CATALYSIS AN OVERVIEW NATIONAL CENTRE FOR CATALYSIS

CATALYSIS – AN OVERVIEW NATIONAL CENTRE FOR CATALYSIS RESEARCH INDIAN INSTITUTE OF TECHNOLOGY MADRAS CHENNAI 600 036 DATED 30 TH NOVEMBER 2014

MOTIVATION FOR THIS PRESENTATION • ONLY ONE GENERAL PRESENTATION- ALL OTHERS WILL BE DEALING WITH SPECIFIC ASPECTS OF THIS FIELD. • TO OUTLINE THE EVOLUTION AND CONCEPTUAL FRAMEWORK OF THIS FIELD • TO PROMOTE MOTIVATION AND TO APPRECIATE THE EFFORTS IN THIS FIELD • THE METHODOLOGY FOR CONCEPTS

OUTLINE OF THE PRESENTATION • • INTRODUCTION BRIEF HISTORICAL OUTLINE CONCEPTUAL EVOLUTION Questions, Enigmas, Illusions, challenges, realities, and emergent strategies of design of catalysts Descriptors and data mining – how it will be useful Theory - has it relevance in this field? Perception and Assimilation? Questions – This should evolve as the habit!

QUESTIONS? What areas of fundamental research are most helpful to support commercial catalyst/catalysis activity in industry? Should the dispersal of federal research grants to academic researchers be based on demonstrated excellence in science or focused to support the national laboratories? What type of linkage with academia/national laboratories is most useful to, and supportable by, industry? What elements in science or technology provided the edge to your commercial business in catalyst/catalytic processes? What novel catalytic processes do you expect to be developed in the next 10 to 15 years? What will be the nature of the exploratory and basic research that leads to these developments? Is academic and industrial catalytic research well positioned to play a leadership role in creating this new technology and, if not, what needs to be done?

Iidentify areas of catalyst science and technology is (1)behind competitors, (2) even with competitors, and (3) ahead of competitors. Identify problems that have longterm payoff. What areas are ''mature'' or "dead"? Has too much emphasis been placed on one area in the past? What would be the ideal mix of industrial and academic research in catalysis? What are the major unsolved problems in catalysis, and what would the solution to these problems provide in economic and technical terms? Are there new areas where catalysis could be used?

Some benchmark discoveries in the science and technology of catalysis. 100 years ago: Paul Sabatier (Nobel Prize 1912) at the University of Toulouse started work on his method of hydrogenating organic molecules in the presence of metallic powders. 70 years ago: Irving Langmuir (Nobel Prize 1932) at General Electric laid down the scientific foundations for the oxidation of carbon monoxide on palladium. 50 years ago: Vladimir Ipatieff and Herman Pines at UOP developed a process to make highoctane gasoline that was shipped just in time to secure the victory of the Royal Air Force in the Battle of Britain. 30 years ago: Karl Ziegler and Giulio Natta (Nobel Prize 1963) invented processes to make new plastic and fiber materials. 17 years ago: W. S. Knowles at Monsanto Company obtained a patent for a better way to make the drug L-Dopa to treat Parkinson's disease. 16 years ago: General Motors Corporation and Ford Motor Company introduced new devices in cars to clean automotive exhaust. These devices found worldwide acceptance. 10 years ago: Tennessee Eastman Corporation started a new process for converting coal into chemicals used for the production of photographic film. Yesterday: Procter and Gamble Company manufactured a new environmentally safe bleach mixed with laundry soap. Today: Thomas Cech (Nobel Prize 1989) at the University of Colorado received U. S. patent 4, 987, 071 to make ribozymes, a genetic material that might, one day, be used to deactivate deadly virus

The Central point in Catalysis Research is the identification and optimization of active sites- variety of active sites inherent in the solid surface itself Sites that are generated at the call of the molecules and sites which are not active by themselves but becomes active as a result of species generation at the adjacent sites so called spill over effect and thus it is a dynamic concept today from the 3/17/2018 NCCR 8 original static concept

The Concept of Active Centres in Material Science How are they relevant? What are the factors that contribute to material science? Why the dynamics of processes in Material science different from conventional dynamics? How the processes are initiated in material science and how are they different from conventional chemical processes? And many more

Why revisit this Concept Now? 1925 first H S Taylor brought this concept to catalysis at that time it was only at molecular level and on reactivity and not selectivity

Materials Science • Ages have been only based on materials- stone age, iron age, bronze age • Every decade has been throwing up at least one material • Advances in sciences have largely dependent on materials • Comforts arising out of scientific discoveries dependent on materials.

Surface to Volume Ratio • Surface to volume ratio is important in devices • Many such systems have been performing with greater efficiency • These systems are brain, leaf, chips and so on • Why are they so special? • What make them so special?

Why surfaces are important? • Surface free energy decides which species is responsible • Opposing properties can be induced like hydrophilic or hydrophobic character • Area modulation, functional modulation, and a variety of other modifications are possible • Sensing behaviour increases and hence response time is decreased

Changes • Materials science departments have been opened all over the institutions. • Metallurgical departments have taken new avatar in the form of materials department • Material science is evolving a new branch of science • Materials science research is focussing on devices • Synthesis, fabrication and design appear to merge • Scales appear to shrink • Morphologies appear to be no barrier • Fabrication has a new meaning now

Catalysis 1949 to 1999

1 st DECADE: 1949 - 1958 • Late 1940 s- Robert M. Milton and Donald W. Breck, Union Carbide, develop • Early 1950 s: commercial synthesis for zeolites - A, X, and Y types. • Late 1940 s- Eugene Houdry develops monolithic platinum catalyst system for • Early 1950 s: Treating exhaust gases from internal combustion engines, founds — and begins commercial operations at Yardley, Pennsylvania. Houdry is later inducted into the Inventor's Hall of Fame. • June 11, 1949: First meeting of organization that became the Catalysis Club of Philadelphia was held at the University of Pennsylvania. Paper were presented by R. C. Hansford (Mobil), A. G. Oblad (Houdry), A. V. Grosse (Temple U), T. I. Taylor (Columbia U. ) and K. A. Krieger (U. Pennsylvania). A. Farkas, organizer of this symposium, was selected chairman of a committee to form a permanent organization.

1 st DECADE: 1949 - 1958 • December 1949: Prof. Paul Emmett presented a lecture at Temple University and afterwards the Catalysis Club of Philadelphia was officially formed, electing A. Farkas chairman and A. Oblad as Secretary-Treasurer. Almost one hundred signed up as members. • 1949: First commercial operation of UOP's Platforming Process for naphtha reforming, Old Dutch Refining, Muskegon, Michigan; patents for Pt-Cl-Al 2 O 3 catalysts to Vladimir Haensel. • 1949: P. W. Selwood published his first paper on nuclear induction and begins a series of classic publications on the application of magnetic techniques in catalysis. The results are summarized in his book [P. W. Selwood, "Adsorption and Collective Paramagnetism, " Academic Press, 1962. ] • March 2, 1950: The Bylaws of the Catalysis Club of Philadelphia, as written by Grace Kennedy (wife of Robert Kennedy, prominent catalysisscientist at Sun Oil), were adopted and still serve as the model for later formed clubs/societies.

1 st DECADE: 1949 - 1958 • 1950: MILESTONE MEETING: The Discussions of the Faraday Society, Heterogeneous Catalysis, No. 8, 1950. Topics included: O. Beeck, Relates % dcharacter of metal and catalytic activity for ethylene hydrogenation. • D. D. Eley, Calculates the heat of adsorption of hydrogen on metals. • G. M. Schwab, Alloy catalysts for dehydrogenation. • D. D. Dowden and P. W. Reynolds, Electronic effects in catalysis by metal alloys. • P. W. Selwood and L. Lyon, Magnetic susceptibility and catalyst structure. • M. W. Tamele, Surface chemistry and catalytic activity of silica-alumina catalysts. • John Turkevich, H. H. Hubbell and James Hillier, Electron microscopy and small angle X-ray scattering. • 1950: Linear relationship between quinoline chemisorption and catalytic activity for gasoil cracking - G. A. Mills, E. R. Boedeker and A. G. Oblad, JACS, 72, 1554 (1950). • 1950: Hydroformylation catalytic species identified as HCo(CO)4 - I. Wender, M. Orchin and H. H. Storch, JACS, 72, 4842 (1950). • 1951: A. Wheeler defines role of diffusion in determining reaction rates and catalytic selectivity - Advan. Catal. , 3, 250 -326 (1951).

1 st DECADE: 1949 - 1958 • 1951: Paul Emmett utilizes 14 C radioisotope in Fischer-Tropsch mechanism studies - New York Times reports that "Gulf Oil scientist makes radioactive gasoline. " • 1953: Naphtha reforming involves dual functional catalysts - mechanism for reforming with these catalysts - G. A. Mills, H. Heinemann, T. H. Milliken and A. G. Oblad, Ind. Eng. Chem, 45, 124 (1953). • 1953: Karl Ziegler discovers a catalyst system for polymerizing ethylene at low temperature and pressure to produce linear, crystalline polyethylene- Nobel Prize awarded to Ziegler in 1963. • 1954: Guelio Natta invents stereospecific polymerization of propylene to produce crystalline polypropylene- Nobel Prize awarded to Natta in 1963. • 1954: "Beginning" of catalyst characterizations using instruments with i. r. spectra for CO adsorption on copper (R. P. Eischens, W. A. Pliskin and S. A. Francis, J. Chem. Phys, 22, 1786 (1954)). This pioneering work soon included approaches to characterize active sites for adsorption on metal, metal oxide and acidic sites as well as distinguishing Brønsted and Lewis acid sites. • 1954: John P. Hogan and R. L. Banks, Phillips Petroleum, discovers chromia catalyst for polyethylene production.

1 st DECADE: 1949 - 1958 • 1955: Sasol begins commercial operation of Fischer-Tropsch circulating fluid bed reactors. • 1956: Phillips Process - high pressure (500 psi) in hot solvent with supported chromia catalyst did not, on the surface, look attractive compared to Ziegler-Natta; however, engineering advances, cheap and high activity catalyst, and ever increasing scale made the Phillips Process the world's leading source of polyethylene. • 1956: First International Congress on Catalysis held in Philadelphia - more than 600 attendees. This has become an independent organization and the 11 th ICC will be held during 2000 in Granada, Spain. • 1957: On June 18, Hercules opens the first Zigler catalyst based plant in the U. S. • 1958: Merox Mercaptan Oxidation Process _ UOP • 1953 - 1959: Patents granted in these years led to the commercial production of three significant linear polyolefins: high-density polyethylene (1955 - 56 by Hoechst, W. R. Grace, Hercules and Phillips), polypropylene (1957 -8 by Hercules, Montecantini and Hoechst) and stereo -specific rubbers (1958 -9 by Goodrich-Gulf, Phillips and Shell).

2 nd DECADE: 1959 - 1968 • 1960's: Major advances in heterogeneous photocatalysis • 1960's: Catalytic advances to allow low-temperature water-gas shift • 1960 s: Scientific Design developed processes to make chlorinated solvents and maleic anhydride. A major breakthrough was the development of a catalyst to oxidize p-xylene into purified terphthalic acid. • 1960 s: Development of the concepts of demanding and facile metal catalyzed reactions - introduced by Boudart and coworkers. M. Boudart, Adv. Catal. , 20, 153 (1969) • 1959: Observation of olefin metathesis at Phillips Petroleum - R. L. Banks and G. C. Bailey, Ind. Eng. Chem. Prod. Res. Dev. , 3, 170 (1964); R. L. Banks, "Discovery and Development of Olefin Disproportionation (Metathesis)" in "Heterogeneous Catalysis: Selected American Histories, " (B. H. Davis and W. P. Hettinger, Jr. , Eds. ), ACS Symp. Series, 222, 403 (1983)). • 1959: Dabco (trimethylene diamine) was introduced by Houdry Corp. as a catalyst for the production of urethane foams from isocyanates and alcohols.

