Lectures in the field of materials, spectroscopy and catalysis
Thursday, June 30, 2011 at 4.00 p.m.
(Department of Chemical Engineering, University of Virginia, Charlottesville, VA, USA)
Introduction Prof. Robert Davis
Robert Davis obtained his Ph.D. degree in Chemical Engineering from Stanford University in 1989. He subsequently worked as a postdoctoral research fellow in the Chemistry Department at the University of Namur in Belgium. He joined the faculty in Chemical Engineering at the University of Virginia in 1990 as an assistant professor, was promoted to associate professor in 1996, full professor in 2002, and Earnest Jackson Oglesby Professor in 2009. Professor Davis has also served as the Chair of Chemical Engineering at the University of Virginia since 2002. He has received the Emmett Award of the North American Catalysis Society, the NSF Young Investigator Award, the DuPont Young Professor Award, the Union Carbide Innovation Recognition Award, and the UVa Rodman Scholars Award for Excellence in Teaching. Professor Davis has co-authored more than 100 publications, 1 patent and 1 textbook, entitled “Fundamentals of Chemical Reaction Engineering”. He has delivered over 100 invited lectures at conferences, academic departments and industrial research groups, and has co-authored over 100 additional presentations at technical meetings. Professor Davis has served as President of the Southeastern Catalysis Society, Chair of the 2006 Gordon Research Conference on Catalysis, Chair of Catalysis Programming of the AIChE, Chair of a US government panel charged with worldwide assessment of Catalysis by Nanostructured Materials, Director of the Catalysis and Reaction Engineering Division of the AIChE, Director of the North American Catalysis Society, Co-chair of an International Catalysis Workshop in China, member of the Advisory Board of the International Conferences on Solid Acid and Base Catalysis, and member of the editorial boards of Journal of Catalysis, Applied Catalysis A and B, Journal of Molecular Catalysis A, ChemCatChem and ACS Catalysis.
Some Current Challenges in the Conversion of Biorenewable Molecules over Supported Metal Catalysts
The conversion of biorenewable feedstocks to fuels and chemicals is one approach to partially relieve our growing dependence on fossil fuels. However, there are many scientific and engineering challenges to overcome. In this work, the selective catalytic oxidation of the model polyol glycerol to glyceric acid has been investigated over supported Au catalysts in alkaline water solutions. The influences of solution pH, reactor configuration, gold particle size and addition of Pd were studied in detail. Although the smallest of Au nanoparticles revealed the highest turnover frequency, large Au particles and even bulk Au powder catalyzed the oxidation reaction at high pH. Results from isotopic labeling experiments with 18O showed direct participation of hydroxide from the solution instead of gaseous oxygen in the oxidation reaction, which accounts for the very strong influence of solution pH on the reaction rate and product selectivity as well as the production of peroxide during the reaction. These results are extended to the oxidation of hydroxymethylfurfural in basic solution.
The selective reduction of glycerol to propanediols was also studied over supported metals in aqueous solution. By directly comparing the reaction of glycerol to propylene glycol and ethylene glycol over Pt and Ru catalysts under identical conditions, we concluded that a C-C cleavage path exists on Ru that is not favored on Pt. Moreover, the higher rate of glycerol conversion and shift in product distribution with increasing solution pH indicated solution-phase reactions can be strongly coupled to metal-catalyzed reactions. Although supported Pt catalysts produced mainly 1,2-propanediol under the conditions of study, promotion of Pt by Re resulted in the formation of some 1,3-propanediol that was not observed with monometallic Pt catalysts. The influences of catalyst composition and solution pH on the reaction rate and product distribution during oxidation and reduction reactions will be discussed.
Friday, November 19, 2010 at 4.00 p.m.
(LACCO, Laboratory of Catalysis, CNRS, University of Poitiers, France)
Introduction Prof. Charles Kappenstein
Prof. Charles Kappenstein was born in Lorraine, France in 1946. After a primary school teacher study in Metz, he left this career and started chemistry study at the University of Strasbourg (France). After his graduation, he got a position as assistant professor at the University of Reims in 1968 in the field of coordination and solid state chemistry. He obtained his Ph.D. in 1977 on the coordination chemistry of copper(I) with cyanide ligands in solution and solid state. Then in 1978, he was postdoc at the TU, Munich by Prof. E.O. Fischer, in the field of organometallic chemistry of carbenes and carbines.
In 1981, he moved to the University of Poitiers as associate professor, and spent a sabbatical semester in 1985 by Prof. H. Knözinger, at the LMU, Munich to start his work in catalysis. He was appointed as full professor in 1992 and distinguished professor in 2007. He is emeritus professor since September 2010.
After starting on the preparation and characterization of supported metallic catalysts, he moved in 1994 in the applications of catalysis to propulsion, focusing in the synthesis, development and control of catalyst for the decomposition of propellants. His work was supported by numerous contracts with French Space Agency (CNES), European Space Agency (ESA), European Community (FP7 project GRASP), and French and foreign companies. More recently, he proposed with success the use of different types of structured supports to replace the traditional alumina pellets.
