Manos Mavrikakis

Paul A. Elfers Professor

Room: 2010
Engineering Hall
1415 Engineering Drive
Madison, WI 53706

Ph: (608) 262-9053
Fax: (608) 262-9053
manos@engr.wisc.edu


Profile Summary

New materials with properties tailored to specific applications often represent the heart of novel chemical processes and important technological advances. The fundamental understanding of the correlation between materials structure and properties is the key to designing new materials with the desired properties. The primary focus of our research is on the atomic-scale materials design, based on first-principles electronic structure calculations. We are applying state-of-the-art theoretical methods to study a range of important surface phenomena including adsorption, diffusion and chemical reactions on a variety of catalytic and semiconductor surfaces.

These quantum chemical and solid-state physics methods take advantage of the impressive computational speed provided by arrays of fast workstations running in parallel both locally and at the national supercomputer centers. Recent progress in theory allows for approximate solutions to the exact electronic structure problem to be obtained with reasonable accuracy, compared to experimental data. As a result, we can now calculate good estimates for binding energies and diffusion barriers of atoms and molecules on, for example, transition metal surfaces. Moreover, site preferences, adsorbate interactions, nature of specific bonds can all be investigated thoroughly and complement the information provided by advanced experimental techniques. Sophisticated computational algorithms are implemented for the determination of the detailed reaction paths connecting reactants and products of elementary reaction steps of important reaction schemes.

In the course of revealing all this information at the atomic and molecular level, important reaction intermediates, often spectroscopically elusive, can be discovered, thus guiding new experimental efforts towards unexplored territory. The detailed study of competing reaction paths, through the calculation of the corresponding activation energy barriers, allows for the isolation of electronic and geometric factors determining reaction selectivity in a way that is not accessible to experiments, where usually a set of overlapping factors act simultaneously.

Our general research strategy is to study trends in chemical reactivity of solid surfaces and identify discontinuities in their behavior. Explaining trends and discontinuities can help us understand the fundamental reasons behind changes in reactivity. We can then proceed, in strong interaction with experiments, to design surfaces characterized by the desired properties.

The major focus of our current research efforts is on the fundamental reactivity studies for a wide range of important applications, including: fuel cells catalytic electrodes, bimetallic catalysis, selective partial oxidation of hydrocarbons, and the development of novel low temperature and environmentally benign catalytic processes.

Education

  • MS, PhD (Chemical Engineering & Scientific Computing), University of Michigan
  • MS (Applied Mathematics), University of Michigan
  • Diploma, National Technical University of Athens

Research Interests

  • thermodynamics
  • kinetics and catalysis
  • surface science
  • computational chemistry
  • electronic materials
  • fuel cells applications
  • environmental chemical engineering

Awards, Honors and Societies

  • R. H. Wilhelm Award in Chemical Reaction Engineering, AIChE (2014) 
  • Byron Bird Award for Excellence in a Research Publication, College of Engineering, University of Wisconsin - Madison (2014)
  • Kellett Mid-Career Faculty Researcher Award, University of Wisconsin-Madison (2014-2015)
  • APS Fellow (2013)
  • Editor-in-Chief, Surface Science (2012- )
  • Top 100 Chemists of the 2000-2010 decade, Thomson - Reuters (2011)
  • H. I. Romnes Faculty Fellow, University of Wisconsin-Madison (2009-10)
  • Paul H. Emmett Award in Fundamental Catalysis, North American Catalysis Society (2009)
  • Paul A. Elfers Chair in Chemical Engineering, University of Wisconsin-Madison (2008-)
  • Honored Instructor Award, University of Wisconsin-Madison (2008, 2009)
  • S.C. Johnson Distinguished Fellow (2005-2008)
  • NSF CAREER Award (2002-2006)
  • 3M Non-tenured Faculty Award (2002-2004)
  • Shell Oil Company Foundation Faculty Career Initiation Award (2000-2003)
  • Editorial Board, Surface Science (2008-2012)
  • Editorial Board, ACS Catalysis
  • Editorial Board, Catalysis Today
  • Editorial Board, Journal of Molecular Catalysis A: Chemical
  • Editorial Committee, Inaugural, Annual Review of Chemical & Biomolecular Engineering
  • National Academy of Engineering 2006 German-American Frontiers of Engineering Symposium (GAFOE)
  • Visiting Professor - Catalysis Research Center - Hokkaido University, Sapporo, Japan (Summer 2010)
  • Visiting Professor - Chemical Engineering - Technical University of Denmark (Fall 2006)
  • Marie Curie Postdoctoral Fellow, Center for Atomic-scale Materials Physics/Design, Technical University of Denmark (1997-99)
  • ACS, AIChE, APS, AVS, MRS

