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Institute for Integrated Catalysis

Frontiers in Catalysis Science and Engineering

2014

Joachim Sauer

Joachim Sauer
Institut für Chemie, Humboldt-Universitat, Berlin, Germany
"Chemical Accuracy for Molecule-Surface Interactions: Ab Initio Energies and Entropies"
Friday, August 15, 2014
EMSL Auditorium - 1:30PM

A hybrid method that combines MP2 on cluster models with DFT+dispersion on periodic models is presented that yields binding energies of molecules on metal oxide surfaces ab initio and with chemical accuracy. Examples are the binding of CO and CH4 on Mg(001), of H2, CH4, CO and CO2 on the internal surfaces of metal organic frameworks, as well as the adsorption of hydrocarbons in zeolites. Entropies of adsorption can also be calculated with chemical accuracy from vibrational partition functions calculated by DFT+dispersion, when anharmonicities are included. This is shown for adsorption of CH4 on MgO(001) and in a zeolite with Bronsted sites (H-chabazite).


Gerhard Erker

Gerhard Erker
Universität Münster, Organisch-Chemisches Institut, Germany
"Frustrated Lewis Pair Chemistry: Principles and Some Recent Results"
Thursday, August 7, 2014
EMSL Auditorium – 10:00AM

Some general features of frustrated Lewis pair chemistry will be discussed. Most characteristic of FLP behavior is metal -free heterolytic dihydrogen splitting and utilization of this property for the development of metal-free catalytic hydrogenation processes. Consequently, several examples will be presented and discussed. This will be followed by the description and discussion of several newly found reaction types. These involve reactions of borane carbonyls at intramolecular frustrated Lewis pair templates and the reactions of the resulting formylborane type products. Frustrated Lewis pairs have opened a novel entry to methylene phosphonium systems, the phosphorus analogues of the ubiquitous iminium ions. This has led us to a development of a phosphorus relative of the Stork reaction. Eventually, a similarity between coordination of small organic donor molecules to typical transition metal complexes and to the bifunctional intramolecular main group element phosphane/borane frustrated Lewis pairs is discussed. This has led to the development of persistent FLP-NO radical chemistry, systems that have become very easily available by the reaction of various intramolecular vicinal P/B FLPs with nitric oxide (NO). Some features of the chemistry of these new persistent nitroxide radicals will be presented.


2013

Aditya Bhan
Associate Professor, Department of Chemical Engineering and Materials Science,
University of Minnesota
"Catalytic Deoxygenation"
Wednesday, December 3, 2013
EMSL Auditorium - 9:00AM

The (CH2O)n stoichiometry of biomass implies that its conversion to energy carriers and other petroleum-derived hydrocarbons centers on the removal of oxygen. This talk will discuss cases studies of deoxygenation chemistry on metal carbide catalysts. Specifically, the talk will include a discussion of (i) the potential for using CH4 – instead of molecular hydrogen – so that in essence, CH4 serves as a surrogate for molecular hydrogen for biomass deoxygenation while biomass serves as the oxygen carrier for hydrogen removal from CH4; and (ii) the site requirements and mechanism for selectively cleaving C=O and C-O linkages in sugar and lignin monomers for the synthesis of bulk and specialty chemicals.


Clifford Kubiak
Distinguished Professor of Chemistry and Biochemistry
Harold C. Urey Chair in Chemistry
University of California, San Diego

"The Electrocatalytic Reduction of Carbon Dioxide and Oxidation of Formate and Formaldehyde"
Tuesday, February 14, 2013
EMSL Auditorium - 10:00AM

Catalysis of the conversion of carbon dioxide to liquid fuels using solar and electrical energy is a global challenge that could impact the carbon balance by recycling CO2 as fuels. A related challenge is the direct conversion of chemical energy contained in liquid fuels to electrical energy in fuel cell applications. Recent results in the study of artificial catalysts for the chemical reduction of CO2 will be reviewed.


2012

Jack D. Griffith
Jack D. Griffith, Ph.D.

