October 11th, 2013 14:15/17:15 Aula N15 Edificio 2-Padiglione Nord 1°piano (14:15/17:15 Room N15, Building 2-North pavillion, 1st floor) Georges Guiochon, Professor and Distiguished Scientist of Analytical Chemistry Department of Chemistry, University of Tennessee, USA The Good, the Bad and the Ugly. Preparative Chromatography, with gas, liquid or supercritical fluids? Chromatography is a physico-chemical method used to purify compounds or to eliminate some particular impurities. From its inception, it has suffered from its use of dilute solutions, thus requiring the handling of large volumes of solvents under high pressures. This is a most costly process. In practice, it is used essentially for the production of pharmaceuticals. The nature of the mobile phase used in chromatography has a profound influence on the performance of the process. An obvious critical requirement is that the feed be soluble in the mobile phase. However, the density, the compressibility, and the viscosity of the mobile phase play important roles on the performance of this process. The solubility requirement has practically eliminated preparative gas chromatography from the realm of the practical industrial separation processes. The very strange properties of the critical and supercritical fluids have considerably delayed the development of practical applications of preparative supercritical fluid chromatography. This method is now beginning to attract great interest from separation engineers in pharmaceutical companies. Due to the low viscosity of supercritical fluids and the high diffusion coefficients of compounds of moderate molecular weights in these fluids, this method is growing in practical importance; it has found a significant niche, the preparative production of pure enantiomers; it might even replace some day preparative liquid chromatography in many current applications. So it is time to begin learning about its peculiar properties, its possible advantages and its specific constraints. November 25th, 2013 14:15/17:15 Aula N15 Edificio 2-Padiglione Nord 1°piano (14:15/17:15 Room N15, Building 2-North pavillion, 1st floor) Gregory Stephanopoulos W.H. Dow Professor of Biotechnology & Chemical Engineering Department of Chemical Engineering, MIT, USA Metabolic Engineering Metabolic Engineering is emerging as a new synthetic chemistry aiming at the construction of microbial biocatalysts for the production of chemicals and fuels from renewable feedstocks such as sugars, glycerol, volatile fatty acids, but also recently discovered abundant stores of natural gas. This is accomplished through the engineering of proper pathways in microorganisms such as bacteria and yeast, which convert the substrate to the designated target product. Principles of catalysis and chemical reaction engineering are fundamental in guiding the process of biocatalyst design, which is the essence of metabolic engineering. November 29th, 2013 10:45 Aula MA1 Mancinelli 10:45 Room MA1 Mancinelli Research at the Interface of Chemistry and Reaction Engineering for Sustainable Oxidation Technologies Prof. Ive Hermans Catalysis as an enabling technology for the sustainable synthesis of chemicals and the production of energy has changed the world significantly. Improving the performance of existing technologies, and/or enabling more sustainable reactions, which were hitherto unknown, or unfeasible on a large scale, can both have a significant impact. Within my research group, we unravel complex catalytic systems to their elementary reactions, in order to identify the rate‐ and selectivity‐determining step(s). To do so, we use various experimental and computational tools, ranging from chemical kinetics to (in situ) spectroscopy. Subsequently, we aim to put the mechanistic pieces together in order to optimize the macroscopic performance, either through improved reaction engineering or catalyst synthesis. During the lecture, this multidisciplinary approach will be illustrated by case studies form both homogeneous and heterogeneous catalysis, focusing on selective oxidations. December 6th, 2013 14:15/17:15 Aula N15 Edificio 2-Padiglione Nord 1°piano (14:15/17:15 Room N15, Building 2-North pavillion, 1st floor) Maria Flytzani-Stephanopoulos Robert and Marcy Haber Endowed Professor in Energy Sustainability Department of Chemical and Biological Engineering, Tufts University, USA Sustainable solutions to low-temperature hydrogen production: atomically dispersed supported metal catalysts A portfolio of energy solutions are envisioned for the foreseeable future, encompassing both renewable and traditional fuels and processes to meet the ever growing demand for energy worldwide. From the