2 nd DECADE: 1959 - 1968 • 1959: Nalco introduces 1/16", and later 1/32, " extrudate Co. Mo- alumina hydrotreating catalysts and introduced in Exxon Baytown refinery. • 1960: Ethylene to acetaldehyde - Wacker Chemistry • 1960: UOP introduces Hydrar Process for converting benzene to cyclohexene. • 1960: Completion of Sohio's acrylonitrile plant at Lima, Ohio, based upon catalyst discovered by J. D. Idol. • 1961: Paring reaction in hydrocracking, R. F. Sullivan, C. J. Egan, G. E. Langlois and R. P. Sieg, JACS, 83, 1156 (1961). • 1962: Steam reforming with Ni. K 2 Al 2 O 3 • 1962: Observation of reversible binding of H 2 and C 2 H 4 by Vaska's Complex, Ir. Cl(CO)(PPh 3)2, L. Vaska and J. W. Di. Luzio, JACS, 84, 679 (1962). • 1962: Journal of Catalysis, the first scientific journal devoted solely to catalysis, begins publication with J. H. de Boer and P. W. Selwood as editors.

2 nd DECADE: 1959 - 1968 • 1962: Description of "Vaska's Complex, " the first to show reversible bonding of hydrogen and ethene within the coordination sphere (L. Vaska and J. W. D. Luzio, JACS, 84, 679 (1962)). • 1963: Sachtler proves, using 14 C-labeled propene, that a p-allyl complex is formed during propene oxidation (W. M. H. Sachtler, Rec. Trav. Chim. , 82, 243 (1963)). • 1963: Ammoxidation of propene to acrylonitrile. • 1963: Theoretical model for describing elementary redox reactions for electrodes (R. A. Marcus, J. Phys. Chem. , 43, 679 (1963)). • 1964: Introduction of rare earth metal stabilized X-zeolite for catalytic cracking by Mobil Oil - C. J. Plank, E. J. Rosinski and W. P. Hawthoren, 3, 165, (1964). Plank and Rosinski in the Inventors Hall of Fame. • 1964: Olah announces "Magic Acid, " a mixture of HF and Sb. F 5 reacts with hydrocarbons to produce stable carbocations that are observable using NMR. G. Olah awarded the 1994 Nobel Prize in Chemistry.

2 nd DECADE: 1959 - 1968 • • • • 1964: Olefin metathesis announced [R. L. Banks and G. C. Bailey, Ind. Eng. Chem, Prod Res. Dev. , 3 170 (1964)] commercialized in 1966. 1964: Mechanism for hydrocracking - H. L. Coonradt and W. E. Garwood, Ind. Eng. Chem. , Process Design Dev. , 3, 38 (1964). 1964: K. Tamaru summarizes transient catalytic studies emphasizing IR techniques (Adv. Catal. , 15, 65 (1964)). 1964: Spillover of Hydrogen from Pt/Al 2 O 3 to WO 3 (S. Khoobiar, J. Phys. Chem. , 68, 411 (1964)). 1964: Blyholder (J. Phys. Chem. , 68, 2772 (1964)) suggested that CO adsorption on transition metals can be described by a molecular orbital picture of two contributions to bonding, partial donation of CO-5 s charge to metal ds orbitals and back donation from metal dp to CO 2 p* antibonding orbitals. 1964: Startup by Monsanto of the world's first biodegradable detergents plant based upon C 10 -C 14 linear olefins obtained by selective catalytic dehydrogenation of n-paraffins. 1965: Wilkinson's homogeneous hydrogenation catalyst, J. F. Young, J. A. Osborn, F. H. Jardine and G. Wilkinson, Chem. Commun. , (1965) 131. G. Wilkinson is the 1973 Nobel Laureate in Chemistry. 1966: ICI developed a moderate-pressure, low-temperature methanol synthesis process employing a Cu. Zn. O/Al 2 O 3 catalyst in a gas-recycle reactor. 1966: Introduction of concept of hard and soft acids and bases to catalysis (R. G. Pearson, Science, 151, 172 (1966)). 1966: Development of a method to calculate the coordination numbers of surface atoms in the stable forms of small metal particles (R. van Hardeveld and A. van Montfoort, Surface Sci. , 4, 396 (1966)). 1967: Introduction of first bimetallic naphtha reforming catalyst - Pt-Re-Al 2 O 3 - need for presulfidation of a naphtha reforming catalyst. 1967: Catalysis Reviews begins publication with H. Heinemann as editor. 1967: Atlantic Richfield and Halcon (formerly Scientific Design) formed a joint venture, Oxirane, to produce styrene, propylene oxide and tert-butyl alcohol. 1967: Summaries of Linear Free Energy Relationships (LFER) in Heterogeneous Catalysis (M. Kraus, Adv. Catal. , 17, 75 (1967); I. Mochida and Y. Yoneda, J. Catal. , 7, 386 (1967)). 1968: Shape selective catalysis - Selectoforming with erionite

3 rd DECADE: 1969 - 1979 • 1970's: Rh-catalyzed hydroformylation of propene. • 1970's: Improved selectivity for oxidation of ethene to ethylene oxide using Cs (or Cl) promoted Ag catalysts. • 1970's: Introduction of use of controlled atmospheric transmission electron microscopy for catalyst characterization and kinetics of catalysis. • 1972: Extensive studies of metal alloy catalysts by Sinfelt and coworkers results in demonstration of different activity patterns as alloy composition changes for the hydrogenolysis of ethane to methane and dehydrogenation of cyclohexane to benzene (J. H. Sinfelt, J. L. Carter and D. J. C. Yates, J. Catal. , 24, 283 (1972)). • 1974: UOP Purzaust Auto Exhaust Treatment system accepted by Chrysler and is installed on 1975 models. • 1974: F. Sherwood Roland M. Molina discover chlorine-catalyzed ozone depletion in the atmosphere. • 1975: B. Delmon organizes the first meeting for the Scientific Basis for the Preparation of Heterogneous Catalysts. • 1975: State of dispersion of small Pt and Pd metal particles in zeolites (P. Galleyot et. al. , J. Catal. , 39, 334 (1975)). • 1975: Demonstration that poisons of metallic catalysts are selective, decreasing rates of structure-sensitive and structure-insensitive reactions differently (R. Maurel, G. Leclercq and J. Barbier, J. Catal. , 37, 324 (1975)). • 1976: Mobil Oil management announces the discovery

3 rd DECADE: 1969 - 1979 • 1976: Mobil Oil management announces the discovery of methanol-to-gasoline conversion using their ZSM-5 zeolite catalyst (Chemtech, 6, 86 -9 (1976)). • 1978: Discovery of the strong metal support interaction (SMSI) and its role in altering the adsorptive properties of the metal function. (S. J. Tauster, S. C. Fung and R. L. Garten, JACS, 100, 170 (1978)). • 1979: Tennessee Eastman selects rhodium as catalyst for producing acetic anhydride from coal.

• • • 4 th DECADE: 1979 - 1988 1980's: Introduction of SCR (Selective Catalytic Reduction) for NOx control on stationary power generators. 1980's: New catalytic technology commercialized in the U. S. during the 1980's (J. Armor, Appl. Catal. , 78, 141 (1991)). 1980's: Union Carbide and Shell develop the UNIPOL process for linear low-density polyethylene, which allows precise control over the product's material properties. The process was extended to polypropylene in 1985. 1980's: Demonstration that strongly electronegative elements relative to nickel modify chemisorptive behavior far more strongly than a simple site- blocking mechanism would allow, supporting an electronic effect (D. W. Goodman, "Chem. Phys. Solid Surf, " Springer-Verlag, 1986, pp. 169 -195. 1980's: Experimental evidence demonstrating the restructuring of surfaces during catalytic reactions - e. g. , the conversion of ethylene to ethylidyne with expansion of the metal atoms around the carbon atom (R. J. Koestner, M. A. Van Hove and G. A. Somorjai, Surf. Sci. , 121, 321 (1982) and showing the parallel restructuring of Pt and oscillation in CO oxidation (G. Ertl, Ber. Buns. Phys. Chem. , 90, 284 (1986)). 1980: Very rapid ethene polymerization by homogeneous catalyst (CP 2 Zr (CH 3)2 activated with cocatalyst aluminoxane) (H Sinn et. al. , Angew. Chem. , 92, 396 (1980)). 1981: Applied Catalysis begins publication with B. Delmon as Editor-in-Chief. 1981: Adsorbate induced restructuring of surface (M. A. van Hore et. al. , Surf. Sci. , 103, 190, 218 (1981)) 1981: Introduction of constraint index as a diagnostic test for shape selectivity using cracking rate constants for n-hexane and 3 -methylpentane (V. J. Frilette, W. O. Haag and R. M. Lago, J. Catal. , 67, 218 (1981)).

4 th DECADE: 1979 - 1988 • 1982: Definition of Energy Profile for Ammonia Synthesis (G. Ertl in "Solid State and Material Sci. ", CRC Press, 1982, 349). • 1982: The first of a series of silicaaluminophosphate molecular sieves prepared by Union Carbide (now part of UOP) • 1982: The concept of transition state selectivity for zeolite catalysis introduced (W. O. Haag, R. M. Lago and P. B. Weisz, J. Chem. Soc. , Farad. Disc, 72, 317 (1982)). • 1983: Ashland Petroleum introduces RCC (Reduced Crude Cracking) with 40, 000 blb/day plant. • 1983: Enichen scientists report the use of titanium silicalite (TS-1) as a catalyst for selective oxidations with aqueous hydrogen peroxide, including olefin epoxidation (M. Taramasso, G. Pereyo and B. Natari, U. S. 4, 410, 501).

5 th DECADE: 1989 - 1999 • 1990's: Fischer-Tropsch as a source of alpha-olefins. • 1990's: Combinatorial approaches to catalyst screening and new catalyst discovery (e. g. , K. D. Shimizu et al. , Chem. Eur. J. , 4, 1885 (1998)). • 1990's: Selective oxidation of benzene to phenol using (Fe) ZSM-5 catalysts. • 1992: Commercial use of non-iron catalyst for ammonia synthesis. • 1992: Synthesis of MCM-41, the first uniformly structured mesoporous aluminosilicate, announced by Mobil Oil (J. S. Beck, et al. , JACS, 114, 10834 (1992). • 1994: Topics in Catalysis begins publication with Gabor Somorjai and Sir John Thomas as Co-Editors. • 1995: Introduction of oxone catalytic converter for airplane air purification. • 1996: Catalytic converter selected by Fellows of the Society of Automotive Engineers as one of the top ten achievements in the auto industry during the past 100 years. • 1996: Global Overview of Catalysis - A Series of Reports for many countries begins to appear in Applied Catalysis A: General. • 1996: Magna. Cat Process for separation and removing

5 th DECADE: 1989 - 1999 • 1996: Magna. Cat Process for separation and removing aged FCC catalyst operates at a commercial scale. • 1996: Members of original acrylonitrile research team (l to r; J. L. Callahan, G. C. Cross, E. C. Milberger, E. C. Hughes and J. D. Idol (F. Veatch, deceased)) at dedication of plant site as National Historical Landmark by the ACS. • 1999: UOP Cyclar Process for the production of aromatics for LPG. • All these are reproduced from the site http: //crtc. caer. uky. edu/text. htm

Alex Mills: the catalyst chemist

Eric Derouane- a visonary with high intellectual mobility (1944 -2008 • ) Eric Derouane had an unusual working efficiency. He had a high intellectual mobility and was always attracted by new materials and new concepts. Among them, one can mention ZSM-5/MFI new zeolite in the early 70 s, leading to a 30 year collaboration with J. C. Védrine, cuprate-type superconductors, confinement effect and molecular traffic control in zeolitic materials. He also studied reaction mechanisms using isotopic labelling and in-situ MAS-NMR in the 80 s, combinatorial catalysis and high throughput technology in the late 90 s. During his 20 years of dedicated service to the University of Namur, Eric Derouane developed new concepts, which had an important impact on the catalysis and zeolite communities. In 1986, he was elected Head of the Chemistry Department. He then embarked upon an impressive re-structuring programme to improve its efficiency. The model, which he initiated, is still in service today. His laboratory was recognized as an outstanding school of scientific research and education in catalysis. Very early, Eric Derouane realized the importance of interdisciplinarity, which lead him to play a key role in the creation of the Institute for Studies in At Liverpool, the aim of the LCIC was to promote creative fundamental catalytic science and often to take-up industrial challenges. Eric Derouane defined innovation as “the creation of a new or better product or process, . In 1999, he co-founded with Prof. S. Roberts the spin-off Liverpool-based company “Stylacats”, of which he became director. He provided wise suggestions and ideas, which lead the company to pioneer new technologies, in particular catalysts for asymmetric hydrogenation, microwave -induced reactions and enzyme mimetics. At the University of Faro, Eric Derouane developed a research project, jointly with the Instituto Tecnico de Lisboa, on Friedel-Crafts reactions. He also collaborated closely on various research projects with Prof. F. Ramôa Ribeiro’s zeolite group of the Instituto Superior Tecnico of the University of Lisbon.