Publications

  • \"Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces\", (with C. Chen, Y. Kang, Z. Huo, Z. Zhu, W. Huang, H. L. Xin, J. D. Snyder, D. Li, J. A. Herron, M. Chi, K. L. More, Y. Li, N. M. Markovic, G. A. Somorjai, P. Yang, and V. R. Stamenkovic), Science 343, 1339 (2014).
  • \"Formic Acid Decompostion on Au catalysts: DFT, microkinetic modeling, and kinetics experiments\", (with S. Singh, S. Li, R. Carrasuillo-Flores, A. C. Alba-Rubio, and J. A. Dumesic), AIChE Journal, 60, 1303 (2014). 
  • \"Water-Mediated Proton Hopping on an Iron Oxide Surface\", (with L. R. Merte, G. Peng, R. Bechstein, F. Rieboldt, C. A. Farberow, L. C. Grabow, W. Kudernatsch, S. Wendt, E. Lægsaard, and F. Besenbacher), Science 336, 889 (2012).
  • \"Mixed-Metal Pt Monolayer Electrocatalysts with Improved CO Tolerance\", (with A. U. Nilekar, K. Sasaki, C. A. Farberow, and R. R. Adzic), Journal of the American Chemical Society, 133, 18574 (2011).
  • \"Mechanism of Methanol Synthesis on Cu through CO2 and CO Hydrogenation\", (with L. C. Grabow), ACS Catalysis , 1, 365 (2011).
  • \"Alkali-stabilized Pt-OHx species catalyze low-temperature water-gas-shift reactions\", (with Y. Zhai, D. Pierre, H. Saltsburg, R. Si, W. Deng, P. Ferrin, A. U. Nilekar, G. Peng, J. A. Herron, D. C. Bell, and M. Flytzani-Stephanopoulos), Science , 329, 1633 (2010).
  • \"Low temperature CO oxidation on Ni(111) and on a Au/Ni(111) surface alloy\", (with J. Knudsen, L. R. Merte, G. Peng, R. T. Vang, A. Resta, E. Laegsgaard, J. N. Andersen, and F. Besenbacher), ACSNano , 4, 4380 (2010) - Cover page image.
  • \"Kinetically relevant steps and H2/D2 isotope effects in Fischer-Tropsch synthesis on Fe and Co catalysts\", (with M. Ojeda, A. Li, R. Nabar, A. U. Nilekar, and E. Iglesia), Journal of Physical Chemistry C , 114, 19761 (2010).
  • \"Preferential CO oxidation in hydrogen: Reactivity of core-shell nanoparticles\", (with A. U. Nilekar, S. Alayoglu, and B. Eichhorn), Journal of the American Chemical Society , 132, 7418 (2010).
  • \"On the mechanism of low-temperature CO oxidation on Ni(111) and NiO(111)surfaces\", (with G. Peng, L. R. Merte, J. Knudsen, R. T. Vang, E. Laegsgaard, and F. Besenbacher), Journal of Physical Chemistry C , 114, 21579 (2010).
  • \"Partial and complete reduction of O2 by hydrogen on transition metal surfaces\", (with D. Ford, A. U. Nilekar, and Y. Xu), Surface Science , 604, 1565 (2010).
  • \"Platinum monolayer electrocatalysts for O2 reduction: Pt monolayer on carbon-supported PdIr nanoparticles\", (with S. L. Knupp, M. B. Vukmirovic, P. Haldar, J. A. Herron, and R. R. Adzic), Electrocatalysis , 1, 213 (2010).
  • \"CO activation pathways and the mechanism of the Fischer-Tropsch synthesis\", (with M. Ojeda, R. Nabar, A. U. Nilekar, A. Ishikawa, and E. Iglesia), Journal of Catalysis , 272, 287 (2010).
  • \"Hydrogen on and in selected overlayer near-surface alloys and the effect of subsurface hydrogen on the reactivity of alloy surfaces\", (with S. Kandoi, and P. Ferrin), Topics in Catalysis , 53, 384 (2010).
  • \"Reduction of FeO/Pt(111) thin films by exposure to atomic hydrogen\", (with J. Knudsen, L. R. Merte, L. C. Grabow, F. M. Eichhorn, S. Porsgaard, H. Zeuthen, R. T. Vang, E. Lagsgaard, and F. Besenbacher), Surface Science , 604, 11 (2010).
  • \"Structure sensitivity of methanol electrooxidation on transition metals\", (with P. Ferrin), Journal of the American Chemical Society , 131, 14381 (2009).