He published more than 160 publications and was full or co-supervisor for 37 Ph.D. theses.
He was awarded the coordination chemistry price by the Société Chimique de France in 1981 and Professeur d'Honneur of the University Cuza, Iasi (Romania) in 2003; he received the Bronze Medal of the University Safarik, Kosice (Slovakia) in 2004.
He developed cooperation with several countries to improve international relationships between students and teachers: Hungary, Romania, Slovakia, Korea, China, India, Egypt, Algeria, Morocco, USA, Kuweit.
Catalysis and Propulsion
The use of catalysis in the field of propulsion began just before WWII in Germany with the catalytic decomposition of hydrogen peroxide H2O2 through liquid injection of permanganate salts: He-176 plane; V1 catapult; V2 turbo-pump gas generator. Hydrogen peroxide was also used for torpedo and submarine propulsion with diesel oil. After WWII, the UK Black Knight rocket program associated kerosene with H2O2 (bipropellant propulsion system) and silver screen catalyst bed.
During the late fifties, the start of the space programs lead to the development of monopropellant propulsion system, using pure hydrazine and Ir/Al2O3 catalysts, to control orbit and orientation of launched satellites.
But in the late nineties, the toxicity of hydrazine associated with environmental concerns promoted the search for less toxic monopropellants. The most currently studied substitutes are energetic aqueous ionic mixtures containing an oxidizer and a fuel in water. The proposed oxidizers are HAN (hydroxylammonium nitrate [NH3OH][NO3]) or ADN (ammonium dinitramide [NH4][N(NO2)2]). Different fuels are associated with these oxidizers: molecular fuels (glycine, glycerol, urea, methanol, etc.) or ionic fuels. The challenge is to develop a catalyst active at low temperatures and resistant at the high temperatures of the product gases.
Other hydrazine substitutes have also been proposed: highly concentrated hydrogen peroxide (90-98 wt-%) and nitrous oxide N2O(g), with the challenge to find an active catalyst, able to survive at 1600°C.
Current objectives, prospective applications, and corresponding challenges are:
Wednesday, February 10, 2010 at 4.00 p.m.
Introduction Prof. Anders Holmen
Anders Holmen is professor of Chemical Engineering at the Norwegian
University of Science and Technology (NTNU) in Trondheim, Norway.
Performance of supported Co
catalysts for Fischer-Tropsch synthesis
Prof. Freek Kapteijn
(TU Delft)Introduction Prof. Freek Kapteijn
Freek Kapteijn (TU Delft) graduated in 1974 at the university of Amsterdam in Chemistry and Mathematics. His Ph.D. on the metathesis of alkenes was received at the same university. As postdoc he focused on Coal Science and Heterogeneous Catalysis. In 1987 he received a tenure position at the University of Amsterdam and he moved to Delft University of Technology in 1993. In 1999 he was nominated ‘Anthonie van Leeuwenhoek’ professor in Delft and he leads per 2008 the section of Catalysis Engineering.
Prof. Kapteijn spent several periods abroad among which in Nancy, France (Villermaux, ENSIC) and Zürich, Switzerland (Prins, ETH), and is guest professor at Zehjiang Normal University, China.
Structured catalysts or structure in catalysis?
Catalytic conversions are the heart of many industrial processes and of activities that improve directly or indirectly our living environment. The catalyst applied is the essential element in these operations, and is usually the result of intensive R&D effort to an optimal selectivity, activity and stability. This development, however, does not end with the catalytic material, which is in essence a primary condition; the mode of application in a reactor and process is at least as important.
Random packed beds and slurry reactors are most commonly used but structured reactors provide a good alternative. Why would one use structured reactors?
The lecture will focus on examples of structuring in multiphase and multifunctional catalytic reaction systems. These include on the reactor level the monolith applied to heterogeneous and enzymatic catalysis, the monolithic stirrer, heat transport in various catalytic structures, the zeolite membrane reactor and the capillary reactor. On the catalyst level results with porous crystalline materials as zeolites and MOFs are presented for photo-catalysis and basic reactions.
Prof. Johannes Lercher
(Technischen Universität München)
Introduction Prof. Johannes A. Lercher
Johannes Lercher is professor at the Department of Chemistry at the TU München. His research is focussed on fundamental and applied aspects of alkane activation and functionalization, design of amine synthesis routes, molecular sieve based sorption and catalysis and in situ characterization of catalytic processes.
In 1981, Johannes Lercher obtained his doctoral degree at the TU Wien, under supervision of Heinrich Noller. In 1982, he had a lectureship at Yale University with Gary Haller and John Fenn.
Prof. Lercher is author of over 330 papers and 10 patents. He is chairman of the Bavarian section of the German Society for Coal Gas and Oil, editor of Journal of Catalysis and member of the board of several catalysis journals. Before, he was President of the International Zeolite Association.