Eric Derouane- a visonary with high intellectual mobility (1944 • 2008 ) Eric Derouane co-authored over 400 scientific papers, 11 books and 61 patents. Eric Derouane also contributed to the development and strengthening of the european catalysis community. He created in 1975 the European Association in Catalysis (EUROCAT), a consortium of European laboratories under the auspices of the Council of Europe and promoted standardisation of characterisation of catalysts: Euro-Pt 1 to -Pt 4, Euro-Ni 1 & -Ni 2, Eurocat zeolite, Eurocat oxides, etc. This Eurocat group paved the way to the creation of the European Federation of Catalysis Societies (EFCATS) and of the François Gault lectureship. He was elected President of EFCATS in 1995 for two years. He became Editor-in-chief of J. Mol. Catal. in 1982 and was member of the Editorial Boards of several scientific journals and member of the scientific committees of many congresses and colloquia. He coorganized several congresses himself, in particular with F. Lemos and F. Ramôa Ribeiro in Portugal several NATO Advanced Studies Institutes on topics including “the conversion of light alkanes”, “combinatorial catalysis and high throughput catalyst design and testing”, “principles and methods for accelerated catalyst design and testing” and “sustainable strategies for the upgrading of natural gas”. Eric Derouane’s contributions to catalysis have been recognised by many awards and academic honors, including the Wauters Prize (1964), the Mund Prize (1967) of the “Société Royale de Chimie”, the Stas. Spring Prize (1971) and the Adolphe Wetrems Prize (1975) of the “Académie Royale de Belgique”, the Rosetta Briegel-Barton Lecturership at the University of Oklahoma (1973), the Prize of the “Cercle of Alumni de la Fondation Universitaire de Belgique” (1980), the Ciapetta Lectureship of the North American Catalysis Society (1981), the Catalysis Lectureship of the Société Chimique de France (1993) and the prestigious Francqui Prize, B (1994), the highest honor for all Sciences in Belgium. He was made “Officier de l’Ordre Léopold” in Belgium (1990), corresponding Member of the “Académie Royale des Sciences, des Lettres et des Beaux Arts de Belgique” (1991), member of the

Eugene Houdry: Catalytic Cracking of low-grade fuel into gasoline(18921962)

Eugene Houdry: Catalytic Cracking of low-grade fuel into gasoline (1892 -1962) • One of the first improvements in petrochemical production was the process developed by Eugene Houdry for "cracking" petroleum molecules into the shorter ones that constitute gasoline. (Earlier commercial processes for cracking petroleum relied instead on heat. ) Eugene Houdry (1892– 1962) obtained a degree in mechanical engineering in his native France before joining the family metalworking business in 1911. After he served in the tank corps in World War I—for which he received honors for extraordinary heroism in battle—he pursued his interest in automobiles (especially race cars) and their engines. On a trip to the United States he visited the Ford Motor Company factory and attended the Indianapolis 500 race. His interest soon narrowed to improved fuels. Because France produced little petroleum—and the world supply was thought to have nearly run out—Houdry, like many other chemists and engineers, searched for a method to make gasoline from France's plentiful lignite (brown coal). After testing hundreds of catalysts to effect the hoped-for molecular rearrangement, Houdry began working with silica-alumina and changed his feedstock from lignite to heavy liquid tars. By 1930 he had produced small samples of gasoline that showed promise as a motor fuel.

Eugene Houdry: Catalytic Cracking of low-grade fuel into gasoline(1892 -1962 • In the early 1930 s Houdry collaborated with two American oil companies, Socony Vacuum and Sun Oil, to build pilot plants. Oil companies that did not want to resort to the new additive tetraethyl lead were eagerly looking for other means to increase octane levels in gasoline. In 1937 Sun Oil opened a full-scale Houdry unit at its refinery in Marcus Hook, Pennsylvania, to produce high-octane Nu-Blue Sunoco gasoline. By 1942, 14 Houdry fixedbed catalytic units were bearing the unanticipated burden of producing high-octane aviation gasoline for the armed forces. (One limitation of the process was that it deposited coke on the catalyst, which required that the unit be shut down while the coke was burned off in a regeneration cycle. Warren K. Lewis and Edwin R. Gilliland of the Massachusetts Institute of Technology, who were hired as consultants to Standard Oil Company of New Jersey [now Exxon. Mobil], finally solved this problem with great ingenuity and effort. They developed the "moving bed" catalytic converter, in which the catalyst was itself circulated between two enormous vessels, the reactor and the regenerator. ) Houdry continued his work with catalysts and became particularly fascinated with the catalytic role of enzymes in the human body and the changes in enzyme-assisted processes caused by cancer. About 1950, when the results of early studies of smog in Los Angeles were published, Houdry became concerned about the role of automobile exhaust in air pollution and founded a special company, Oxy-Catalyst, to develop catalytic converters for gasoline engines—an idea ahead of its time. But until lead could be eliminated from gasoline (lead was introduced in the 1920 s to raise octane levels), it poisoned any catalyst.

Heinz Heinemann: One of the accomplished founders of the Catalysis Society

Heinz Heinemann: One of the accomplished founders of the Catalysis Society • During a 60 -year career in industry and academia, Heinz contributed to the invention and development of 14 commercial fossil fuel processes, received 75 patents and was the author of more than a hundred publications. Among his inventions was a process for converting methanol to gasoline. At his death, he was a distinguished scientist in the Washington office of LBNL. During the period 2001 to 2004, he served as a manager of the Washington Chemical Society (ACS) and as president of its Retired Chemists Group. After retirement from a career in industry, Heinz was a long-time lecturer in the College of Chemistry at the University of California, Berkeley, and a chemistry researcher at Lawrence Berkeley National Laboratory. Born in Berlin, Germany, he attended the University and Technische Hochschule in Berlin. When his doctoral dissertation was rejected because he was Jewish, he made his way to Basel, Switzerland, where he received his Ph. D in physical chemistry from the University of Basel, before coming to the United States in 1938. He became a U. S. citizen in 1944. He worked for several petroleum companies in Louisiana and Texas and won a postdoctoral fellowship at then-Carnegie Institute of Technology, now Carnegie-Mellon University. The fellowship was funded by the government of the Dominican Republic and involved research into ethanol, which was made from the Dominican Republic's primary cash crop, sugar cane.

Heinz Heinemann: One of the accomplished founders of the Catalysis Society • He published more than 150 papers and over 50 patents in catalysis and petroleum chemistry, mostly while working for Houdry Process Corp. , the MW Kellogg Co. as director of chemical and engineering research, and the Mobil Research and Development Co. as manager of catalysis research. During those years he actively participated in the research and development of 14 commercial processes, including the process for converting methanol to gasoline. After retiring from industry in 1978, he joined the Lawrence Berkeley National Laboratory as a researcher and became a lecturer in the Department of Chemical Engineering at UC Berkeley. His research involved coal gasification, catalytic coal liquefaction, hydrodenitrification, nitrogen oxide emission control and the development of a special catalyst that enables methane, the major component of natural gas, to be used to make petrochemicals. The research team he led invented and patented a process known as catalytic oxydehydrogenation. He was a co-founder of the Philadelphia Catalysis Club, the Catalysis Society of North America and the International Congress of Catalysis, serving as its president from 1956 to 1960. He was the founder of Catalysis Reviews, and worked as its editor for 20 years. He also was Consulting Editor for over 90 books in the Chemical Industries Series, published by Marcel Dekker, Inc. He received many honors, among them election to the National Academy of Engineering , the Houdry Award of the Catalysis Society, the Murphree Award of the American Chemical Society, the H. H. Lowry Award presented for research he pursued in his seventies, and a Distinguished Scientist/Engineer award of the U. S. Department of Energy. In addition, he was elected a member of the Spanish Council for Scientific Research for his support in founding its Institute of Catalysis and Petrochemistry

Herman Pines: he revolutionized the general understanding of catalysis

• Herman Pines: he revolutionized the general understanding of catalysis Herman Pines was born in Lodz, Poland, in 1902. After earning his degree at the École Supérieure de Chimie in Lyon, France, he came to the U. S. in 1928. He was the closest associate of Vladimir Nikolayevitch Ipatieff from the day they met in 1930, until Ipatieff's death in 1952. Ipatieff, who was 35 years older than Pines, then held two jobs: he was an employee of Universal Oil Products (UOP) in Des Plaines and a research professor at Northwestern University. As a consequence of the close interaction of these two devoted scientists, Herman Pines, an employee at UOP, became involved in Ipatieff's research at Northwestern. What started spontaneously and unofficially, was formalized in 1941, when Herman was appointed Research Assistant Professor at Northwestern, with the stipulation that he should spend his Wednesdays working here. This appointment coincided with the relocation of Ipatieff's lab from the basement of University Hall to the newly erected Technological Institute. One of the first actions of this new professor was to write, with Ipatieff, a memorandum to the Chemistry Department proposing the creation of a Catalysis Teaching and High Pressure Laboratory. This document was dated September 29, 1941, but it was not until 1947 that the Catalysis Lab officially opened in the Technological Institute. A special High Pressure Laboratory was built in 1952 and officially dedicated August 14, 1953, in the presence of the Presidents of Northwestern University and of UOP. Professor Sir Hugh Taylor of Princeton University gave a lecture on catalysis for the occasion. Shortly thereafter, a bronze plaque honoring Vladimir N. Ipatieff was mounted over the entrance of the High Pressure Lab; it is now located in the reception area of the Catalysis Center.

Herman Pines: revolutionized the general understanding of catalysis • Meanwhile, Herman Pines had been promoted, in 1951, to the rank of Associate Research Professor; after Ipatieff's death, in 1952, he became the first V. N. Ipatieff Professor of Organic Chemistry. On January 1, 1953, he left UOP and began officially as a full-time professor at Northwestern. Only a few of the outstanding scientific achievements of Herman Pines can be mentioned here; it is not an overstatement to say that his work revolutionized the general understanding of chemistry, in particular the chemistry of hydrocarbons interacting with strong acids. An unchallenged dogma of the chemistry of the 1930's was that paraffins would not react with anything at low temperature; even the name of this class of compounds, "parum affinis, " was based on this assumed lack of reactivity. It must have been quite a shock to the scientists of those days, when Pines and Ipatieff showed, in 1932, that in the presence of a strong acid the paraffin iso-butane would react, even at -35ºC, with olefins. This was the basis of the alkylation process, patented in 1938 and industrially developed soon after. Its most spectacular application is the synthesis of iso-octane from n-butene and isobutane. Iso-octane improves the quality of gasoline and airplane fuel; it played a decisive role in the victory of the Royal Air Force during the Battle of Britain in 1941. The catalysis of converting paraffins to isoparaffins is, of course, one of the cornerstone of the petroleum industry.

