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Home , Gerhard Ertl, Gerhart Jander, Peter Adolf Thiessen, Walter Grotrian

Andrzej Lech Kawczyński Instytut Chemii Fizycznej PAN Warszawa Seminarium Ogólnoinstytutowe 6 czerwiec 2008

„Gerhard Ertl – laureat nagrody Nobla z dziedziny chemii w 2007 r.” “for his studies of chemical processes on solid surfaces”

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Paul Sabatier –Nobel 1912

"for his method of hydrogenating organic compounds in the presence of finely disintegrated metals whereby the progress of organic chemistry has been greatly advanced in recent years" – Nobel 1918

"for the synthesis of from its elements" – Nobel 1932

"for his discoveries and investigations in surface chemistry" •Curriculum Vitae: •Years • •Function • •Institution •2004-now • •Professor emeritus • •Dept. of Physical Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, •1986-2004 • •Director • •Dept. of Physical Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin •1981-1982 • •Visiting Professor • •Dept. of Chemistry, University of California, Berkeley •1979 • •Visiting Professor • •Dept. of Physics, University of Wisconsin, Milwaukee •1976-1977 • •Visiting Professor • •Dept. of Chemical Engineering, California Institute of Technology, Pasadena •1973-1986 • •Professor & Director • •Inst. for Physical Chemistry, Ludwig Maximilians University, •1968-1973 • •Professor & Director • •Inst. for Physical Chemistry, Technical University, Hannover (presently Gottfried Wilhelm Leibniz University) •1965-1968 • •Assistant & Lecturer • •Technical University, Munich •1962-1965 • • •Technical University, Munich: Dr. rer. nat in 1965 •1959-1961 • • •Technical University, : Dipl. Phys. in 1961 •1958-1959 • • •Ludwig Maximilians University, Munich •1957-1958 • • • •1955-1957 • • •Technical University, Stuttgart •1936 • •born • •October 10, in Stuttgart, Diploma thesis „Eine Temperatursprungmetode zur Untersuchung schneller Dissozationsreaktionen mit Hilfe eines Mikrowellenimpulses” -”Temperature jump experiments to study fast dissociation reactions using microwave pulses”- promotor prof. Heinz Gerischer; 1961

Ph.D. thesis „Über die Kinetik der katalytischen Oxidation von Wasserstoff an Germanium Einkristallen” – „On the kinetics of the catalytic hydrogen oxidation on Germanium single crystals” -promotor prof. Heinz Gerischer, 1965

Habilitation thesis „Untersuchung von Oberfläschenstrukturen und -reaktionen mittels Beugung langsamer Elektronen” – „Surface structural and reactivity studies using low energy diffraction”, 1967 676.G. Ertl: Reaktionen an Oberflächen: vom Atomaren zum Komplexen (Nobel-Vortrag).Angew. Chem. 120, 3578-3590 (2008). Reactions at Surfaces: From to Complexity (Nobel Lecture).Angew. Chem. Int. Ed. 47, 3524-3535 (2008). G. Ertl, H. Knözinger, F. Schüth, and J. Weitkamp (eds.), Handbook of Heterogeneous Catalysis, 2nd ed., 8 vols. Wiley-VCH, Weinheim (2008). 675.G. Ertl: Non-Linear Dynamics: Oscillatory Kinetics and Spatio- Temporal Pattern Formation, Chapter 5.2.4 in: Handbook of Heterogeneous Catalysis, 2nd ed. pp. 1492-1516. 674.G. Ertl: Dynamics of Surface Reactions, Chapter 5.2.2 in: Handbook of Heterogeneous Catalysis, 2nd ed. pp. 1462-1479. •Honors and Awards: •Year • •Designation • •Organization • 2008 • •Großes Bundesverdienstkreuz mit Stern • •President of the Federal Republic of Germany • 2008 • •Dr. honoris causa • •Technische Universität München • 2008 • •Dr. honoris causa • •Queen’s University Belfast • 2008 • •Verdienstmedaille • •Land Baden-Würtemberg • 2007 • • in Chemistry ••The Nobel Prize Foundation • 2007 • •Otto-Hahn-Preis • •Gesellschaft Deutscher Chemiker, Deutsche Physikalische Gesellschaft, & the City of Fra • 2007 • •Gold Medal • •Slovak Chemical Society • 2007 • •Baker Lectureship ••Cornell University, Ithaca (NY) • 2007 • •Faraday Lectureship ••Royal Society of Chemistry • 2006 • •Guptill Lecture • •Dalhousie University, Halifax • 2005 • •Angström Lecture • •University of Uppsala • 2005 • • Lecture • •California Institute of Technology • 2003 • •Dr. honoris causa • •University of Aarhus • 2003 • •Dr. honoris causa • •Chalmers University of Technology, Goeteborg • 2003 • •Dr. honoris causa • •University of Leuven • 2002 • •FMC Lectureship • •Princeton University • 2002 • • Visiting Professor • •Max Planck Institute Mulheim • 2002 • •Spiers Memorial Medal and Lectureship • •Royal Society of Chemistry • 2001 • •G.F. Smith Lecture • •University of Illinois, Urbana • 2001 • •Kelly Lecture • •Purdue University • 2001 • •Schuit Lecture • •Technical University of Eindhoven • 2001 • •Pitzer Lecture • •University of California, Berkeley The principle of heterogeneous catalysis. Energy diagram illustrating the progress of a chemical reaction with and without a catalyst. STM image from a Pt(111) surface (5.3x5.5 mm) after exposure to a small concentration of O2 molecules at 165 K STM snapshots from O atoms adsorbed on a Ru(001) surface at 300 K: a) at very small coverage; b) at higher coverage. The Sabatier reaction or Sabatier process involves the reaction of hydrogen with carbon dioxide at elevated temperatures and pressures in the presence of a nickel catalyst to produce methane and water. Optionally ruthenium on alumina makes a more efficient catalyst. It is described by the following reaction:

CO2 + 4H2 → CH4 + 2H2O Since the work of Sabatier there was a longstanding question of how hydrogen is organized on metals like palladium, platinum and nickel.

Haber-Bosch process

N2 + 3H2 → 2NH3

The Haber-Bosch process was the first industrial chemical process to make use of extremely high pressures (200 to 400 atmospheres) and high temperatures (670 to 920 K).

Catalyst composed mostly of .

The efficiency of the reaction is a function of pressure and temperature - greater yields are produced at higher pressures and lower temperatures. Surface topography and chemical composition of an industrial ammonia synthesis catalyst (the Mittasch catalyst). P. H. Emmett, one of the pioneers of catalysis research in 1974 concluded:

“The experimental work of the past 50 years leads to the conclusion that the rate-limiting step in ammonia synthesis over iron catalysts is the chemisorption of nitrogen. The question as to whether the nitrogen species involved is molecular or atomic is still not conclusively resolved …”.

The variation of the relative coverage N atoms (y) chemisorbed at 693 K at various Fe single-crystal surfaces with exposure to gaseous N2 (1 L=1.33x106 mbars is about the exposure that would suffice to form a complete monolayer if each incident moleculeis adsorbed). Kinetic oscillations in the catalytic oxidation CO The mechanism of CO oxidation.

Energy diagram for the catalytic oxidation of CO on Pt. Onset of temporal oscillations of the rate of CO2 formation -5 on a Pt(110) surface. T=470 K; pCO=3š10 mbar.

3D plots (only CO-1x1 and hex). Cycle numbers: a=10, b=52, c=70, d=128, e=160, f=228. Structures of CO (a), O (b), and O+CO (c) chemisorbed on a Rh(111) surface. Distances are given in Å. Structures of the Pt(110) surface: a) the 1x2 structure of the clean surface; b) the 1x1 structure representing termination of the bulk structure. Target patterns in catalytic oxidation of CO on a Pt(110)surface as imaged by PEEM. PEEM image of the formation of spiral waves in catalytic CO -4 oxidation on a Pt(110) surface. T=448 K; pO2=4x10 mbar; -5 pCO=4.3x10 mbar. The diameter of the picture is 500 μm. PEEM image from a Pt(110) surface in the state of chemical turbulence. -4 -4 T=548 K; pO2=4x10 mbar; pCO=1.2x10 mbar. The image size is 360x360 μm.

Conversion of oxygen islands. Subsequent PEEM images separated by equal time intervals Δ t are shown from top left to bottom right. The parameters are: (a)T= 400 K, Δt=120 s, image size 150 μm x 420 μm; (b)T=453 K, Δ t=60s, 220 μm x 420 μm; and (c) T=503 K, Δ t=30s, 165 μm x 420 μm. -4 A typical two-into-one wave collision at T=533 K, pCO=1.84x10 mbar, -4 and pO2=4x10 mbar. Subsequent PEEM images of size 170 μm x 130 μm are separated by equal time intervals Δt=1.92 s. A wave collision of the two-into-two type. The reaction parameters are -5 -4 T=503 K, pCO=9x10 mbar, and pO2=4x10 mbar. Subsequent PEEM images of size 180 μm x 130 μm are separated by equal intervals Δt=0.8 s.