Jack D. Griffith, Ph.D.
Kenan Distinguished Professor of Microbiology and Immunology and Biochemistry
University of North Carolina School of Medicine
"Electron microscopic visualization of telomeres, DNA repair factors, and nanoparticles bound to cells"
Tuesday, October 23, 2012
EMSL Auditorium - 9:00AM

High-resolution electron microscopy provides a unique window into the architecture of DNA and DNA-protein complexes. In our studies of the ends of chromosomes (telomeres), we have shown that human chromosomes end in giant duplex loops. The telomeric factors and DNA repair factors involved will be described and EM and biochemical studies used to illustrate how these factors are central to both cancer and aging. A new approach using cryo methods combined with freeze drying and high-resolution metal coating is providing an exciting means to visualize cell structures including actin networks and nanoparticles being taken up by cells. The method and applications will be discussed.


Jack R. Norton
Department of Chemistry
Columbia University

"H• Transfer from Transition-Metal Hydrides. Applications to Radical Polymerizations and Cyclizations"
Tuesday, February 14, 2012
EMSL Auditorium - 10:00AM


Steric as well as electronic factors affect the rate at which H• is transferred between a transition metal and the carbon of a double bond.  However, the weak M-H bonds of the first-row metals, particularly vanadium, make them uniquely effective in this regard. 

Such reactions can be used in the catalysis of chain transfer during radical polymerizations.  In this process a metalloradical abstracts H• from a chain-carrying radical, transfers it to the double bond of a monomer, and starts a new chain.  The resting state of traditional cobalt chain-transfer catalysts is the Co(II) metalloradical, but both the metalloradical and the hydride are present during the operation of newer (Cr) catalysts. Success at catalyzing chain transfer requires (1) that the M-H bond not be too much stronger than the 50 kcal/mol C-H bond in chain-carrying radicals, and (2) that M• be stable enough to discourage the formation of bonds other than that to hydrogen. 

CpCr(CO)3H and HV(CO)4(P-P) can be used to initiate radical cyclizations by transferring H• to activated terminal olefins. However, the resulting radicals must cyclize quickly; competing reactions include transfer of a second H• (resulting in hydrogenation) and removal of an H• (resulting in isomerization).  Cp(CO)3CrH is relatively slow at H• transfer, but can be regenerated with H2 gas, enabling it to carry out reductive cyclizations catalytically; vanadium hydrides HV(CO)4(P-P) are faster but operate stoichiometrically.


Douglas W. Stephan
Department of Chemistry
University of Toronto

"Frustrated Lewis Pairs": Metal-Free Hydrogenations and Small Molecule Activation
Thursday January 26, 2012
EMSL 1077 - 1:00PM


graphic

The activation of hydrogen has been the purvue of transition metals for 100 years. In recent work we have discovered the first metal-free system capable of H2 activation. Sterically encumbered Lewis acid and base combinations do not form "classical" Lewis acid-base adducts. Rather, the unquenched Lewis acidity and basicity of such sterically "frustrated Lewis pairs (FLPs)" is available for reactivity. Such systems have been shown to effect the heterolytic cleavage of hydrogen and applied to develop metal-free hydrogenations for C=N bonds in a variety of organic substrates. In addition, we have shown that FLP hydrogenation can be used to effect aromatic reductions. FLPs are also shown to exhibit unprecedented reactivity with a variety of other small molecules, including olefins, dienes, alkynes, cyclopropanes, CO2 and N2O. The implications of the discovery of such systems to catalysis and further details will be presented in this lecture.


2011

Daniel E. Resasco
Douglas and Hilda Bourne Chair
George Lynn Cross Professor
School of Chemical, Biological and Materials Engineering
University of Oklahoma


"MODEL COMPOUND STUDIES TOWARDS THE CATALYTIC UPGRADE OF PYROLYSIS OIL IN VAPOR AND LIQUID PHASES"
Tuesday, August 16, 2011
EMSL Auditorium - 9:00AM