Herman Pines: he revolutionized the general understanding of catalysis • The alkylation process was not discovered by accident. It was the pinnacle of research that started with an observation that puzzled Herman Pines in 1930. At that time he was working in the analytical lab of UOP; his task was to vigorously shake petroleum fractions with concentrated sulfuric acid in a calibrated glass cylinder and to determine how much of the oil dissolved in the aqueous acid phase. It was known that only unsaturated hydrocarbons would be dissolved in the acid; this experiment of shaking the petroleum and reading the meniscus was the standard procedure to determine how many unsaturated products were present in a petroleum fraction. Herman observed, however, that after a few hours the phase boundary between oil and acid had shifted again: more oil was formed-oil that would not dissolve in the aqueous phase. Apparently paraffins had been formed from olefins; Herman concluded that this process required the simultaneous formation of a highly unsaturated coproduct which remained dissolved in the aqueous phase. They called this process "conjunct polymerization, " and years later analytical methods were found which permitted identification of this unsaturated coproduct as a mixture of substituted cyclopentadienes. The step which led from this early observation to the alkylation process was later described by Herman: "On a hunch we thought that paraffins might even react with olefins in the presence of acids; we therefore introduced a stream of ethylene and hydrogen chloride to a stirred mixture of the pentanes and Al. Cl 3. We observed that the ethylene was absorbed and that the hydrocarbons recovered from the reaction consisted of saturated hydrocarbons only, an indication that ethylene must have reacted with the pentanes. " On this basis, Herman Pines and Vladimir Ipatieff developed the new chemistry of acid catalyzed reactions; it

Herman Pines: revolutionized the general understanding of catalysis • formed the cornerstone of their scientific work and was brought to its present beauty by Herman in his years at Northwestern. Major discoveries led to new processes for the isomerization of paraffins and the alkylation of aromatic compounds, but also to base catalyzed organic reactions. Two hundred and fifty publications in the scientific literature, one hundred and forty-five U. S. patents and the book "The Chemistry of Catalytic Hydrocarbon Conversions" demonstrate the wealth of Herman's scientific legacy. The forty-one graduate students and thirty-three postdoctoral fellows who performed research in his lab helped carry his scientific message to the world. As U. S. editor of Advances in Catalysis, he keenly looked for and critically evaluated new concepts of catalysis, and assured that their originators described them carefully to the scientific community. In 1957 he was chairman of the Chicago Catalysis Society, in 1960 chairman of the Gordon Conference of Catalysis. He received three awards from the ACS, an honorary degree from the University of Lyon and invitations to lecture and advise in Israel, Brazil, Venezuela, Argentina, Poland, Czechoslovakia and Spain. The Catalysis Center remained his scientific home. He rarely missed a seminar and often asked critical questions. He could be quite sharp when speakers used catalysis only as a buzzword for the introduction of their lectures and spoke about work of rather questionable relevance to "real" catalysis. Although he could be critical, he was never insensitive; his gentle and friendly nature made it quite impossible for him to do any harm to anyone. While there is a unanimous consensus that he was one of the towering scientists of this century, he always remained very modest; when his trendsetting discoveries of the 1930's were mentioned, he always referred them to Ipatieff. He worked assiduously his entire life, bringing his last book to completion at the age of ninety. Future generations can learn from his example how revolutionary discoveries arise from sharp observations by an investigating mind. Herman Pines passed away on April 10, 1996.

John Sinfelt: Removal of lead from gasoline with bimetallics

John Sinfelt: Removal of lead from gasoline with bimetallics • Use of lead alkyls, primarily in the form of tetraethyllead, to enhance the octane number and performance of U. S. motor gasolines nearly doubled from 235, 000 tons in 1955 to 445, 000 in 1975. As the harmful health effects of tailpipe-exhausted lead compounds became increasingly apparent, legislative initiatives, beginning in 1975, mandated the complete removal of lead additives from U. S. motor fuels by year-end 1991. Dr. Sinfelt's research on alternate petroleum conversion chemistries allowed refiners to remove lead alkyls from gasoline years before the mandated deadline. Application of novel, highly active and selective bimetallic cluster catalyst systems he invented and championed made it possible to produce high-octane motor gasoline without the use of lead additives. Dr. Sinfelt’s distinctive research methodology emphasized entirely new concepts in the understanding and use of catalyst materials containing bimetallic clusters. Earlier work on metal alloys emphasized the relation between catalytic performance of a metal and its electron band structure. However, little attention had been paid to the possibility of catalytically influencing the selectivity of chemical transformations (product selectivities). One of Dr. Sinfelt’s most important discoveries, achieved through in-depth studies on bimetallic catalysts, concerns control of chemical reaction selectivity. He discovered that it is, in fact, possible to catalyze one type of chemical reaction in preference to other reactions that are themselves thermodynamically favorable. He clearly showed that bimetallic catalysts could be tailored to effectively reduce undesirable competing reactions, and thus control the kinetic specificity of surface reactions. This made possible the economical conversion of low octane number molecules to ones with high octane numbers. The public benefited greatly from the environmental improvements due to lead-free gasoline, and motorists did not pay a hugh price for it.

John Sinfelt: Removal of lead from gasoline with bimetallics • While Dr. Sinfelt’s research has made far-reaching contributions to our understanding of hydrocarbon conversion processes, the practical benefits of his research are equally profound. The application of bimetallic catalysts in petroleum refining was crucial to making high-octane “lead-free” motor fuels widely available. Today, bimetallic catalysts have replaced traditional catalysts in catalytic reforming (the major commercial process used in increasing the octane rating of motor fuels) allowing thereby elimination of lead-based, octane improving additives. Dr. Sinfelt is the inventor both of a Pt-Ir catalyst that has been widely used in catalytic reforming and of a staged reforming process that has also found wide application. The latter uses two different bimetallic catalysts in separate reactors to optimize performance. The classic work of Sinfelt on the kinetics of catalytic reforming reactions in the late 1950's and early 1960's provided the foundation for these important industrial advances. In addition to eliminating the hazard of lead in gasoline, Sinfelt’s work enabled the development and application of multi-metallic catalysts for the exhaust systems of automobiles to decrease the emission of pollutants such as carbon monoxide, unburned hydrocarbons and nitrogen oxides. The catalysts commonly used today contain a combination of metals; i. e. , they are bi-metallic or tri-metallic. These catalysts, like reforming catalysts, perform better when more than one metallic element is present. Current exhaust catalyst systems are based on Sinfelt’s ground breaking discoveries. Finally, since these catalysts are poisoned by lead, its removal from gasoline made the application of auto exhaust catalysts technically feasible.

John Sinfelt: Removal of lead from gasoline with bimetallics • The basic studies of Dr. Sinfelt on bimetallic catalysts generated much interest in the field and called attention to their importance for catalytic reforming and for the production of lead-free gasoline. The discovery was first reported in two U. S. Patents to Sinfelt et al. (3, 442, 973, which issued in 1969 and 3, 617, 518, which issued in 1971) and in two papers in the Journal of Catalysis 24, 283 (1972) and 29, 308 (1973). These early publications stimulated much interest in bimetallic catalysts as a major area of research that is still flourishing. For these contributions to the lead phase-down in the United States, Dr. Sinfelt was awarded the National Medal of Science by the President of the United States in 1979 and the prestigious Perkin Medal in 1984. His is among the most important contributions enabling the worldwide reduction of environmental lead and the elimination of the associated risks to human health. In a tribute to John Sinfelt in I&EC, 42 (2003) 1537, Professor Michel Boudart comments, "His impact has been uniquely important because John combined the inventiveness required for scientific discovery with the ability to engineer his work to many successful applications in industry. John succeeded though repeated scientific discoveries and engineering applications, without ever preaching. . John managed to become a role model to those who practice catalytic science, not only in the secretive industrial environment but also in universities worldwide. . The legacy of John Sinfelt is his unshakable belief in chemical kinetics to advance catalytic science and engineering. John’s impact on the field exceeds by much the impact of his own scientific and engineering contributions. "

Pioneer of Catalytic Cracking: Almer Mc. Afee at Gulf Oil • With the support of Gulf Refining Company, Almer Mc. Duffie Mc. Afee developed the petroleum industry's first commercially viable catalytic cracking process-a method that could double or even triple the gasoline yielded from crude oil by then-standard distillation methods. Based partly on an 1877 Friedel-Crafts patent, the Mc. Afee cracking process required anhydrous aluminum chloride, a catalyst that was prohibitively expensive. In 1923 Mc. Afee and Gulf would solve that problem by developing a way to synthesize the catalytic reagent at low cost, on an industrial scale. Indeed, each time Mc. Afee's methods appeared to become obsolete, circumstances changed in his favor. Today the results of Mc. Afee's further work with aluminum chloride, which led to the Alchlor process, are still on the scene.

Robert L. Burwell, Jr. , - helped established catalysis concepts

Robert L. Burwell, Jr. , - helped established catalysis concepts • Robert L. Burwell, Jr. , Ipatieff Professor Emeritus of Chemistry at Northwestern University, will always be remembered by his many friends, colleagues, and students as a learned gentleman of high moral standard, a dedicated educator, and a thorough and brilliant researcher in heterogeneous catalysis. He was a leading figure in guiding the development of the catalysis community in the U. S. and the world. His many contributions to the community included serving on the governing body of the (North American) Catalysis Society from 1964 to 1977 as Director, Vice President, and in 1973 -77, President. From 1955 -84, he served on the Board of Director, as U. S Representative to the Congress, Vice President, and President (1980 -84) of the International Congress on Catalysis. He chaired the Gordon Research Conference on Catalysis in 1957, and was Associate Editor and a member of the Editorial Board of Journal of Catalysis. Robert Burwell received his Ph. D. in 1936 from Princeton University under the guidance of Sir Hugh Taylor. After three years as a Chemistry Instructor at Trinity College, in 1939 he joined the Chemistry Department at Northwestern University. Except for the World War II period from 1942 until 1945, when, having enlisted, he worked at the Naval Research Laboratory, Dr. Burwell served at Northwestern until he retired in 1980. As Ipatieff Professor Emeritus, he continued his research and intellectual activities for another decade after retirement. During his career he published over 170 original research articles, served on National Research Council Committees, IUPAC Committees, the Petroleum Research Fund Advisory Board, the National Science Foundation Chemistry Advisory Board, and others, as well as Chairing the Chemistry Department at Northwestern University. In 1994, he moved to Virginia with Elise, his wife of over sixty years.

Robert L. Burwell, Jr. , - helped established catalysis concepts • Professor Burwell was among the first scientists who understood the critical connection between general chemistry and catalysis. He introduced and popularized concepts that are now familiar to and even commonplace within the entire catalysis community. His research themes centered around elucidation of the reaction mechanisms, nature of surface intermediates, and characterization of active sites of solid catalysts. He was well known for the use of H-D exchange for such studies. Using this technique, he identified the importance of 1, 2 -diadsorbed alkane on noble metal surfaces in the exchange and the hydrogenation reaction, and the irreversibility in the adsorption of alkene during hydrogenation. He established the “rollover” mechanism for cyclic hydrocarbons in these reactions, and the term “surface organometallic zoo”. He carefully documented the importance of surface coordination unsaturation in catalysis by metal oxides, and developed new catalysts of unusual activities by deposition of organometallic complexes on alumina and silica, and by modifying silica surface. His many scientific contributions and their industrial applications were recognized in his day, as evidenced by the many awards and honors he received. They included the ACS Kendall Award in Colloid and Surface Chemistry, the Lubrizol Award in Petroleum Chemistry, and the Humboldt Senior Scientist Award. In addition, the Robert L. Burwell Lectureship Award of the (North American) Catalysis Society was established in recognition of his outstanding contributions to the field of catalysis. Professor Burwell was also known for the first short course in heterogeneous catalysis that he taught for several years together with Michel Boudart.

Robert L. Burwell, Jr. , - helped established catalysis concepts • To those who knew him personally, Burwell was not only an imposing intellect, but a warm, deeply caring, pleasant person, a complicated person with many facets. For instance, while wise and judicious, he nevertheless conducted himself with a great sense of humor and wit. Any who he favored soon realized he could engage in lively conversation on practically any subject. Many of his coworkers also remembered him for his numerous perceptive scientific advice and suggestions. Very often in seminars, students felt that they learned more about a subject from his probing questions than the actual seminar itself. His family remembered him also as a caretaker extraordinaire. His devotion to his wife, particularly during the last year of her life, will be remembered by all. Dr. Burwell was a walking encyclopedia—indeed he was scientific consultant to the World Book Encyclopedia. He read extensively on virtually every subject. He particularly enjoyed a commanding knowledge of the birds, flora and fauna and could be seen bird watching in the snowy early springs in Evanston. He enjoyed cultural matters and sharing of his knowledge with his colleagues, friends, and post-doctoral and graduate students, a trait he continued even after he retired to Virginia with his wife, where he became an active member of many local Virginia museums and a variety of genealogical societies (and a founder of the Computer Club and Wine Club at the retirement community). He was often expected to be the cultural guide for his group of friends on tours around the world. He particularly enjoyed teaching American culture and the nuances of the English language to his international post-doctoral and graduate students. Dr. Burwell loved to refer to the 4 th of July as “the day we celebrate English becoming a foreign language”. He also possessed a cultivated taste for wine, and was proud of his collection of antique porcelain. Perhaps the most appropriate reference to Robert Burwell was from Marie Westbrook, the Department Secretary of Chemistry at Northwestern, who referred to him always as “Mr. Burwell”, not as “Doctor” or “Professor”. When asked why, she replied: “A lot of people can become a Professor or a Doctor, and I use Mister just for him”. On May 15, Mr. Burwell passed away at the age of 91. He was buried on June 28 th, 2003 in Christ Episcopal Church in West River, Maryland next to his beloved wife, Elise.

