Catalysis Catalysis Applications Catalysis Applications World catalysts World catalysts • 9 G$ business in 1999 • 24% for Refining, 24% for Chemicals, 23% for Polymers, 29% for Environment oxidation According to Dept. Energy, USA, in 2003 Catalysis & Catalytic processes are •responsible for about 20% of the U.S. gross domestic product (all goods and services) •the keys to future gains in energy efficiency, environmental stewardship and attendant economic prosperity for the country The twelve principles of Green Chemistry 1. It is better to prevent waste than to treat or clean up waste after it is formed. 2. Synthesis methods must be designed to maximize the incorporation of all materials used in the process into the final product. 3. Whenever practicable, synthetic methodologies should be designed to use and generate substances that possess little or no toxicity to human health and the environment. 4. - - - - 9. Catalytic reagents (as selective as possible) are superior to stoichiometric reagents. 10 - - - Early History of Catalysis •Neolithic age (新石器時代 ~5000B.C.) Biocatalytic fermentation in wine manufacture •500B.C. Soap manufacture (hydrolysis of animal fats with potash lye) •1500A.C. Alchemists formed sulfuric acid by a mysterious catalytic process •1831 Pelegrine Phillips (a Bristol vinegar manufacturer) obtained the 1 st known patent in catalysis for the reaction SO 2 + air → SO 3 (Pt sponge as catalyst) The catalyst used now-a-day is V 2 O 5 / SiO 2 •1835 J.J. Berzelius coined the word “catalysis” Greek words “cata”means “down” “lysis”means “split”or “break” “This new force, which is unknown until now, is common to both organic and inorganic nature. I do not believe that it is a force completely independent of electrochemical affinities; … It is more convenient to give this force a separate name. I would therefore call this the catalytic force. I would furthermore, call the decomposition of substances resulting from this force catalysis, just as the decomposition of substances resulting from chemical affinity is called analysis.” •1880 Carl Groebe accidentally broke a thermometer while stirring a mixture of hot naphthalene and H 2 SO 4 ⇒ phthalic anhydride & phthalic acid ⇒ dye chemistry •1899 Arrhenius equation k = A exp(-Ea/RT) •1903 Ostward process 2NH 3 + 7/2 O 2 → 2NO 2 + 3 H 2 O (Pt sponge as catalyst) ⇒ HNO 3 industry •1909 Ostward (German) received Nobel Prize for studies of reaction rate over catalysts •1912 Paul Sabatier (French) received Nobel Prize for studies of catalytic hydrogenation of organic compounds •1915 Haber Process N 2 + 3 H 2 → 2 NH 3 (Fe catalyst) •1919 Fritz Haber (German) received Nobel Prize •1920 Sabatier published the 1 st book on catalysis •1923 Methanol synthesis CO + 2 H 2 → CH 3 OH (Cr 2 O 3 -ZnO catalyst) •1930 Fischer-Tropsch Process CO + H 2 → (CH) n (Fe catalyst) [...]... Catalytic cracking of petroleum (acid treated clays as catalyst) BET surface area Deuterium discovery ⇒ isotope research • 1963 Ziegler (German) & Natt (Italian) received Nobel Prize for stereoregulated polymerization catalyst Three Classes of Catalysts • Heterogeneous- The catalyst and the reactants are in different phases • Homogeneous- The catalyst and the reactants are in the same phase • Biological... Heterogeneous catalysis requires balance of adsorption, reaction, and desorption Catalyst strongly adsorbing ––> no rxn Catalyst weakly adsorbing ––> no rxn A Surface-Catalyzed Reaction Nanostructured Materials ( . catalysts World catalysts • 9 G$ business in 1999 • 24% for Refining, 24% for Chemicals, 23% for Polymers, 29% for Environment oxidation According to Dept. Energy, USA, in 2003 Catalysis &. after it is formed. 2. Synthesis methods must be designed to maximize the incorporation of all materials used in the process into the final product. 3. Whenever practicable, synthetic methodologies. research • 1963 Ziegler (German) & Natt (Italian) received Nobel Prize for stereoregulated polymerization catalyst Three Classes of Catalysts • Heterogeneous- The catalyst and the reactants