An effective approach to stabilize pyrolysis oil is conducting the refining before condensation of the vapors occurs. Degradation by further reaction (oligomerization) occurs in the liquid phase and accelerates when the liquid is subsequently heated for fractionation or other processing. The proposed "catalytic cascade" incorporates a series of reactions that include: (a) formation of C-C bonds to extend the carbon backbone of short oxygenates to the desired gasoline/diesel range; (b) incorporation of short carbon fragments (C1-C3) into the aromatic ring of phenolic compounds; (c) deoxygenation of the resulting products to monofunctional compounds or hydrocarbons. The different catalysts used in this cascade include: basic catalysts (MgO, ZrO2, CsX zeolites), acidic catalysts (H-ZSM5, H-beta zeolites), mixed oxides (CeZrO2), supported metal catalysts (Cu, Ni, Ru, Pd supported on carbon nanotubes and monolith). These catalysts are used in the vapor phase or in liquid (biphasic) systems. The latter employs nanoparticle catalysts to stabilize water/oil emulsions and to conduct reactions at the liquid/liquid interface to benefit from the differences in solubility exhibited by the reactants (bio-oil) and products (bio-fuels) and achieve continuous reaction/separation.


Prof. Jingyue (Jimmy) Liu
Director, Center for Nanoscience
Professor, Department of Physics & Astronomy
Professor, Department of Chemistry & Biochemistry
"Nanostructures for Catalysis and Energy Production"
Friday, May 13, 2011
EMSL Auditorium - 1:30PM


» Research Highlight: Large Problem, Tiny Answer

Energy is not only the driver for improving the quality of human life but also critical to our survival. To power the planet for a better future, it is imperative to develop new processes for effective use of energy and to develop sustainable and clean energy resources. Catalysis, the essential technology for accelerating desired chemical transformations, plays an important role to realizing environmentally friendly and economically feasible processes for producing energy carriers and for converting them into directly usable energy. Design and synthesis of controlled nanostructures can help us address some key issues encountered in understanding the fundamental processes and dynamics of catalyzed reactions. We have recently synthesized both nanostructured metal oxides and shape-controlled metal nanocrystals, and applied them to the systematic investigation of catalytic processes for steam reforming of alcohols and the oxidation of carbon monoxide on nanoscale facets. Aberration-corrected scanning transmission electron microscopy techniques have been used to elucidate the atomic structures of the active phases. The ability of sub-Ångström resolution imaging with in situ capabilities available in a modern aberration-corrected TEM/STEM provides us excellent opportunities to study the dynamic behavior of nanostructures and to understand their synthesis-structure-performance relationships. Recent progresses in synthesizing novel metal oxide nanostructures for energy harvest and storage will also be discussed.


Prof. Manos Mavrikakis
University of Wisconsin - Madison
Department of Chemical & Biological Engineering
"On the role of hydrogen in heterogeneously catalyzed reactions"
Monday, March 14, 2011
EMSL Auditorium - 1:00PM


Hydrogen is a frequent participant in several heterogeneously catalyzed reactions, including Fischer-Tropsch Synthesis (FTS) of fuels, ammonia synthesis, oxygen reduction reaction (ORR), NO reduction, preferential oxidation of CO in the presence of H2 (PROX), etc. Having analyzed the detailed aspects of the reaction mechanism for a number of these reactions on various transition metal and alloy surfaces using first-principles methods, some common principles governing the role of hydrogen in a wide range of catalytic transformations begin to emerge. In this presentation, we will discuss these common mechanistic principles by examples, including FTS, NO-reduction, ORR, PROX, through an analysis of the energetics of alternative elementary reaction steps and the resulting potential energy diagrams. Connections to observations from experimental studies provide an invaluable perspective for the evaluation of our theoretical assessments.


Prof. Thomas B. Rauchfuss
University of Illinois
Department of Chemistry
William H. & Janet B. Lycan Professor of Chemistry
"Synthetic Analogues for the Active Sites of the Hydrogenase Enzymes"
Monday, February 28, 2011
EMSL Auditorium - 10:00AM


The lecture will summarize recent progress in modeling the behavior of the hydrogenase enzymes. Emphasis will be on reactivity of reduced diiron and nickel-iron thiolates toward protons, oxidizing equivalents, and other electrophiles. Work on the FeFe models, which is more advanced, will show the importance of both the redox and internal base modules of this active site. Work on NiFe systems will highlight progress—the preparation of Ni-Fe-hydrides—and gaps.