Sir Eric Rideal

Sir Eric Rideal who was one of the founders of catalysis in Great Britain and who was the eponym of the famous Eley Rideal mechanism. Professor E Rideal was famous for the work of the Colloid Science Laboratory which he set up in Cambridge University in the 1930 s. He was born in 1890 and was first involved in surface chemistry during the First World War when, with H. S. Taylor, he worked on catalysts for the Haber process for the production of ammonia from nitrogen and hydrogen, and for the selective oxidation of carbon monoxide in mixtures of CO and hydrogen. Later Taylor and Rideal wrote a pioneering book Catalysis in Theory and Practice. The Rideal Conference is so named in his honor; this triennial series of UK research conferences on surface chemistry and catalysis was initiated by Charles Kemball and others in the late 1960 s

Vladimir Nikolaevich Ipatieff

Vladimir Nikolaevich Ipatieff • Vladimir Nikolaevich Ipatieff was born on 21 November 1867 in Moscow, Russia. His early career was that of a military man: in 1887 he graduated from the Mikhailovskoe artilleriiskoe uchilishche, and in 1892 from the Mikhailovskaia artilleriiskaia akademiia. But his interest in chemistry diverted him from a strictly military path. Teaching the subject at the Artillery Academy, he went on to get a doctorate from St. Petersburg University in 1907, while advancing in military rank to major general in 1910. From 1906 to 1916, he taught chemistry at the University as well, and was made a member of the Imperial Academy of Sciences in 1916. As a lieutenant general during the First World War, he served as Director of the Commission for Preparation of Explosives and Chairman of the Chemical Committee. Following the revolution, he remained in the Soviet Union, where he founded the High Pressure Institute in 1927. But in 1931, while on a trip abroad, he decided not to return and came to the United States, where he taught at Northwestern University from 1931 to 1935. In 1939 he was elected a member of the National Academy of Sciences. Ipatieff died in Chicago on 29 February 1952. Northwestern University dedicated a laboratory in his honor.

Vladimir Nikolaevich Ipatieff • [A slightly different version about his move to the USA (from Professor Peter Stair of Northwestern Univeristy): Ipatieff had been a General under Tsar Nicholas II and Chairman of the Chemical Administration and winner of the Lenin Prize under the Soviets. Shortly after Ipatieff emigrated from the USSR to avoid the Stalin purges, he was approached by representatives of Universal Oil Products (UOP) who invited him to work in the USA in the dual capacity of Director of Chemical Research at UOP and Professor of Chemistry at Northwestern University. He worked together with Herman Pines to discover and develop the important processes of isomerization and alkylation with liquid acids based upon the reaction of paraffin molecules in petroleum reacting with an aqueous solution of sulfuric acid. In early 1940, at the beginning of World War II, the first alkylation plant came on stream in the US. The boost in aircraft fuel octane made possible by this plant played a significant role in the success of the British Royal Air Force in the Battle of Britain. ] Ipatieff authored hundreds of articles on chemistry in a number of languages, as well as textbooks, such as Kolichestvennyi analiz, which he wrote while still a student (St. Petersburg, 1891); a scientific autobiography, Catalytic Reactions at High Pressures and Temperatures (New York, 1936); and personal memoirs, Zhizn' odnogo khimika (New York, 1945), translated into English as The Life of a Chemist (Stanford, 1946). He also held several hundred patents, marking his most significant contributions to science: the formulation of high-octane gasoline, the "cracking" method now used to refine gas, and other discoveries relating to catalytic reactions (especially under high pressures and temperatures), and the synthesis of petroleum and its

W. Keith Hall: One of the giants in catalysis

W. Keith Hall: One of the giants in catalysis • Keith Hall passed away in his farm/home at Mill Run, Pennsylvania on 3 January 2001 at the age of 82. The catalytic community has lost a major family-member and leader. Keith was born in Mc. Comb, Ohio and graduated from Emory University in 1940. Shortly thereafter, a summer course in high explosives at Georgia Tech undoubtedly led Frank Long to hire him to work on Manhattan Project at the Bruceton Experimental Station as directed by the U. S. Bureau of Mines. Working under the direction of George Kistiakowski and Louis Hammett, Keith met and married his wife Gladys, a secretary earning money for college ("they paid better than anyone else!") in 1945 while at Bruceton. As the war ended, Keith continued at the Bureau with H. H. Storch and Robert B. Anderson where he was introduced to catalysis, specifically to Fischer-Tropsch synthesis. Concurrently, he received his MS in 1948 from Carnegie Institute. The end of the war had generated an interest in synthetic fuels, and Sol Weller, Irving Wender and Milton Orchin joined the group. This concerted effort was finally terminated by congress in 1956. In 1951 Keith moved across town to work on his Ph. D at Mellon Institute under Paul Emmett. Keith received his Ph. D in 1956 from University of Pittsburgh. His son Burl (now a physicist at LBL) was born in 1955. Contemporaries working at the Mellon Institute with Emmett included Dick Kokes, Joe Kummer, Don Mc. Iver, Bob Anderson (? ), Bob Zabor, and Bob Haldeman. When Emmett left Pittsburgh in 1954, Hall was named as his successor.

W. Keith Hall: One of the giants in catalysis • Keith continued to work at the Mellon Institute as a Senior Fellow until 1970 when he took a Senior Scientist position with Gulf Research outside Pittsburgh. Keith retired from Gulf in 1973. George Keulks convinced Keith to accept the position of Distinguished Professor of Chemistry at the University of Wisconsin-Milwaukee. Many students and postdoctoral students worked with Keith at Milwaukee. While there he coordinated the US-USSR exchange in chemical catalysis. Keith is well remembered for his mandatory Saturday research meetings to keep the troops in order. These meetings developed an international reputation themselves and were known to last well into the afternoon by visitors world wide. Keith retired from this position in 1985 to return to his farm in Mill Run. But his retirement was short lived, as once again he was convinced to become a Distinguished Professor, this time at the University of Pittsburgh, his Ph. D alma mater. Keith finally retired, for the third and final time, from this position in 1998. Keith started his catalysis research on Fischer-Tropsch synthesis with Bob Anderson and continued with Emmett [J. Am. Chem. Soc. 82, 1027 (1960)]. But he also initiated studies of hydrogenation over metals and alloys to test Dowden's electronic theories of catalysis [J. Phys. Chem 62, 816 (1958) and 63, 1102 (1959)]. His employment of isotopic techniques was highly visible throughout his career [J. Am. Chem. Soc. 79, 2091 (1957)]. He published seven papers with Emmett. After Emmett left to again take a position at Johns Hopkins University, Keith continued his interest in hydrogen on solids, primarily metals supported on oxides. He employed a variety of techniques including ESR and NMR often coupled with isotopic studies [J. Catal. 2, 506 (1963) and 2, 518 (1963)]. Keith soon became interested in acidity of silica alumina [J. Catal. 1, 53 (1962) and 3, 512 (1964)]and eventually on zeolites, an interest that would continue throughout his research. He studied hydrocarbon isomerization over a variety surfaces (J. Catal. 13, 161 (1969), Trans. Faraday Soc. 566 -66, 477 (1970)]. Keith also became involved in studies of oxidation on metals and eventually on metal oxides, most notably Mo/Al 2 O 3 [J. Catal. 34, 41 (1974)]. Again isotopic studies and a variety of spectroscopic techniques were employed [J. Catal. 53, 135 (1978)], including infrared. In the 1980's Keith initiated a series of studies related to auto exhaust catalysis. These started with Fe/zeolites [J. Catal. 166, 368 (1997)] and eventually Cu/zeolites [Catal. Let. 15, 311 (1992), J. Phys. Chem. 97, 1204 (1993)] where he developed considerable insight into SCR [J. Catal. 149, 229 (1994)] and NOx reactions [Appl. Catal. B-Env. 2, 303 (1993)]. In parallel, Keith's interest in the reasons for catalytic acidity and in the role of hydrogen on metals and oxides continued well into the 1990's.

W. Keith Hall: One of the giants in catalysis • Keith's publications have had a profound impact on the catalytic community. Over a score of these have been cited more than a hundred times by others. These include each of those mentioned in the previous discussion as we traced Keith's areas of research. Altogether he had more than 4, 000 citations to his work. Keith served and led the Catalytic and Chemical community in several ways. He was the editor on the Journal of Catalysis from 1967 to 1989, a period when J. Catalysis became the primary Journal in heterogeneous catalysis. Frank Stone was the European editor and they were close friends. Keith was the president of the Catalysis Society of North America from 1981 -85 and founded the Catalysis Society Trust, which has given the society on a strong fiscal base. Keith gave five lectures at Gordon Conferences, was chairman of the Gordon Conference on Catalysis, and served as a Trustee of the Gordon Conferences from 1981 -87. Who can forget his perennial presence in the front row of the Gordon Conferences where he would challenge and extrapolate the concepts presented as well as remind the speakers of the prior-art they may have neglected to mention? He had the same room at the conference for many years which was closest to the late night discussions in which he participated actively. In the afternoon he would sail and discuss the concepts of the catalytic science presented. Keith was also active in the ACS and served on the executive committee on the Colloid and Surface Chemistry Division.

W. Keith Hall: One of the giants in catalysis • Keith received numerous awards, including the Kendall Award, the ACS Petroleum Chemistry Award, and the Exxon Award for Excellence in Catalysis. One of the most notable aspects of Keith Hall's research career is the large number of people with whom he worked and to whom he graciously attributed their joint accomplishments. He learned from as he taught each of his students, postdoctoral students, and research colleagues. More than a dozen students received their graduate degrees under Keith's supervision. These include: Suhil Abdo, L. Christner, Michel Deeba, José Goldwasser, Chuck Kibby, Dave Kreske, Y. Li, J. Larson, Edwardo Lombardo, R. Schneider and L. Wang. Keith had over two dozen postdoctoral colleagues including: John Bett, Victor Borokov, Noel Cant, W. Curt Conner, Michel Crespin, Gary Delzer, Joseph Engelhardt, Xiaobing Feng, G. Fierro, Chia-Min Fu, H. Gerberich, Joe Hightower, Marwan Houalla, V. Korchak, T. Komatsu, Sheldon Lande , K. -Y Lee, H. Leftin, Jacques Leglise, Mario Lo Jocono, Ross Madon, William Millman, Mikoto Misono, Jaun Petunchi, Ko-ichi Segawa, Henri Van Damme, Frank Witzel, Jan Uytterhoeven and Jozsef Valyon. Fifteen of these graduate and postdoctoral students hold faculty positions and continue to teach. In addition, Keith has collaborated with over ninety other catalytic research scientists around the world. His collaborators included: Paul H. Emmett, Dick Kokes, Vladim Kazanski, Bob Anderson, Henry H. Storch, H. R. Gerberich, F. H. Van Cauwelaert, M. Missono, Frank Massoth, Kh. Minichev, George Keulks, W. Nick Delgass, Jim Dumesic, Gerhart Ertl, Helmut Knözinger, Dave Hercules, Farrell Lytle, Jose Fripiat, Bernie Gerstein and Julie d'Itri. Keith had over one hundred and twenty co-authors in his more than three hundred and fifty publications. It is obvious that Keith Hall's influence on catalytic research has been profound not only in what he has accomplished directly but in his vast network of interactions throughout the catalytic world. Moreover, Keith readily served as a leader in the catalytic research community through the Journal of Catalysis, the Gordon Conferences and the Catalysis Society.

1956 - Photo First ICC meeting in Philadelphia in 1956

2 nd ICC- Paris: Photos of Emmett/Oblad

2 nd ICC- Photo of Officers 1960 from left: Selwood; Farkas; Ciapetta; Heinemann; van Grosse; Oblad

2 nd ICC- Photos Selwood, Farkas and Heinemann (right to left) Selwood, Farkas and Heinemann(podium)

Left to right/standing: Enrique Iglesia, Henrik Topsoe, Jens Rostrup-Nielsen, Alex Bell, Jim Dumesic, Fabio Ribeiro, Mark Davis; Seated: Nan Topsoe, Marina and Michel Boudart, Tatiana Bell, 20 th North American Catalysis Meeting, Houston, TX, June 2007

SOME CHALLENGES Simplified scheme of the photocatalytic processes on Ti. O 2 during anaerobic water splitting, oxidation of organic compounds and photo-reforming processes.