  • \"Modeling ethanol decomposition on transition metals: a combined application of scaling and Bronsted-Evans-Polanyi relations\", (with P. Ferrin, D. Simonetti, S. Kandoi, E. Kunkes, J. A. Dumesic, and J. K. Norskov), Journal of the American Chemical Society , 131, 5809 (2009).
  • \"Molecular and atomic hydrogen interactions with Au-Ir near-surface alloys\", (with P. A. Ferrin, S. Kandoi, J. L. Zhang, and R. Adzic), Journal of Physical Chemistry C , 113, 1411 (2009) - Cover page image.
  • \"Surface segregation energies in low-index open surfaces of bimetallic transition metal alloys\", (with A. U. Nilekar, and A. V. Ruban), Surface Science , 603, 91 (2009).
  • \"Effectiveness of in-situ NH3 annealing treatments for the removal of oxygen from GaN surfaces\", (with L. C. Grabow, J. J. Uhlrich, and T. F. Kuech), Surface Science , 603, 387 (2009).
  • \"Ru-Pt core-shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen\" (with S. Alayoglu, A. U. Nilekar and B. Eichhorn), Nature Materials, 7, 333 (2008).
  • \"Nanocatalysis beyond the Gold-Rush era\" (with L. C. Grabow), Angewandte Chemie, International Edition, 47, 7390 (2008).
  • \"On the mechanism of low-temperature water gas shift reaction on copper\" (with A. A. Gokhale and J. A. Dumesic), Journal of the American Chemical Society, 130, 1402 (2008).
  • \"Mechanism of the water gas shift reaction on Pt: First-principles, experiments, and microkinetic modeling\" (with L. C. Grabow, A. A. Gokhale, St. Evans and J. A. Dumesic), Journal of Physical Chemistry C, 112, 4608 (2008).
  • \"Improved oxygen reduction reactivity of platinum monolayers on transition metal surfaces\" - Highlighted Article (with A. U. Nilekar), Surface Science, 602, L89 (2008).
  • \"Reactivity descriptors for direct methanol fuel cell anode catalysts\", (with P. Ferrin, A. U. Nilekar, J. Greeley, and J. Rossmeisl), Surface Science , 602, 3424 (2008).
  • \"Manipulation and patterning of the surface concentration of hydrogen on Pd(111) by electric fields\" (with T. Mitsui, E. Fomin, F. Ogletree, M. Salmeron and A. U. Nilekar), Angewandte Chemie International Edition, 46, 5757 (2007).
  • \"A Cu/Pt Near-Surface Alloy for water-gas shift catalysis\" (with J. Knudsen, A. U. Nilekar, R. T. Vang, J. Schnadt, E. Kunkes, J. A. Dumesic and F. Besenbacher), Journal of the American Chemical Society, 129, 6485 (2007).
  • \"On the role of subsurface oxygen and ethylenedioxy in ethylene epoxidation on silver\" (with J. Greeley), Journal of Physical Chemistry C, 111, 7992 (2007).
  • \"The effect of co-adsorbed oxygen on the adsorption and diffusion of potassium on Rh(110): A first-principles study\" (with Y. Xu, H. Marbach, R. Imbihl and I. G. Kevrekidis), Journal of Physical Chemistry C, 111, 7446 (2007).
  • \"A theoretical comparative study of surfactant effect of Sb and Bi on GaN growth\" (with A. A. Gokhale and T. F. Kuech), Journal of Crystal Growth, 303, 493 (2007).
  • \"Platinum monolayer electrocatalysts for oxygen reduction\" (with M. B. Vukmirovic, J. Zhang, K. Sasaki, A. U. Nilekar, F. Uribe and R. R. Adzic), Electrochimica Acta, 52, 2257 (2007).
  • \"Computational Methods: A search engine for catalysts\", Nature Materials, 5, 847 (2006).
  • \"A simple rule of thumb for diffusion on transition-metal surfaces\" (with A. U. Nilekar and J. Greeley), Angewandte Chemie International Edition, 45, 7046 (2006).
  • \"Lattice strain effects on CO oxidation on Pt(111)\", (with L. C. Grabow and Y. Xu), Physical Chemistry Chemical Physics, 8, 3369 (2006) - Cover page image.