Prof. Michael T. Klein
University of Delaware, Energy Institute
Department of Chemical Engineering
"Molecule-based Modeling of Heavy Hydrocarbon Structure and Reaction"
Wednesday, February 23, 2011
EMSL Auditorium - 10:00AM


The considerable interest in molecule-based models of heavy hydrocarbon structure and reaction is motivated by the need to predict both upstream and downstream properties of these materials. This is because the molecular composition is an optimal starting point for the prediction of mixture properties. The potential advantages of molecule-based modeling are thus clear. Less readily apparent, however, is that the development and operation of molecular models comes with a large requirement for model construction and solution time as well as analytical and reactivity information.


Prof. Christopher W. Jones
Georgia Institute of Technology
School of Chemical & Biomolecular Engineering
School of Chemistry and Biochemistry
J. Carl & Sheila Pirkle Faculty Fellow
"Heterogenized M-Salen Catalysts for Enantioselective Reactions: Catalyst Design, Structure-Reactivity Trends, and Deactivation Pathways"
Monday, January 31, 2011
EMSL Auditorium - 1:00PM


» Research Highlight: A Personality Change for a Catalyst

Metal salen complexes are widely applied as catalysts for numerous important enantioselective reactions. The reactions catalyzed by metal salen complexes generally follow either (i) monometallic mechanisms (e.g. Mn-salen for epoxidation or Ru-salen for cyclopropanation), whereby a single metal complex promotes the catalytic reaction or (ii) bimetallic mechanisms, where cooperation between two metal complexes is required for efficient catalysis (e.g. Co-salen for epoxide ring-opening or Al-salen conjugate additions of cyanide). The design of effective heterogenized catalysts should therefore take into account the reaction mechanism, as reactions in category (i) are hypothesized to be optimized by accessible yet isolated supported metal salen complexes, whereas reactions of type (ii) are hypothesized to require efficient complex mobility, facilitating metal salen—metal salen cooperative interactions.

Here, several new designs for (a) soluble polymer or oligomer supported metal salen complex catalysts, (b) insoluble polymer resin supported complexes, and (c) insoluble porous silica supported are described. Their utility in the cooperative Co-salen catalyzed hydrolytic kinetic resolution of epoxides and the monometallic Ru-salen catalyzed enantioselective cyclopropnantion of olefins is reported. The kinetics of the reactions using both fresh and recycled catalysts are compared. Most catalysts are shown to deactivate during use, and the mechanisms of deactivation are explored. Strategies to reduce or mitigate catalyst deactivation are described.


2010

Date Speaker Title
November 17, 2010 Prof. Raul F. Lobo Small Pore Zeolites: Effective Catalysts for the Selective Catalytic Reduction of NOx
Flier | Article
September 29, 2010 Prof. T. Brent Gunnoe Development of Transition Metal Catalysts for the Hydroarylation of Olefins
Flier | Article
September 13, 2010 Prof. Dionisios G. Vlachos Complexity and Emergent Behavior in Catalytic Reactions: CO Oxidation on Gold, Biomass Processing, and Ammonia Decomposition
Flier | Article
July 13, 2010 Prof. George Huber Breaking the Chemical and Engineering Barriers to Lignocellulosic Biofuels
Flier | Article
March 17, 2010 Prof. Abhaya Datye Bimetallic PdZn Catalysts for the Steam Reforming of Methanol
Flier | Article
March 1, 2010 Joost VandeVondele Cutting Through Questions for a Molecular-Level Understanding of Solar Cells
Flier | Article
February 24, 2010 Jingguang G. Chen Experimental and Theoretical Studies of Cathode Electrocatalysts for Fuel Cells
Flier | Article

2009

Date Speaker Title
September 8, 2009 Dr. Stefan Vajda Bond-Selective chemistry on Catalysts Designed at the Subnanometer to the Nanometer Scale
Flier | Article
June 23, 2009 Prof. Dr. Jean-Pierre Gilson New Insights on Zeolite chemistry by Advanced IR and NMR characterization Tools
Flier | Article
March 31, 2009 Dr. Marc J.A. Johnson Tuning the Strength and Reactivity of Metal-Ligand Bonds: Reactive Nitrides and Stable Carbides in Catalytic Multiple-Bond Metathesis Reactions
Flier | Article