Carbon dioxide – Waste or Resource Scheme of photo-electrochemical (PEC) reactor for the conversion of CO 2 to long-chain alcohols and hydrocarbons using solar light and water. The same PEC reactor could be used also for the physically separate production of H 2 and O 2 in anaerobic water splitting.

Challenges I Dream reactions waiting for a catalyst Jens Rostrup-Nielsen: XVII Sympósio Iberoamericano de Catálisis, July 16 -21 , 2000

Challenges II Dreaming on …. Heterogeneous catalysts for assymmetric synthesis Photolytic water splitting (hydrogen economy) Biomimetics, synthetic enzymes Non-thermal processes in general (e. g. electro- and photocatalysis) … See: E. Derouane, CATTECH 5, 226 (2001)

Challenges III The science of heterogeneous catalysis: A comprehensive scientific basis Much has been done Much more is needed (oxides, size effects, photocatalysis, electrocatalysis, relation to homogeneous and enzyme catalysis …) Making the insight useful! The ultimate test

Opportunities - design at the nano-scale • Rational catalyst design - Discovery on the basis of insight • Data-driven methods - Accelerated discovery by access to large amounts of data • Bio-inspired catalysis

SIZE EFFECTS IN CATALYSIS Pictorial representation of structure sensitive and insensitive reactions according to the original classification by Boudart

• NANO SCIENCE AND CATALYSIS • Nano Science-contribution to the fundamental understanding and also for designing and fabricating catalytic systems with optimization of the performance. • It is a misconception that the prefix ‘Nano’ implies the dimensionality of the materials, but means the new state of matter which has completely altered behavior as compared to bulk or molecular state materials. • However, the advent of nano state for materials has added another dimension to the science of materials. Even though the advent of this new state has many remarkable and revolutionary changes in various fields, its introduction as a concept in the field of catalysis has remarkable consequences. • This presentation is restricted to examining some of the facets of the changes in the field of catalysis and hence is not comprehensive but only leads to some doors in this exciting area.

Rational catalyst design 1. What determines the catalytic activity/selectivity/lifetime ? 2. How can we affect it? - We have tremendous new possibilities

Ammonia synthesis N 2+3 H 2 2 NH 3 Ozaki and Aika, Catalysis 1 (Anderson and Boudart, Ed. )

Ammonia synthesis over Ru Logadottir, Nørskov

Lessons from Biology Catalysis at ambient temperature and pressure Extreme selectivity Direct coupling of energy into the important reaction coordinate (nonthermal catalysis)

Nitrogenase nitrogenase ATP complex formation Fe protein + Mo. Fe protein 4 Fe-4 S cluster P-cluster nucleotide replacement ATP cleavage electron transfer reduction Fe. Mo cofactor Fe protein + complex dissociation Burgess, Lowe, Chem. Rev. 96, 2983 (1996) Schindelin, Kisker, Schlessman, Howard, Rees, Nature 387, 370 (1997)

Concept of change from actual catalysts to new generation of catalysts based on the concept of catalytic nanofactories

Nano Engineering Concept of nanoengineering of oxide catalytic surface in terms of nanoreactor array, some of the possibilities offered by this concept (in particular in terms of realizing multi-functional catalysts for cascade reactions in nanoconfined liquids) and a SEM image of an array of Ti. O 2 nanotubes produced by anodic oxidation of Ti foils.

Steps do everything Au decorates steps: Hwang, Schroder, Gunther, Behm, Phys. Rev. Lett. 67, 3279 (1991) Dahl, Logadottir, Egeberg, Larsen, Chorkendorff, Törnqvist, Nørskov, Phys. Rev. Lett. 83, 1814 (1999)

The Brønsted-Evans-Polanyi relation Logatottir, Rod, Nørskov, Hammer, Dahl, Jacobsen, J. Catal. 197, 229 (2001)

Calculated ammonia synthesis rates 400 C, 50 bar, H 2: N 2=3: 1, 5% NH 3 Logatottir, Rod, Nørskov, Hammer, Dahl, Jacobsen, J. Catal. 197, 229 (2001)

Interpolation in the periodic table Jacobsen, Dahl, Clausen, Bahn, Logadottir, Nørskov, JACS 123 (2001) 8404.

Interpolation in the periodic table Jacobsen, Dahl, Clausen, Bahn, Logadottir, Nørskov, JACS 123 (2001) 8404.

Interpolation in the periodic table Jacobsen, Dahl, Clausen, Bahn, Logadottir, Nørskov, JACS 123 (2001) 8404.

Measured ammonia synthesis rates 400 C, 50 bar, H 2: N 2=3: 1 Jacobsen, Dahl, Clausen, Bahn, Logadottir, Nørskov, JACS 123 (2001) 8404.

Data driven methods • High throughput screening – Direct testing of many catalysts, fast, efficiently • Data mining – Correlating catalytic activity/selectivity/ durability to descriptors that can be tabulated

H. Toulhoat and P. Raybaud Using DFT calculations in the search of prospective catalysts Workshop Catalysis from First Principles Vienna 02/02 The object of the game… • Find sets of descriptors {Dik} of solid materials Mi , and a mathematical model F such that Aij being the Turn Over Frequency of Mi as catalyst for the reaction j at operationg conditions Cj one has: • Identify ranges of Dik that maximize F • Screen Databases of Materials Properties before screening real materials • Better if one descriptor is sufficient, but do not take it for granted • Much better if F has a sound physical basis • Adsorbate/substrate bond strengths should provide good descriptors according to the Sabatier principle

H. Toulhoat and P. Raybaud Using DFT calculations in the search of prospective catalysts Workshop Catalysis from First Principles Vienna 02/02

H. Toulhoat and P. Raybaud Using DFT calculations in the search of prospective catalysts • E MC @ Fm-3 m carbides is rather consistent with simple chemisorption models • Onset of dissociative chemisorption as MC bond strength increases Workshop Catalysis from First Principles Vienna 02/02

H. Toulhoat and P. Raybaud Using DFT calculations in the search of prospective catalysts • The experimental Alloying effects is correctly predicted Workshop Catalysis from First Principles Vienna 02/02

Getting data/descriptors • • • Structure (in situ) Spectroscopy (in situ) Surface thermochemistry Calculations … There is a large need for systematic data - and for good descriptors

Structure-activity Correlation Hydrodesulfurization of thiophene HDS activity (x 102/mol/g/h) 1. 5 10 Topsøe, Clausen, Massoth Hydrotreating Catalysis, Science and Technology (Anderson and Boudart (Eds. ), Springer (1996). 0. 5 0 0 1 2 3 Number of Co edge atoms (x 1020/g catalyst)

Descriptors from spectroscopy CO TPD shift Core level shift Goodman and Rodriguez, Science 279 (1992) 897

Single crystal microcalorimerty Cu/Mg. O Ag/Mg. O Pb/Mg. O Larsen, Starr, Campbell, Chem. Thermodyn. 33, 333 (2001) Brown, Kose, King, Chem. Rev. 98, 797 (1998).

Descriptors from DFT Correlation between adsorption energies and activation barriers and the d-band center Mavrikakis , Hammer, Nørskov Phys. Rev. Lett. 81, 2819 (1998)

CO tolerance of Pt alloy anodes for PEM fuel cells Pt M S. Gottesfeld et al. , J. Electrochem. Soc. 148 (2001) A 11. Christoffersen, Liu, Ruban, Skriver, Nørskov, J. Catal. 199, 123 (2001)

How can the d-band center be changed? Calculated d band shifts: Overlayer Host Ruban, Hammer, Stoltze, Skriver, Nørskov, J. Mol. Catal. A 115, 421 (1997)

Methane activation Transition state for CH 4 dissociation on Ni(211) Bengaard, Rostrup-Nielsen, Nørskov b

Methane activation on Ni/Ru Egeberg, Chorkendorff, Catal. Lett. 77, 207 (2001)

Lessons from biology • Catalysis at ambient temperature and pressure • Extreme selectivity • Direct coupling of energy into the important reaction coordinate (non-thermal catalysis)

Nitrogenase nitrogenase ATP complex formation Fe protein + Mo. Fe protein 4 Fe-4 S cluster P-cluster nucleotide replacement ATP cleavage electron transfer reduction Fe. Mo cofactor Fe protein + complex dissociation Burgess, Lowe, Chem. Rev. 96, 2983 (1996) Schindelin, Kisker, Schlessman, Howard, Rees, Nature 387, 370 (1997)

N 2 hydrogenation on Fe. Moco Rod, Nørskov JACS 122, 12751 (2000)

The Fe Protein cycle Mo. Fe protein ATP E 1) Fe. Moco P-cluster 4 Fe-4 S cluster 2) E 3) ADP E 4) See also: Spee, Arendsen, Wassnik, Marrit, Hagen, Haaker, FEBS Lett. 432, 55 (1998)

Comparing the Fe. Moco and Ru(0001) Rod, Logadottir, Nørskov J. Chem. Phys. 112, 5343 (2000)

Status • • • Well developed basic understanding – theory-experiment Beginning to be able to use it directly in catalyst design Some activity-descriptor correlations Host of new in situ methods for catalyst characterization New very powerful screening methods We have a starting point which is radically different from the situation 5 or 10 years ago!

Moving forward • More basic understanding –theory-experiment • Integration of the conceptual framework for heterogeneous, homogeneous and enzyme catalysis • More systematic data (descriptors) • Better synthesis methods • Better coupling of catalyst design and process engineering • INTEGRATION

Promoting development An integrated approach: Experiments, models Synthesis testing characterization Theory

Schematic representation of the electro-catalytic conversion of CO 2 to isopropanol in carbon nano-tubes based electro-catalysts

Challenges in oxidation reactions The first challenge is to use dioxygen, preferably air instead of any other oxidants. Since dioxygen is a triplet biradical, free radical chain autoxidation (FRCA) dominates both gas–liquid-phase homogeneous and heterogeneous catalysis, even in cases in which the catalytic transformation itself is rather selective. The final result is usually an apparent lack of selectivity in the overall transformation. . The second challenge is to avoid overoxidation because usually the oxygenate is more sensitive to oxidation as the feedstock. The cobalt-catalyzed oxidation of toluene yields only a minor percentage of benzaldehyde amongst the main product, benzoic acid. . The third challenge is to overcome the hurdle that many feedstocks lack functionality, and might be susceptible to several oxidative transformations, still leading to an overall loss of selectivity though the catalytic transformation itself is selective. nbutane, cyclohexane, and benzene are obvious examples Challenges in oxidation reactions

SUMMARY Catalysis in an enabling technology to promote sustainability, environment, energy, health and quality of life. There is an increase of interest on catalysis, but at the same time a fast evolution of this area. Various factors driving the changes in catalysis research , such as the need to go to more sustainable and modular-design of the chemical processes, the use of biomasses and renewables, the use of solar energy and/or electro-catalysis. However, to fully implement catalysis as a enabling technology for societal challenges, not only an excellent research is necessary, but it is also need to overcome fragmentation barriers, particularly in catalysis areas (homo-, hetero- and bio-) and in academy–industry interactions. This requires to create a longer term vision and strong collaborations to develop a knowledge platform, in order to accelerate the innovation path. The realization of catalysis–society interactions, e. g. the creation of interfaces and structures to promote dissemination and spreading to society, is another relevant component for this objective. Finally, the need to develop new catalytic materials, extend the use of catalysts to other areas, and address key societal issues (for example CO 2 conversion, sustainable energy) were emphasized.

Heterogeneous catalysis: enigmas, illusions, challenges, realities, and emergent strategies of design (J M Thomas considers the question of how to design new solid catalysts for a variety of industrial and laboratory-orientated purposes. A generally applicable strategy, illustrated by numerous examples, is made possible based on the use of nanoporous materials on to the (high-area) inner surfaces of which well-defined (experimentally and computationally) active centers are placed in a spatially separated fashion. Such single-site catalysts, which have much in common with metal-centered homogenous catalysts and enzymes, enable a wide range of new catalysts to be designed for a variety of selective oxidations, hydrogenations, hydrations and hydrodewaxing, and other reactions that the "greening" of industrial processes demand. Examples are given of new shape-selective, regio-selective, and enantio-selective catalysts, many of which operate under mild, environmentally benign conditions. Also considered are some of the reasons why detailed studies of adsorption and stoichiometric reactions at singlecrystal surfaces have, disappointingly, not hitherto paved the way to the design and production of many new heterogeneous catalysts. Recent work of a theoretical and high-throughout nature, allied to some experimental studies of well-chosen model systems, holds promise for the identification of new catalysts for simple, but industrially important reactions.