  • \"Near-surface alloys for hydrogen fuel cell applications\", (with J. Greeley), Catalysis Today, 111, 52 (2006).
  • \"Prediction of experimental methanol decomposition rates on platinum from first principles\", (with S. Kandoi, J. Greeley, M. A. Sanchez-Castillo, S. T. Evans, A. A. Gokhale and J. A. Dumesic), Topics in Catalysis, 37, 17 (2006).
  • \"Mixed-Metal Pt Monolayer Electrocatalysts for Enhanced Oxygen Reduction Kinetics\" (with J. Zhang, M.B. Vukmirovic, K. Sasaki, A.U. Nilekar, and R.R. Adzic), Journal of the American Chemical Society, 127, 12480 (2005).
  • \"Effect of Subsurface Oxygen on the Reactivity of the Ag(111) Surface\" (with Y. Xu, and J. Greeley), Journal of the American Chemical Society, 127, 12823 (2005).
  • \"Controlling the Catalytic Activity of Platinum Monolayer Electrocatalysts for Oxygen Reduction with Different Substrates\" (with J. Zhang, M. B. Vukmirovic, Y. Xu, and R. R. Adzic), Angewandte Chemie International Edition, 44, 2132 (2005).
  • \"Surfactant effect of Sb on GaN growth\", (with A. A. Gokhale and T. F. Kuech), Journal of Crystal Growth ,285, 146 (2005).
  • \"Surface and subsurface hydrogen: Adsorption properties on transition metals and near-surface alloys\" (with J. Greeley), J. Phys. Chem. B, 109, 3460 (2005).
  • \"Trends in low-temperature water-gas shift reactivity on transition metals\", (with N. Schumacher, A. Boisen, S. Dahl, A. A. Gokhale, S. Kandoi, L. C. Grabow, J. A. Dumesic, and I. Chorkendorff), Journal of Catalysis, 229, 265 (2005).
  • \"Alloy Catalysts Designed from First Principles\" (with J. Greeley), Nature Materials, 3, 810 (2004).
  • \"Strain-Induced Formation of Subsurface Species in Transition Metals\" (with J. Greeley and W. P. Krekelberg), Angewandte Chemie International Edition , 43, 4296 (2004).
  • \"Adsorption and Dissociation of O2 on Pt-Co and Pt-Fe Alloys\" (with Y. Xu and A. Ruban), Journal of the American Chemical Society, 126, 4717 (2004).
  • \"Competitive Paths for Methanol Decomposition on Pt(111)\" (with J. Greeley), Journal of the American Chemical Society, 126, 3910 (2004).
  • \"Modifications of the Electronic Structure of GaSb Surface by Chalcogen Atoms: S, Se, and Te\" (with Z. Y. Liu, A. A. Gokhale, D. A. Saulys and T. F. Kuech), Journal of Applied Physics , 96, 4302 (2004).
  • \"Effect of Sn on the Reactivity of Cu Surfaces\" (with A. A. Gokhale, G. W. Huber and J. A. Dumesic), J. Phys. Chem. B, 108, 14062 (2004).
  • \"Why Au and Cu are More Selective Than Pt for Preferential Oxidation of CO at Low Temperature\" (with S. Kandoi, A. A. Gokhale, L. C. Grabow and J. A. Dumesic), Catalysis Letters, 93, 93 (2004).
  • \"On the origin of the catalytic activity of nanomenter gold particles for low temperature CO oxidation\" (with N. Lopez, T. V. W. Janssens, B. S. Clausen, Y. Xu, T. Bligaard and J. K. Norskov),Journal of Catalysis - Priority Communication, 223, 232 (2004).
  • \"Atomic and Molecular Adsorption on Ir(111)\" (with W. P. Krekelberg and J. Greeley), J. Phys. Chem. B, 108, 987 (2004).
  • \"Atomic Scale Evidence for an Enhanced Catalytic Reactivity of Stretched Surfaces\" (with J. Wintterlin, T. Zambelli, J. Trost and J. Greeley), Angewandte Chemie International Edition (frontispiece), 42, 2849 (2003).
  • \"A first-principles study of surface and subsurface hydrogen on and in Ni(111): Diffusional Properties and Coverage-Dependent behavior\" (with J. Greeley), Surf. Sci., 540, 215 (2003).
  • \"The adsorption and dissociation of O2 molecular precursors on Cu: the effect of steps\" (with Y. Xu), Surf. Sci., 538, 219 (2003).