∂u ∂2u ∂2u = k p ()1−u3 −k u −k uv+ D + D ∂t 1 CO 2 3 x ∂x2 y ∂y2 ∂v = k p [s w + s ()()1− w ] 1− u − v 2 ∂t 4 O2 O,1×1 O,1×2 () − k3uv − k6uv 1− s + k7 s(1− v) ∂w = k ( f (u, s) − w ∂t 5 ∂s = k vw()1− s − k s 1− ()v ∂t 6 7 δ exp[(u − u ) /δ ]+ exp[(s − s )δ ] f ()u, s = 0 u 0 y 1+ exp[((u − u0 ) / u ]+ exp[(s − s0 )δ y ] u – the local CO coverage; v – the surface oxygen coverage w – the local structural state of the surface: w=0 for 1x2, w=1 for 1x1 s - the local concentration of subsurface oxygen

i= -0.3u -v+ 3s Spatial profiles of PEEM intensity (a) during a two-into-one collision. Spatial profiles of PEEM intensity during a two-into-two collision. Computer simulation of the evolution of spiral waves in catalytic CO oxidation. Computer simulation of the break up of spiral waves to chemical turbulence. Simulation of a complex reflective collision in two dimensions. Subsequent computed PEEM images of size 100 μm x 200 μ m are separated by equal intervals Δ t = 4 s. S.C. Badescu, K. Jacobi, Y. Wang, K. Bedürftig, G. Ertl, P. Salo, T. Ala-Nissila and S.C. Ying: Vibrational states of a H monolayer on the Pt(111) surface. Phys. Rev. B 68, 205401-1-6 (2003).

I.Rabin, W. Schulze and G. Ertl: Mass spectra from Mg clusters in Ar shells. Chem. Phys. Lett. 379, 314-318 (2003).

T.Lei, J. Lee, M.S. Zei and G. Ertl: Surface properties of Ru(0001) electrodes interacting with formic acid. J. Electroanal. Chem. 554-555, 41-48 (2003).

D.N. Denzler, C. Frischkorn, M. Wolf, and G. Ertl: Surface Femtochemistry: Associative Desorption of Hydrogen from Ru(001) Induced by Electronic Excitations. J. Phys. Chem. B 108, 14503-14510 (2004). Foundation of the Institute

The Kaiser-Wilhelm Institutes for Chemistry (left) and for Physical Chemistry and Electrochemistry (right) --(1913). Installing the Institute for Physical Chemistry and Electrochemistry was made possible by a generous endowment by Leopold Koppel, a wealthy industrialist and banker. The endowment act was signed on October 28, 1911 in Berlin by the "Koppel Foundation for the Promotion of Scientific Relations Abroad" and by a representative of the Prussian Minister for Scientific and Educational Affairs. Kaiser Wilhelm II and Adolf von Harnack, followed by and Fritz Haber walking to the opening ceremony of the first two KWG institutes (October 1912). Fritz Haber was appointed director of the institute following the recommendation of the famous Swedish physical .

In 1913/14 the staff amounted to 5 scientists, 10 assistants, and 13 volunteers and students, with a personnel and operating budget of 70,000 Mark excluding the salary of the director. The First World War

Fritz Haber himself offered his services to the War Ministry to carry out research on the supply of raw materials. Inspired by patriotism, Haber made also plans for the usage of chemical weapons. He directed their first large-scale application in 1915. As the war continued the institute developed into a central research laboratory for the development of chemical weapons as well as for methods of protecting against chemical weapons. During this time, many scientists (Ferdinand Flury, , Herbert Freundlich, , Reginald Oliver Herzog, Erich Regener, and Heinrich Wieland) were recruited to work on warfare-related projects, forming a staff of over 1,000 people. At the end of the war Fritz Haber's military activities led the allies to label him as a "war criminal", because using chemical weapons was forbidden since the "The Hague Agreement about the Regulation of Land War " of 1899 and 1907. However, this did not prevent the Swedish Academy of Sciences from awarding him the 1918 Nobel Prize for Chemistry. The years 1919-1933 -"Golden Years„

Hans Beutler, Karl Friedrich Bonhoeffer, Ludwig Ebert, , Ladislaus Farkas, Karl-Hermann Geib, Paul Goldfinger, Walter Grotrian, Paul Harteck, Hartmut Kallmann, Hans Kautsky, Paul Knipping, Hans Kopfermann, Fritz London, Eugen Rabinowitch, Karl Söllner, Hertha Sponer, Eugen Wigner, Joseph Weiss, Karl Weissenberg, Setsuru Tamaru and Hans Zocher. Work performed at the Institute represented milestones in science of the time. Here we mention only a few examples: •the interpretation of predissociation spectra by Bonhoeffer and Farkas (1928), •the demonstration of negative dispersion in a neon gas discharge tube as evidence of stimulated light emission, Kopfermann and Ladenburg (1928), which forms a prerequisite for the development of laser emission detected much later, •the purification of parahydrogen at low temperatures by Bonhoeffer and Harteck (1929), •the quantum-mechanical description of energy transfer between atomic systems by Kallmann and London (1929), •the explanation of the hyperfine structure of atomic spectra by Kopfermann (1931), •the sketch of the basic principles of a heavy ion linear accelerator by Kallmann (1933). National Socialism and the Second World War