Tomorrow: A new, homogeneous catalyst to make methanol may be commercialized following preliminary work at Brookhaven National Laboratory

THE BATTLE OF BRITAIN: CATALYSTS FOR VICTORY Fifty years ago, between July 10 and October 31, 1940, Royal Air Force fighter pilots defeated the Luftwaffe in a heroic air battle over Britain. The British lost 915 planes versus 1733 for the Germans. The impact of the British victory was immortalized by Winston Churchill in the House of Commons when he said, "Never in the field of human conflict was so much owed by so many to so few. " In the Chicago Tribune Magazine of July 15, 1990, Herman Pines reminds us of the critical role played by 100 -octane fuel that provided British planes with 50% faster bursts of acceleration than were available to them during the May 1940 French campaign fought with 87 -octane fuel. With the same planes but new fuel, British pilots were able to outclimb and outmaneuver the enemy. The new fuels that contributed to victory came just in time from the United States, as a result of discovery and development by Universal Oil Products (now UOP Inc. ) of sulfuric acid-catalyzed gasoline alkylation. Vladimir Ipatieff, Herman Pines, and Herman S. Bloch played key roles in this work. Since 1940, hydrofluoric acid has, in part, replaced sulfuric acid as the catalyst for gasoline alkylation. Today, in the battle for the environment, efforts are under way to replace hydrofluoric acid. Eventual success will be another achievement of researchers in catalysis.

The first triumph of large-scale catalytic technology goes back to 1913 when the first industrial plant to synthesize ammonia from its constituents, nitrogen and hydrogen, was inaugurated in Germany. From the outset, and until the present, the catalyst in such plants has consisted essentially of iron. The mechanism of the reaction is now well understood. Small groups of iron atoms at the surface of the catalyst are capable of dissociating first a molecule of nitrogen and then a molecule of hydrogen, and finally of recombining the fragments to ultimately form a molecule of ammonia. The catalyst operates at high temperature to increase the speed of the catalytic cycle and at high pressure to increase thermodynamic yield of ammonia. Under these severe conditions, the catalytic cycle turns over more than a billion times at each catalytic site before the catalyst has to be replaced. This high productivity of the catalyst explains its low cost: the catalyst results in products worth 2000 times its own value during its useful life.

The refining of petroleum to produce fuels for heating and transportation involves a large number of catalytic processes. One of these is the catalytic reforming of naphtha, a component derived from petroleum, used to produce high-octane gasoline. In modern catalytic reforming, many different catalytic reactions proceed on small particles made of platinum and a second metal such as rhenium or iridium. These bimetallic clusters are expensive but chemically robust. They can be reactivated after long-term use, thus making possible the use of precious metals to produce an affordable consumer commodity. The metallic clusters are so small that practically all metal atoms are exposed to the reactants and take part in the catalytic cycle. These metal clusters are supported within the pores of an acidic metal oxide that also takes part in the reforming process.

The next illustration of catalysis shows that industrial catalysts can be biomimetic, in the sense that they imitate the ability of enzymes to produce optically active molecules (i. e. , molecules whose structures are such that the reflection of the molecule in a mirror does not superimpose on the original molecule). Many pharmaceuticals are known to be active in only one form, let us say the left-handed form. It is therefore critical to obtain the left-handed form with high purity. This is particularly important when the drug is toxic, even if only slightly so, and must be administered over many years. It is true of a molecule called L-Dopa used in the treatment of Parkinson's disease. Here, the righthanded molecule is inactive. In ordinary synthesis, both forms (right and left) are produced in equal amounts. Their separation is costly. Is it possible to produce only the left-handed form by means of a synthetic catalyst? The first success of an industrial synthesis of this kind was achieved at Monsanto, and a patent for the selective synthesis of L-Dopa was granted in 1974. The catalytic process used to make L-Dopa today may be regarded as an important achievement in industrial catalysis

Finally, more recent developments in catalytic technology are targeted at the protection of the environment. The best-known example deals with catalytic converters that remove pollutants from the exhaust gases of automobiles. Catalytic converters for automobiles were first installed in the United States in the fall of 1974. These devices were subsequently introduced in Japan and are currently spreading through Europe. The most advanced catalyst now contains three metals of the platinum group and controls the emissions of carbon monoxide, nitrogen oxides, and unburned hydrocarbon molecules by use of a complex network of catalytic reactions. This application has contributed more than any other to public awareness of catalysis and of its many applications for the benefit of mankind.

AN IMMOBILIZED ENZYME AS AN INDUSTRIAL CATALYST While the oil crisis of the 1970 s was front-page news, the soft drink industry was experiencing a less-heralded shock of its own. High sugar cane prices sparked a scramble to other sweeteners—not artificial sweeteners, mind you, but other forms of sugar. Table sugar— sucrose—is just one member of a family of several dozen closely related natural sugars. Other members include fructose, found in fruits; glucose, found in honey and grapes; lactose, found in milk; and maltose, found in malted grain. Fructose became the sweetener of choice, thanks to the adaptation of a catalyst to its large-scale industrial production. The catalyst, glucose isomerase, was derived from Streptomyces, a common, soil-dwelling bacterium best known as the source of many antibiotics, including streptomycin. Glucose isomerase is an enzyme—one of nature's own catalysts. All living things use enzymes, each one tailored to carry out one of the multitude of reactions essential for life itself. An enzyme is essentially a protein molecule, although it may have other atoms or molecules attached that help it do its job. A protein molecule is a long chain made up of hundreds or thousands of smaller units called amino acids assembled in a very specific order. When dissolved in water, this chain naturally kinks and knots up. The sequence of amino acids making up the protein determines the shape that the protein knots itself into, and it is this shape that allows the protein to catalyze its reaction. The molecules that participate in the reaction fit into a crevice in the protein, like a key in its lock. Once inside the crevice, called the "active site, " the molecules are held in just the right relative orientation for the reaction between them to proceed.

Adapting an enzyme to a continuous-flow industrial process requires that the soluble protein be immobilized somehow. (If the protein were left in its soluble form, it would be well-nigh impossible to separate it from the process stream, and it would all wash away in the flow. ) To keep doing its job, the immobilized enzyme must retain its dissolved shape, yet it must also be firmly anchored to its solid support. In addition, the catalyst-support combination must be stable at the processing temperature and strong enough not to break up under processing conditions. Resin and polymer supports were tried first, because these molecules are chemically very similar to enzymes, which makes it easy to attach enzymes to them. Unfortunately, the resin and polymer beads were crushed into a gummy mass under the processing conditions and clogged the works. One way around the problem is to attach the enzyme molecules to a ceramic material. Tiny ceramic particles have a high surface area, allowing a lot of catalyst to be attached to them and increasing the reaction's efficiency. Ceramics are also incompressible, and so thesystem can be run at high pressure without crushing the catalyst or clogging the works. Because proteins do not stick naturally to ceramics, an intermediary is needed. The ceramic particles are coated with a special polymer that adheres well to both the ceramic and the enzyme while allowing the enzyme to retain its shape

The enzyme does tend to decompose slowly under process conditions, but the extra stiffness imparted to it by the ceramic backbone makes it more stable than the natural enzyme, so that each batch of ceramic-supported enzyme lasts longer. The fructose production process has proved to be remarkably efficient. One pound of catalyst-coated ceramic will produce an average of 14 1/4; tons, and sometimes as much as 18 tons, of fructose (measured as a dry solid) before the enzyme loses its activity. The process converts a watery, honey-colored syrup containing 95% glucose— a by-product of the wet-milling process used to make starch from corn—into a 42 -45% fructose syrup—the "corn sweeteners" on a soft drink ingredient label. (Both Coca-Cola and Pepsi-Cola allow their bottlers to replace up to 100% of the sugar in their soft drinks with corn sweeteners. ) Although glucose, fructose, and sucrose are all sugars, they are not equally sweet. Glucose is not picked up by the taste buds as quickly as fructose or sucrose, nor does its sweetness linger as long on the palate. If sucrose scores 100 on a sweetness scale, fructose rates a supersweet 173 and glucose an unsatisfying 74—the main reason glucose itself is not sold as a sweetener.

A complicated separation process keeps recycling unreacted glucose back through the system, while drawing off fructose as it forms. Pure fructose comes out as a 90% solution, which is diluted to 55%—equivalent in sweetness to pure sucrose—before the syrup is sold. Thus fructose is as convenient to use as sucrose—the bottler does not have to install any extra tanks or plumbing to dilute the fructose, or alter the recipes to allow for its greater sweetness. Fructose has the added advantage of being safe for diabetics.

THE FUNCTION OF RESEARCH Research plays a vital role in advancing the frontiers of scientific understanding of catalysis and in assisting the development of catalysts for industrial application. Because of the complexity of catalysts and catalytic phenomena, information must be drawn from a large number of supporting disciplines, in particular, organometallic chemistry, surface science, solid-state chemistry and materials science, biochemistry and biomimetic chemistry, chemical reaction engineering, and chemical kinetics and dynamics. Although research in catalysis is still dominated largely by experimental studies, theoretical efforts are becoming increasingly important. Theory provides a framework for understanding the relationships among catalyst composition, structure, and performance. The advent of supercomputers has made it possible to model a still larger body of catalytic phenomena and even, in some cases, to predict catalyst properties a priori. The availability of high-resolution computer graphics has proved particularly useful in visualizing the results of complex calculations and understanding the spatial relationships between catalysts and reactants on a molecular scale.

The industrial development of catalysts is an expensive and labor-intensive activity because catalysts currently cannot be designed from first principles. Rather, they must be developed via a sequence of steps involving formulation, testing, and analysis. An important aim of research in catalysis is to accelerate this process by providing critically needed knowledge and techniques. Another important function of research is to provide a reservoir of new information and materials that may contribute to the identification of new catalytic materials or processes. Thus, not only does research provide the tools and knowledge needed for direct facilitation of catalyst development, but it also increases opportunities for the discovery of new materials and new techniques.

One example suffices to illustrate the impact of research on catalytic science and technology. Because catalysis is a kinetic phenomenon based on the turning over of the catalytic cycle, the example deals with the prediction of overall kinetics for a catalyzed reaction based on a knowledge of elementary steps in the cycle. This information cannot be obtained theoretically at present, but it can be determined from experimental investigations. In the case of solid catalysts, some of these measurements are carried out on large single crystals, exposing one defined facet about 1 cm in size. These facets are nearly perfect in structure and are extremely pure. The chemistry of elementary processes occurring on such surfaces can be studied in great detail, to determine not only the rate of the process but also what intermediate species are formed. By studying different crystal facets, the effects of catalyst surface structure on reaction dynamics can be established. Information on the rates of elementary reactions can be assembled to describe the kinetics of a multistep process. This approach has been used to understand ammonia synthesis, over iron, and to establish which facet of iron is most effective in promoting this reaction. Such knowledge can be used to guide the preparation of industrial catalysts so as to expose the desired facets of iron preferentially. Recent studies have demonstrated that the best commercially available ammonia synthesis catalysts operate at a rate that is almost equal to that observed on the preferred facet of iron.

catalysts play a vital role in providing society with fuels, commodity and fine chemicals, pharmaceuticals and means for protecting the environment. To be useful, a good catalyst must have a high turnover frequency (activity), produce the right kind of product (selectivity), and have a long life (durability), all at an acceptable cost. Research in the field of catalysis provides the tools and understanding required to facilitate and accelerate the development of improved catalysts and to open opportunities for the discovery of new catalytic processes.

The chemical industry is one of the largest of all U. S. industries, with sales in 1990 of $292 billion and employment of 1. 1 million. It is one of the nations's few industries that produces a favorable trade balance; the United States now exports chemical products amounting to almost twice the value of those that it imports (exports of roughly $37 billion compared to imports valued at about $21 billion). Between 1930 and the early 1980 s, 63 major products and 34 major process innovations were introduced by the chemical industry. More than 60% of these products and 90% of these processes were based on catalysis. Catalysis also lies at the heart of the petroleum refining industry, which had sales in 1990 of $140 billion and employed 0. 75 million workers. Clearly then, catalysis is critical to two of the largest industries in sales in the United States; catalysis is also a vital component of a number of the national critical technologies identified recently by the National Critical Technologies Panel.