point of view of materials, particularly catalytic materials that can be used to optimize the relevant fuel production and utilization processes, there is an urgent need for new active and stable catalysts that comprise only minute quantities of precious metals, thus offering viable solutions to the way we generate energy. Atomically dispersed supported metal catalysts offer new prospects for low-cost, sustainable energy and chemicals production, as was discussed in a recent review [1]. Interest in atomically dispersed supported metal catalysts is demonstrated by the thriving research on the preparation and stabilization of these sites through novel synthesis methods aimed at maximizing the catalyst efficiency [1, 2]. In the area of fuel processing and hydrogen production, a new generation of active and stable water-gas shift catalysts is needed for application to PEM fuel cells. Developmental work along this line has been going on for more than fifteen years and has improved our understanding of how best to design such catalysts. Parallel catalyst studies have been undertaken in recent years for the steam reforming of methanol to produce hydrogen-on-demand in various small-scale applications. Here, the catalyst must possess a high selectivity to hydrogen which requires high activity at low temperatures and a reaction pathway that does not involve the water gas-shift reaction. Recent advances in the design of such catalysts will be highlighted in a two-hour seminar series presentation. a) We will draw from our experience with gold catalysts to demonstrate how atomically-designed gold species catalyze the water-gas shift reaction.[3-5] We will point to similarities with copper as well as the Pt-group metals. “Shape effects” of supports will be presented [4], while the promotion effect of alkali addition will be shown as a general one, enabling unparalleled flexibility in the choice of supports, including inert oxide[6] and carbon surfaces.[7] Generalized designs of low-temperature WGS catalysts will be discussed. b) For the low-temperature steam reforming of methanol, we will compare gold catalysts to platinum, and discuss why the two are different, irrespective of the support or the promoter used. [8,9] The selectivity to hydrogen depends on the metal chosen, even when the latter is present as atoms (cations) on the surface. We will also demonstrate how to tailor the surface properties of oxide supports to maximize their efficiency as carriers of the active metal species. ----------------------------------------------------------------------------------------------------------------------------- ---[1] M. Flytzani-Stephanopoulos, B.C. Gates, Annu. Rev. Chem. Biomol. Eng. 3 (2012) [2] J.M. Thomas, Z. Saghi, P.L. Gai, Top. Catal. 54 (2011) [3] Q. Fu, H. Saltsburg and M. Flytzani-Stephanopoulos, Science 301, 935-938 (2003) [4] R. Si and M. Flytzani-Stephanopoulos, Angew. Chem. Int’l Ed. 47(15), 2884-2887 (2008) [5] M. Yang, L. F. Allard, M. Flytzani-Stephanopoulos, J. Am. Chem. Soc. 135: 3768–3771 (2013) [6] Y. Zhai, D. Pierre, R. Si, W. Deng, P. Ferrin, A. U. Nilekar, G. Peng, J. A. Herron, D. C. Bell, H. Saltsburg, M. Mavrikakis, M. Flytzani-Stephanopoulos, Science 329, 1633-1636 (2010) [7] B. Zugic, D.C. Bell, M. Flytzani-Stephanopoulos, Appl. Catal. B: Environmental, in press; doi.org/10.1016/j.apcatb.2013.07.013 [8] N. Yi, R. Si, H. Saltsburg, M. Flytzani-Stephanopoulos, Appl. Catal. B: Env. 95(1-2), 87-92 (2010) [9] M. B. Boucher, S. Goergen, N. Yi, M. Flytzani-Stephanopoulos, PCCP 13, 2517-2527 (2011) December 13th, 2013 14:15/17:15 Aula N15 Edificio 2-Padiglione Nord 1°piano (14:15/17:15 Room N15, Building 2-North pavillion, 1st floor) Gregory Stephanopoulos W.H. Dow Professor of Biotechnology & Chemical Engineering Department of Chemical Engineering, MIT, USA Biofuels With increasing interest in bioenergy and biofuels, this lecture would address issues of feedstock availability, impact on carbon footprint, available technologies for biofuels and economics. Various platforms for biofuel production, such as the sugar, oil, algae and gas (synthesis or otherwise) platforms could be discussed, along with the issues associated with engineering microbes to achieve cost effective conversion of renewable substrates to various types of biofuels. February/March, 2014 ………….. Maria Flytzani-Stephanopoulos Robert and Marcy Haber Endowed Professor in Energy Sustainability Department of Chemical and Biological Engineering, Tufts University, USA Title to be defined on the design of Single Atom Alloys for selective hydrogenation reactions or on the desulfurization of fuel gases at high temperatures with regenerable sorbents (we can choose)