Fritz Haber submitted his resignation as director of the institute on the 30th April 1933 and requested permission to retire on the 1st October 1933. He emigrated to England in the autumn of 1933 and he died in Basel on January 29, 1934. After Haber's resignation Otto Hahn took over as director of the institute following Haber's request as well as a recommendation by Max Planck. However, in October 1933 the Prussian government appointed Gerhart Jander, formerly professor of inorganic chemistry at Göttingen, as temporary director. Jander notified all scientists in question who had not yet voluntarily resigned and the existing lines of research at the institute were abruptly terminated. While the 1933 yearbook of the institute still included 68 papers by 45 authors published in 1932, the year 1934 produced only 8 papers by 6 authors, all in the field of inorganic chemical analysis. Peter Adolf Thiessen was nominated as director. He had already been installed by Jander as a Department Head at the institute. Thiessen set up additional departments and gradually reinstated scientific work covering a broad spectrum of chemistry. After the outbreak of the Second World War the institute was, for the second time, almost entirely directed to projects of military interest. Only few basic science investigations could by carried on. Here theoretical studies on Ray interference and electron diffraction by Kurt Molière deserve special mention, as do the investigations by Otto Kratky who developed X-ray small angle scattering. In 1944 Iwan N. Stranski, having worked as Professor of Physical Chemistry in Sofia until 1941 and later at the Technical University in Breslau, was appointed Scientific Fellow of the institute and performed pioneering studies on crystal growth and phase formation. The early years after the Second World War

In the early post-war years the institute was supported by the Berlin City Council. Robert Havemann, who had held a scholarship at the institute in 1932 and 1933, was appointed head of the institute by the City Council. In January 1948 he was dismissed as director of the institute. In the spring of 1948 a department was set up for Karl Friedrich Bonhoeffer who was at the same time director of the Institute for Physical Chemistry at the Humboldt-University of East-Berlin. In December 1948 he was appointed director of the institute, but in 1949 he accepted the invitation of the newly founded Max-Planck Society to become director of the new Max-Planck Institute for Physical Chemistry in Göttingen. Nevertheless, he continued to lead the institute until March 31, 1951. Bonhoeffer brought Ernst Ruska, the inventor of the electron microscope, to the institute as leader of a Department of Electron Microscopy. Ruska was to set up this new department (while still retaining his employment at ) in order to encourage fundamental research and further development in the field of electron microscopy. Incorporation into the Max-Planck Society

In 1951, at the age of 71, Max von Laue became chief director of the institute. This started a new period of consolidation in which Max von Laue applied all his influence and his great scientific reputation to the task of rebuilding the institute. The official incorporation into the Max-Planck Society took place in 1953 when the institute was renamed "Fritz-Haber-Institut". At this time Kurt Molière's group was expanded and converted into a department where the structure of surfaces was studied with electron diffraction and by theoretical analysis. Kurt Molière was appointed Scientific Fellow of the institute in 1960. Development into a surface and interface science research center

In October 1958 Rudolf Brill was appointed director of the institute and in March 1959 he succeeded Max von Laue as chief institute director. Amongst other subjects, he was engaged in studies of catalytic properties for heterogeneous reactions which were investigated using X-ray diffraction methods and kinetic measurements. He took a particular interest in catalysts used in the ammonia synthesis as well as in hydrogenation and oxidation catalysts. In 1969 Heinz Gerischer was appointed to succeed Brill as chief institute director. He headed the Department of Physical Chemistry and initiated research in the areas of electrochemistry, photo-electrochemistry, and fast reactions. His department focused also on studies of solid surfaces under ultra-high vacuum conditions and their interaction with gases. Further, exploiting the low temperature technology already developed by von Laue at the institute, a research program on matrix isolation spectroscopy was started. Here the transition between atomic and metallic properties in clusters was investigated. When Gerischer was appointed, Jochen H. Block became Scientific Fellow of the institute. He had been hired by Brill in 1966 and had built up his own department in which kinetic processes on metal surfaces were studied using field electron and field ion microscopies. In 1986 Gerhard Ertl succeeded Gerischer as director of the Department of Physical Chemistry and was appointed Scientific Fellow at the institute. His research interests focus on structure and chemical reactions at solid surfaces.