  • \"Adsorption and Dissociation of O2 on Gold Surfaces: Effect of Steps and Strain\" (with Y. Xu), J. Phys. Chem. B, 107, 9298 (2003).
  • \"CO Vibrational Frequencies on Methanol Synthesis Catalysts: a DFT study\" (with J. Greeley, A. Gokhale, J. Kreuser, H. Topsoe, N-Y. Topsoe and J. A. Dumesic), Journal of Catalysis, 213, 63 (2003).
  • \"DFT Studies for cleavage of C-C and C-O bonds in surface species derived from ethanol on Pt(111)\"(with R. Alcala and J. A. Dumesic), Journal of Catalysis, 218, 178 (2003).
  • \"Microcalorimetric, infrared spectroscopic and DFT studies of CO adsorption on Rh and Rh-Te catalysts\" (with R. He, H. Kusaka and J. A. Dumesic), Journal of Catalysis, 217, 209 (2003).
  • \"A First-Principles Study of Methanol Decomposition on Pt(111),\" (with J. Greeley), Journal of the American Chemical Society, 124, 7193 (2002).
  • \"Methanol Decomposition on Cu(111): A DFT Study,\" (with J. Greeley), J. Cat., 208, 291 (2002).
  • \"Electronic Structure and Catalysis on Metal Surfaces,\" (with J. Greeley and J.K. Norskov), Annu. Rev. Phys. Chem., 53, 319 (2002).
  • \"Structure sensitivity of CO dissociation on Rhodium surfaces,\" (with M. Baumer, H.-J. Freund and J.K. Norskov), Catal. Lett., 81, 153 (2002).
  • \"Universality in Heterogeneous Catalysis,\" (with J.K. Norskov, T. Bligaard, A. Logadottir, S. Bahn, L. B. Hansen, M. Bollinger, H. Bengaard, B. Hammer, Z. Sljivancanin, Y. Xu, S. Dahl and C. J. H. Jacobsen), Journal of Catalysis - Priority Communication, 209, 275 (2002).
  • \"Influence of Bi impurity as a surfactant during the growth of GaN by metalorganic vapor phase epitaxy,\" (with L. Zhang, H.F. Tang, J. Schieke and T.F. Kuech), J. Crystal Growth, 242, 302 (2002).
  • \"The addition of Sb as a surfactant to GaN growth by metal organic vapor phase epitaxy,\" (with L. Zhang, H.F. Tang, J. Schieke and T.F. Kuech), J. Appl. Phys., 92, 2304 (2002).
  • \"Atomic and Molecular Adsorption on Rh(111),\" (with J. Rempel, J. Greeley, L. B. Hansen and J.K. Norskov), J. Chem. Phys., 117, 6737 (2002).
  • \"DFT studies of Acetone and Propanal Hydrogenation on Pt(111),\" (with R. Alcala, J. Greeley and J.A. Dumesic), J. Chem. Phys., 116, 8973 (2002).
  • \"Adsorption and dissociation of O2 on Ir(111)\" (with: Y. Xu), J. Chem. Phys., 116, 10846 (2002).
  • \"Adsorption and dissociation of O2 on Cu(111): thermochemistry, reaction barrier and the effect of strain\" (with: Y. Xu), Surf. Sci., 494, 131 (2001).
  • \"Diffusion of N adatoms on the Fe(100) Surface,\" (with M.O. Pedersen, L. Osterlund, J. J. Mortensen, L. B. Hansen, I. Stensgaard, E. Laegsgaard, J.K. Norskov and F. Besenbacher), Phys. Rev. Lett., 84, 4898 (2000).
  • \"Making Gold Less Noble,\" (with P. Stoltze and J.K. Norskov), Catal. Lett., 64, 101 (2000).
  • \"Molecular N2 Chemisorption - Specific Detection of Step Defect Sites on Pt Surfaces,\" (with C.E. Tripa, T.S. Zubkov, J.T. Yates Jr., and J.K. Norskov), J. Chem. Phys., 111, 8651 (1999).
  • \"Oxygenate Reaction Pathways on Transition Metal Surfaces,\" (with M.A. Barteau), J. Mol. Catal. A, 131, 135 (1998).
  • \"First Synthesis, Experimental and Theoretical Vibrational Spectra of an Oxametallacycle on a Metal Surface,\" (with G.S. Jones, J.M. Vohs and M.A. Barteau), Journal of the American Chemical Society, 120, 3196 (1998).
  • \"Effect of Strain on the Reactivity of Metal Surfaces,\" (with B. Hammer and J.K. Norskov), Phys. Rev. Lett., 81, 2819 (1998)