2008

Date Speaker Title
August 26, 2008 Prof. Dr. Johannes Lercher Catalytic Activation of Hydrocarbons in Confined Spaces
Flier | Article
March 18, 2008 Prof. Dr. Cynthia M. Friend Chemical Reactivity and Surface Restructuring at the Nanoscale: Oxidation Reactions Promoted by Au
Flier | Article
January 30, 2008 Prof. Dr. Peter C. Stair The Chemical Nature of Supported Vanadium Oxide
Flier| Article

2007-2003

Date Speaker Title
October 22, 2007 Prof. Dr. Bert Weckhuysen Utrecht University, The Netherlands A Close-Up View of Catalytic Solids in Action
Flier | Article
October 1, 2007 Prof. Dr. Helmut Schwarz Institute of Chemistry, Technical University, Berlin, Germany

Flier| Article
September 21, 2007 Prof. S. Ted Oyama
Virginia Polytechnic Institute & State University
Nanostructure of a High-Permeability, Hydrogen-Selective Inorganic Membrane
September 12, 2007 Tom Baker
Los Alamos National Laboratory
Molecular Catalysis for Energy Applications
September 10, 2007 Prof. Alexis T. Bell
University of California, Berkeley
Identifying the Relationships between Catalyst Composition and Structure and Catalyst Performance: Challenges for the Experimentalist and the Theoretician
April 12, 2007 Prof. Gabor Somorjai
University of California, Berkeley
Transition of Metal Single Crystals to Monodispersed Nanoparticles (1-10 nm) as Model Catalyst Systems. Bridging the Pressure Gap and Materials Gap in Catalysis
March 9, 2007 Dr. Robert J. Davis
University of Virginia
Selective Oxidation Reactions Catalyzed by Supported Gold Nanoparticles
January 31, 2007 Prof. Robert L. Augustine
Seton Hall University
Anchored Homogeneous Catalysts: The Best of Both Worlds
September 7, 2006 Prof. Wolfgang Sachtler
Northwestern University
Mechanism of NOx Reduction with Acetaldehyde over Zeolite-Based Catalysts
May 25, 2006 Pratibha L. Gai
Dupont Research Fellow
Pioneering development of atomic resolution-operando TEM for catalysis: surface nano-engineering in the 21st Century
May 12, 2006 Dr. Matthias Scheffler
Fritz Haber Institute of the Max Planck Society
Novel Insights into Heterogeneous Catalysis by First-Principles Statistical Mechanics
April 19, 2006 Daniel G. Nocera
Massachusetts Institute of Technology
Powering the Planet: The Challenge to Chemistry in the 21st Century
March 30, 2006 Dr. Tobin J. Marks
Vladimir N. Ipatieff
Northwestern University
Bridges Between Heterogeneous and Homogeneous Catalysis. The Case of Single-Site and Multiple-Site Olefin Polymerization Catalysts
February 2, 2006 Dr. Horia Metiu
University of California, Santa Barbara
Doped oxides as catalysts. Why gold clusters are reactive? CO oxidation by Au2/TiO2(110)
December 7, 2005 Dr. Barry J. Cooper
Johnson Matthey
The Catalytic Control of Motor Vehicle Emissions
September 27, 2005 Dr. Gary McVicker
ExxonMobil Research and Engineering Company
Retired March 2005
Evolution of Enhanced Performance Pt/KL Reforming Catalysts
September 12, 2005 James A. Dumesic
Department of Chemical Engineering
University of Wisconsin - Madison
Catalytic Production of Hydrogen and Alkanes by Aqueous-phase Biorefining of Oxygenated Hydrocarbons
September 7, 2005 Frits Dautzenberg
Consultant
Environmentally Benign Catalysis and Reactor Approaches towards Curing the World's Oil Addiction
July 18, 2005 Bala Subramaniam
NSF Engineering Research Center for Environmentally Beneficial Catalysis (CEBC)
"Catalysis in Carbon Dioxide-Based Media: A Multiscale Approach toward Process Development"
June 28, 2005 Dr. Robert J. Farrauto
Corporate Research Fellow
Engelhard Corporation
On the Road to the Hydrogen Economy