A representation of the molecular structure of HY zeolite. Solid circles represent the Brønsted acid sites responsible for cracking of petroleum. Open circles represent (Al. O 4)- sites, and dashed circles represent Me+ sites. (Figure courtesy of Union Carbide Corporation. )

New Catalytic Oxidation Processes –methanol to ethylene cost A STRONG POINT FOR THE FUTURE Pharmaceuticals Polymers Biologically Derived Products PRODUCTION OF FUELS Advanced Fluidized Catalytic Cracking Catalysts for the Production of Environmentally Acceptable Gasoline Oxygenates for Octane Boosting New Fuels—Methanol Dissociation to Carbon Monoxide and Hydrogen ENVIRONMENTAL PROTECTION CATALYSIS FOR ENERGY INDEPENDENCE Alkylation Catalysts Emission Abatement AUTO EXHAUST CATALYSTS Biodegradation of Organic Waste Replacements for Chlorofluorocarbons Lower-Cost Feedstocks

Research Opportunities in Catalytic Science SYNTHESIS OF CATALYTIC MATERIALS CATALYST CHARACTERIZATION MECHANISM AND DYNAMICS OF CATALYTIC REACTIONS

Some Experimental Techniques for Characterizing Catalysts and Adsorbed Species Technique Acronym Type of information Low energy electron diffraction LEED Two dimensional structure Auger electron spectroscopy AES Elemental analysis X-ray Photoelectron spectroscopy XPS Elemental analysis Ion Scattering spectroscopy ISS Elemental analysis UV photoelectron spectroscopy UPS Electronic structure X ray diffraction XRD Crystal structure Extended x ray absorption fine structure EXAFS Molecular structure Infra red spectroscopy IRS Molecular structure Electron energy loss spectroscopy EELS Molecular structure Transmission electron microscopy TEM Crystal shape, size, morphology Scanning tunnelling microscopy SEM Microstructure

All devices where in surface to volume ratio is high are better performing systems example is brain, leaf and may other natural systems. The reason is that the activation at the surface is different from activation in the bulk

Multi-functionality • Surface site is differently active compared to the sites in the bulk of the material • Multi-functionality is easily possible

Challenges in Catalysis for the Conversion of Fossil Fuels Fossil fuel Function Challenges in catalysis Basic Science challenges coal Utilization Gasification C-C bond activation Clean up CO 2, NOx reduction, S and particulates CO 2, NOx reduction chemistry Utilization Catalytic combustion - Clean up CO 2 reduction CO 2, NOX reduction chemistry Utilization FT, other Gas to liquid processes, H 2 C-H bond activation production Clean up CO 2, NOx, reduction Oil Natural gas CO 2, NOx reduction chemistry

Catalysis is a complex, interdisciplinary science. Therefore, progress toward a substantially improved vision of the chemistry and its practical application depends on parallel advances in several fields, most likely including the synthesis of new catalytic materials and recognition of the reaction path of catalytic reactions. For this reason, future research strategies should be focused on developing methods with the ability to observe the catalytic reaction steps in situ or at least the catalytic site at atomic resolution. There is also a need to link heterogeneous catalytic phenomena to the broader knowledge base in solutions and in well-defined metal complexes.

Substantial progress and scientific breakthroughs have been made in recent years in several fields including atomic resolution of metal surfaces, in situ observation of an olefin complexed to zeolite acid sites by NMR spectroscopy, and in situ characterization of several reaction intermediates by a variety of spectroscopic techniques. Theoretical modeling is ready for substantial growth as a result of progress in computer technology and theory itself. For these reasons, it is desirable to focus on areas in which the extensive scientific and technological resources of academe and industry may lead to the fastest practical results. In order of priority, these areas are in situ studies of catalytic reactions; characterization of catalytic sites (of actual catalysts) at atomic resolution (metals, oxides); synthesis of new materials that might serve as catalysts or catalyst supports; and theoretical modeling linked to experimental verification.

The development of new characterization tools, particularly in spectroscopy, has been mainly the province of academic research, and thus is expected to continue because industry is finding it increasingly difficult to justify the costs associated with technique development. Furthermore, additional steps must be taken to facilitate interaction and, in fact, cooperation between industry, dealing with proprietary catalysts, and academe, developing advanced characterization tools and theory for catalysis.

Enhanced appreciation by academic researchers of industrial technology. Vehicles for this include long-term consulting arrangements involving regular interactions with industrial researchers, sabbaticals for industrial scientists in academic or government laboratories, sabbaticals for academic or government scientists in industrial laboratories, industrial internships for students, industrial postdoctoral programs, and jointly organized symposia on topics of industrial interest.

Increased industrial support of research at universities and national laboratories. Vehicles for this include research grants and contracts; unrestricted grants for support of new, high-risk initiatives; and leveraged funding (e. g. , support of the Presidential Young Investigators program. )

L ACADEMIC INSTITUTIONS 1. A materials – focoussed approach is needed to complement the existing strong efforts on understanding and elucidating cataytic phenomena. More emphasis should be placed on investigation of the optimized design and synthesis of new catalytic materials, in addition to the study of existing ones. It must be kept in mind that a new material deserves consideration as a potential catalytic material only after its successful use as a catalyst, or as a component of such. 2. Further advancement should be made in the characterization of catalysts and the elucidation of catalytic processes, particularly under reaction conditions; existing studies of structure-function relationships should be continued and expanded to focus on catalysts relevant to applications with major potential.

3. Academic researchers should develop cooperative, interdisciplinary projects, or instrumental facilities, in which researchers from a range of disciplines work on various aspects of a common goal, as exemplified by programs carried out in NSFsupported Science and Technology Centers. 4. Academic researchers should be encouraged to work collaboratively on projects with industry that are aimed at enabling the development of catalyst technology through the application of basic knowledge of catalysts and catalytic phenomena. 5. Academic institutions should ease their patent policies with respect to ownership and royalties, to facilitate greater industrial support of research.

National laboratories undertake joint research projects with industry focused on developing a fundamental understanding of the structureproperty relationships of industrially relevant catalysts and catalytic processes, and on using such understanding for the design of new catalysts for major new process opportunities; continue the development of novel instrumentation for in situ studies of catalysts and catalytic phenomena; place greater emphasis on the systematic synthesis of new classes of materials of potential interest as catalysts; and investigate novel catalytic approaches to the production of energy (e. g. , light-assisted catalytic splitting of water), the selective synthesis of commodity and fine chemicals, and the protection of the environment

PERCEPTION and Not the End! • The possibility of viewing the active sites of catalysts that has become possible by the advent of the high resolution microscopy has slowly transforming the field of catalysis science. • The biological systems (especially enzymes) have been transforming molecules in most efficient manner under milder operating conditions than what is demanded by heterogeneous catalysts and are yielding most selective products. • The nanostate of catalytic materials can be approximated to these biological systems and hence it is possible that one can expect catalytic efficiencies similar to the biological efficiencies with respect to specificity up to atom economy. The structural and electronic properties as well as geometric constraints obtainable in biological systems can be replicated in catalytic systems. This possibility opens up another avenue where the catalyst transformations will be controlled by the frontier wave functions of the catalytic systems. • Up to now the new catalyst systems are designed from chemical information only while in future the postulates for new generation catalyst systems will be based on the nature of frontier wave functions of the nanoscale materials with the normally obtainable ‘constraints’ on the fragments of biomolecules which are responsible for the selectivity. Biomolecules adopt unusual geometrical configurations due to internal hydrogen and other non bonding interactions in the species. These are probably the reasons for the generation of active sites which operate as ‘lock and key’. The advent ‘nano state’ of materials and its adoption to catalysis can be expected to turn around a revolution in this field.

QUESTIONS? What areas of fundamental research are most helpful to support commercial catalyst/catalysis activity in industry? Should the dispersal of federal research grants to academic researchers be based on demonstrated excellence in science or focused to support the national laboratories? What type of linkage with academia/national laboratories is most useful to, and supportable by, industry? What elements in science or technology provided the edge to your commercial business in catalyst/catalytic processes? What novel catalytic processes do you expect to be developed in the next 10 to 15 years? What will be the nature of the exploratory and basic research that leads to these developments? Is academic and industrial catalytic research well positioned to play a leadership role in creating this new technology and, if not, what needs to be done?

Identify areas of catalyst science and technology is (1) behind competitors, (2) even with competitors, and (3) ahead of competitors. Identify problems that have long-term payoff. What areas are ''mature'' or "dead"? Has too much emphasis been placed on one area in the past? What would be the ideal mix of industrial and academic research in catalysis? What are the major unsolved problems in catalysis, and what would the solution to these problems provide in economic and technical terms? Are there new areas where catalysis could be used?

Catalyst design driven by fundamental research How do we extrapolate from molecular (picoscale) and nanoscale fundamentals to operating catalytic systems? 1. Is this a worthy/practical goal? 2. What do we need to enable it? 3. Are there alternatives? 4. Are there fundamental differences in the way we answer these questions (and act on them) for homogeneous vs. heterogeneous catalysis?

Vision 2020 Catalyst Technology Roadmap (1997) Primary Needs: 1. Enable catalyst design through combined experimental and mechanistic understanding, and improved computational chemistry. 2. Development of techniques for high throughput synthesis of catalysts and clever new assays for rapid throughput catalyst testing, potential combinatorial techniques, and reduction of analytical cycle time by parallel operation and automation. 3. Better in situ techniques for catalyst characterization 4. Synthesis of catalysts with specific site architecture

Catalyst design = ability to specify and synthesize catalysts to achieve desirable chemical transformations Translate molecular (picoscale) and nanoscale fundamentals to catalyst design at this length scale “Catalyst design driven by fundamental research is the exception rather than the norm. ”

Examples of success in catalyst design driven by fundamental research From understanding known catalysts to inventing new ones: • Translating understanding of ceria function in 3 -way exhaust catalysts into new water-gas-shift catalysts • New supported oxide monolayer catalysts for alcohol oxidation • Selective catalytic oxidation of benzene to phenol using nitrous oxide

Examples of success in catalyst design driven by fundamental research Ligand design in homogeneous catalysis: • Single Site olefin polymerization catalysts • Enzyme analogs: synthetic di-iron complexes that mimic hydrogenases

Examples of success in catalyst design driven by fundamental research Catalyst design from first principles – Theory and Experiment: • Gold-Nickel steam reforming catalyst • Bimetallic ammonia synthesis catalyst • Oxide catalysts for selective ketene synthesis

Central Themes and Concepts: Key characteristics of successes • Recognition of reactivity patterns • Close interaction of theory and experiment • Synthesis and testing of designs • Multidisciplinary approaches/ multidisciplinary collaborations

Critical needs • • • Better understanding of molecular level mechanisms Better access to synthetic capabilities Better ways of creating models of working catalysts Better understanding of attributes that make for successful scale -up (Better communication/collaboration) Fundamental studies of thermodynamics of bonds “Catalysis Informatics” Materials structure of complex systems: from atom connectivity to physical, chemical and electronic properties New ligand platforms New supports New reaction environments (Dynamics of elementary processes)

Goals, Challenges and Opportunities Vision 2020 technology targets remain relevant Selective oxidation Alkane activation Byproduct and waste minimization Stereoselective synthesis Functional olefin polymerization Alkylation Living polymerization Alterative feedstocks and renewables Additions to this list Photocatalytic water splitting Low cost oxidants NO decomposition Methane conversion to useful products Clean transportation fuels Fuel cells Replacement of Pt-group metals New materials that embody nanoscale control of structure and chemical function Catalysis from first principles offers a fresh approach to these challenges

Frontiers in Chemical Engineering (1988) “With sufficient development of theoretical methods, it should be possible to predict the desired catalyst composition and structure to catalyze specific reactions prior to formulation and testing of new catalysts. ”

Opportunities in Chemistry (1985) “We propose an initiative to apply the techniques of chemistry to obtain a molecularlevel and coherent understanding of catalysis that encompasses heterogeneous, homogeneous, photo-, electro-, and artificial enzyme catalysis. ”

A big sign of relief! Where do we stand in international level? Why do we have to evaluate ourselves under this reference and normalize? This must be a question in each one of us who are supposed to indulge in research in this area Thank you all