Lecture: Catalytic conversion of alkanes by bifunctional catalysis
The catalyzed activation and selective conversion of light alkanes from methane to butane are the key routes to utilize a broader basis of fossil carbon resources. Activation is possible through acid base as well as redox chemistry. Carbenium ions are the key intermediates in the acid-base route and hydride transfer reaction the key single process that controls the overall performance of catalysts. At a monofunctional site, the generation of the carbocation requires such a high energy input that it occurs only at drastic reaction temperatures. Bifunctional sites, in contrast, able to polarize C-H bonds are the key to lower reaction barriers. Such active sites require special steric arrangements and it appears critical that soft Lewis acid sites are part of such a site.
It will be shown that complex catalysts and closely coupled reaction steps are needed to activate alkanes at mild temperatures. This will be discussed using isomerization and cleavage of alkanes, alkylation, and oxidative functionalization of methane. Only the subtle control of the functions and the catalytic elementary steps leads to active and stable catalysts. New catalytic materials and new potential process routes may be developed using the rigorous understanding of sorption and elementary steps as guiding principle.
Prof. Hans Niemantsverdriet
Prof. J.W. Niemantsverdriet
“Molecules and their Interactions on Surfaces”
Unraveling reaction mechanisms in terms of elementary reaction steps and determining their kinetic parameters is at the heart of understanding catalytic reactions at the molecular level. Such reactions take place between species adsorbed on surfaces. In catalytic modelling interactions between adsorbed species are generally ignored. However, in this lecture it is shown that lateral adsorbate interactions are very significant and play a key role in determining selectivity patterns of surface reactions. A thorough understanding of adsorbate interactions may eventually open the way to better control over selectivity in catalytic reactions.
The second Geus Lecture in honour of the honorary degree from Utrecht University awarded to
March 28, 2006 at 11.00 am
Professor Avelino Corma (1951) was born in Moncófar (Spain). He studied Chemistry at the Universidad de Valencia (1967-1973) and obtained his PhD at the Universidad Complutense de Madrid in 1976. He has worked with Professor Antonio Cortés Arroyo at the Instituto de Catálisis y Petroleoquímica (C.S.I.C.). Subsequently he moved to Queen’s University (Canada) as a post-doctoral fellow and returned to C.S.I.C. in 1979. In 1987 he became research professor at C.S.I.C. and in 1990 director of the Instituto de Tecnología Química of the Universidad Politécnica de Valencia. He has developed the institute to the highest ranks in the field of heterogeneous catalysis with emphasis on zeolites and mesoporous materials. He has covered an incredibly broad field of catalysis from oil refining, acid catalysis, selective oxidation, base catalysis and catalysis for synthesis of fine chemicals. The synthesis of many new microporous and mesoporous materials has been combined with excellent characterization and catalysis studies.
Professor Avelino Corma has received numerous awards and honours such as the Dupont Award (1995), G. Ciapetta Award of the North American Catalyst Society (1998), the Francois Gault European Award on Catalysis (2001), the Houdry Award of the North American Catalysis Society (2003) and the Breck Award of the International Zeolite Association (2004). He has served on the board of many prestigious journals such as Chemical Communications, the Journal of Catalysis and Catalysis Reviews.
He has published more than 500 papers in high-quality journals (e.g.. Chemical Communications, Journal of the American Chemical Society, Angewandte Chemie and Nature) and has been listed as inventor on about 100 patents, many of which are or have been applied commercially. His publications have been cited more than 15,000 times. Professor Corma combines excellent fundamental work in heterogeneous catalysis with innovation that has led to many industrial applications.
Lecture: "A parallelism between homogeneous and heterogeneous catalysis with gold catalysts"
Major improvements in catalysis will require the understanding of the reaction mechanism and the design of catalysts at the molecular level. Transition metal complexes allow to design the electronic and geometrical characteristics of active sites, and from this we can better understand and design solid catalysts. While metallic gold is chemically inert, and therefore of limited use for adsorption and catalysis, Au(III) and Au(I) can act as Lewis acids and also may go through a redox process. Interestingly, their d8 electronic structure is the same than Pd(II) and Pd(0) respectively. Even though their chemical potential and softness-hardness are different respectively. All this opens the possibility to use Au(III) and Au(I) as active catalytic species. Following the above will show that gold metal complexes can catalyze hydrogenations, oxidations and C-C bond formation reactions, being possible to change the product distribution by changing Au(III) by Au(I), in excellent parallelism with the corresponding Pd complexes. Thus, we will present that when stabilizing Au(III) and Au(I) species on solid supports by interplaying with the size of gold particles and the nature of the support, it is possible to catalyze the same reactions that with the gold metal complexes. Raman and XAFS spectroscopies allow to establish the nature of the gold reactive species in solid based gold catalysts.
The first lecture has been given by
Prof. J.W. Geus
Lecture: "Selective Catalytic Oxidation of Hydrogen Sulfide to Elemental Sulfur"