June 6, 2005 Professor Charles A. Mims
Department of Chemistry
University of Toronto
Studies of Oxygen Activation in Mixed Ionic-Electronic Conducting Oxides using Isotopes
May 10, 2005 Professor John M. Vohs
Carl V.S. Patterson
Professor and Chair
Department of Chemical and Biomolecular Engineering
University of Pennsylvania
Reactivity of Model Supported Vanadia Catalysts
April 1, 2005 Professor Miguel J. Yacaman
Reese Endowed Professor in Engineering
Department of Chemical Engineering University of Texas at Austin
New Frontiers in TEM-STEM of Active Sites in Catalysis: Can we use nanotechnology to tailor selectivity in catalysts?
January 25, 2005 Professor Seong Ihl Woo
Director of the Nano Catalysis and Materials Laboratory
Korea Advanced Institute of Science and Technology
Combinatorial Methods for Catalysis, Fuel Cells, and Electronic Materials
December 15, 2004 Professor Enrique Iglesia
Department of Chemical Engineering
University of California at Berkeley, and E.O. Lawrence Berkeley National Laboratory
Site Requirements and Elementary Steps in Catalytic Reactions of Alkanes and Alkenes
November 9, 2004 Dr. Jens R. Rostrup-Nielsen, Haldor Topsoe
The Catalyst and Technology Company
Limits of Catalytic Steam Reforming Processes for H2 Production
November 1, 2004 Professor John T. Yates, Jr., R. K. Mellon
Professor of Chemistry and Physics
University of Pittsburgh
Photocatalysis on TiO2 Surfaces
September 27, 2004 Dr. John Armor
Global Catalysis, (Recently retired from Air Products and Chemicals, Inc.)
Current and Future Routes to H2 Production
September 16, 2004 Professor Lanny D. Schmidt
Department of Chemical Engineering and Materials Science
University of Minnesota
Hydrogen and Chemicals from Fossil and Renewable Fuels by Autothermal Reforming
Aug. 4, 2004 Dr. Farrel W. Lytle
The EXAFS Company
X-Ray Spectroscopies: From Catalysis to the Red Deserts of Mars
May 12, 2004 Professor Bruce Gates
Department of Chemical Engineering
University of California, Davis
Molecular Catalysts on Supports: Synthesis Characterization and Performance of Metal Complexes And Clusters on Metal Oxides and Zeolites
May 10, 2004 Professor Calvin H. Bartholomew
Pope Professor of Chemical Engineering
Brigham Young University
Evolution of Cobalt Fischer-Tröpsch Catalyst Design
April 16, 2004 Professor Jack H. Lunsford
Department of Chemistry
Texas A&M University
The Direct Formation on Hydrogen Peroxide from Hydrogen and Oxygen over Palladium Catalysts
March 2, 2004 Professor Matt Neurock
University of Virginia
Computational Catalysis Towards the Elucidation and Design of Active Catalytic Environments
February 12, 2004 Professor Jens Norskov
Technical University of Denmark
Computational Catalysis: From Quantum Mechanics to Materials Design
January 15, 2004 Dr. Jennifer Holmgren
UOP LLC
Combinatorial Chemistry: Catalysing Innovation in the Chemical Industry
December 11, 2003 Dr. Leo E. Manzer
Dupont
Industrial Opportunities for the Catalytic Conversion of Biomass Derivatives
October 15, 2003 Professor Mark Barteau
University of Delaware
Predicting Catalytic Performance from STM Measurements on Single Molecules
September 29, 2003 Professor Jim Dumesic
University of Wiscosin
Hydrogen from Catalytic Reforming of Biomass-derived Hydrocarbons in Liquid Water
September 26, 2003 Professor Masatake Haruta
National Institute of Advanced Science and Technology
Catalysis and Applications of Gold
July 16, 2003 Professor Raymond J. Gorte
University of Pennsylvania
Recent Developments on Anodes for Direct Fuel Utilization in SOFC

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