Courses

Fall 2014-2015

  • CBE 990 - Thesis-Research
  • CBE 890 - Pre-Dissertator\'s Research
  • CBE 790 - Master\'s Research or Thesis
  • CBE 735 - Kinetics and Catalysis
  • CBE 599 - Special Problems
  • Profile Summary

    New materials with properties tailored to specific applications often represent the heart of novel chemical processes and important technological advances. The fundamental understanding of the correlation between materials structure and properties is the key to designing new materials with the desired properties. The primary focus of our research is on the atomic-scale materials design, based on first-principles electronic structure calculations. We are applying state-of-the-art theoretical methods to study a range of important surface phenomena including adsorption, diffusion and chemical reactions on a variety of catalytic and semiconductor surfaces.

    These quantum chemical and solid-state physics methods take advantage of the impressive computational speed provided by arrays of fast workstations running in parallel both locally and at the national supercomputer centers. Recent progress in theory allows for approximate solutions to the exact electronic structure problem to be obtained with reasonable accuracy, compared to experimental data. As a result, we can now calculate good estimates for binding energies and diffusion barriers of atoms and molecules on, for example, transition metal surfaces. Moreover, site preferences, adsorbate interactions, nature of specific bonds can all be investigated thoroughly and complement the information provided by advanced experimental techniques. Sophisticated computational algorithms are implemented for the determination of the detailed reaction paths connecting reactants and products of elementary reaction steps of important reaction schemes.

    In the course of revealing all this information at the atomic and molecular level, important reaction intermediates, often spectroscopically elusive, can be discovered, thus guiding new experimental efforts towards unexplored territory. The detailed study of competing reaction paths, through the calculation of the corresponding activation energy barriers, allows for the isolation of electronic and geometric factors determining reaction selectivity in a way that is not accessible to experiments, where usually a set of overlapping factors act simultaneously.

    Our general research strategy is to study trends in chemical reactivity of solid surfaces and identify discontinuities in their behavior. Explaining trends and discontinuities can help us understand the fundamental reasons behind changes in reactivity. We can then proceed, in strong interaction with experiments, to design surfaces characterized by the desired properties.

    The major focus of our current research efforts is on the fundamental reactivity studies for a wide range of important applications, including: fuel cells catalytic electrodes, bimetallic catalysis, selective partial oxidation of hydrocarbons, and the development of novel low temperature and environmentally benign catalytic processes.


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