)." Journal of Catalysis 295:31-44. doi:10.1016/j.jcat.2012.07.018
Stott AC, JI Brauer, A Garg, SV Pepper, PB Abel, C DellaCorte, RD Noebe, G Glennon, EJ Bylaska, and DA Dixon. 2010. "Bonding and microstructural stability in Ni55Ti45 studied by experimental and theoretical methods." Journal of Physical Chemistry C 114(46):19704-19713.
Stott AC, TP Vaid, EJ Bylaska, and DA Dixon. 2012. "Tuning Band Gap Energies in Pb3(C6X6) Extended Solid-State Structures." Journal of Physical Chemistry C 116(15):8370-8378. doi:10.1021/jp211967u
Svenum IH, JA Herron, M Mavrikakis, and HJ Venvik. 2012. "Adsorbate-Induced Segregation in a PdAg Membrane Model System: Pd3Ag(1 1 1)." Catalysis Today 193(1):111-119. doi:10.1016/j.cattod.2012.01.007
Tyo EC, C Yin, M Di Vece, Q Qian, G Kwon, S Lee, B Lee, JE Debartolo, S Seifert, RE Winans, R Si, B Ricks, S Goergen, M Rutter, B Zugic, M Flytzani-Stephanopoulos, ZW Wang, RE Palmer, M Neurock, and S Vajda. 2012. "Oxidative Dehydrogenation of Cyclohexane on Cobalt Oxide (Co3O4) Nanoparticles: The Effect of Particle Size on Activity and Selectivity." ACS Catalysis 2(11):2409-2423. doi:10.1021/cs300479adoi:10.1021/cs300479a
Vasiliu M, S Li, AJ Arduengo, III, and DA Dixon. 2011. "Bond Energies in Models of the Schrock Metathesis Catalyst." Journal of Physical Chemistry 115(24):12106-12120. doi:10.1021/jp202668p
Wang TH, AM Navarrete-Lopez, S Li, DA Dixon, and JL Gole. 2010. "Hydrolysis of TiCl?: The Initial Steps in the Production of TiO?." Journal of Physical Chemistry A 114(28):7561-7570. doi:10.1021/jp102020h
Zeuthen H, W Kudernatsch, G Peng, LR Merte, LK Ono, L Lammich, Y Bai, LC Grabow, M Mavrikakis, S Wendt, and F Besenbacher. 2013. "Structure of Stoichiometric and Oxygen-Rich Ultrathin FeO(111) Films Grown on Pd(111)." Journal of Physical Chemistry C 117(29):15155–15163. doi:10.1021/jp4042638
Zhao YF, RJ Rousseau, J Li, and D Mei. 2012. "Theoretical study of syngas hydrogenation to methanol on the polar Zn-terminated ZnO(0001) surface." Journal of Physical Chemistry C 116(30):15952-15961. doi:10.1021/jp211055s
Zhou WP, X Yang, MB Vukmirovic, BE Koel, J Jiao, G Peng, M Mavrikakis, and RR Adzic. 2009. "Improving Electrocatalysts for O2 Reduction by Fine-Tuning the Pt-Support Interaction: Pt Monolayer on the Surfaces of a Pd3Fe(111) Single-Crystal Alloy." Journal of the American Chemical Society 131(35):12755-12762. doi:10.1021/ja9039746
Zope B, DD Hibbitts, M Neurock, and RJ Davis. 2010. "Reactivity of the Gold/Water Interface During Selective Oxidation Catalysis." Science 330(6000):74-78. doi:10.1126/science.1195055