"La sfida della sostenibilità nel XXI secolo e il

1. Inquietudini nella modernità 2012 La verità della materia "La sfida della sostenibilità nel XXI secolo e il  ruolo del CNR per la Chimica Sostenibile e le Energie Rinnovabili" Maurizio Peruzzini ICCOM CNR Firenze

2. L’importanza dei numeri “Tutto Disponesti in misura, numero e peso” (Libro della Sapienza, XI, verso 20) Firenze, 16 dicembre 2012

3. L’importanza dei Numeri Firenze, 16 dicembre 2012 ~ ~ The kilowatt-hour (symbolized kWh) is a unit of energy equivalent to one kilowatt (1 kW) of power expended for one hour (1 h) of time 1 W·h = 1 W × 3 600 s = 3 600 W·s = 3 600 J (1 kwh = 3.600.000 J; 864.000 cal !!!!!!)

4. 1 kWh = 122,8 g coal ~ 1 ton coal = 8141 kwh !!!!!!

5. Telemaco Signorini, “L’alzaia”, 1864

6. HUMMER H3: 5 cilindri a benzina di 3700 cm3 che sviluppa una potenza di 245 CV (180 kW ≈ 1700 uomini ≈ 22,1 kg coal/h)  Il lavoro di 5 persone: solo poco più di 500 W !!! F IRENZE HYDROLAB 1 CV = 735 W !!! Telemaco Signorini, “L’alzaia”, 1864

7. Providing the mankindwith (cheap & distributed) ENERGY The problem: POWERING THE PLANET

8. EARTHRISE: Taken by Apollo 8 crewmember Bill Anders on December 24, 1968, showing the Earth seemingly rising above the lunar surface.

9. 2100 TWh electrical power consumed every year for lighting 200 billion Euros spent for energy per year 1800 millions of tons of CO2 per year 10 to 15 % ofworldwideenergy production spentforlighting Lighting is the most visible human creation

10. 1 tep = 1628 kWh 13 GTep/year 1000 oil barrels / sec 2l oil/day man We are eager for ENERGY!

11. 1859 Edwin Drake oil well Titusville, PA V. Balzani, Angew. Chem. 2007, 46, 52

12. C + O2 → CO2 50 kton/min 72 Mton/day C + O2 → CO2 26 Gton/year 4 tons/man

13. World Energy consumption (1850-2000) -Science 309 (2005) 550 S U S T A I N A B I L I T Y ENERG Y Provide energy to our planet will be the most important problem of XXI century for mankind Our society is looking for more and more energy: is this an out-of-control parameter? Sustainability & Energy an indissoluble binomial of our century

14. ENERGY DEMAND IS GROWING UP IN A CONTINUOUS AND UNRESTREINABLE WAY 1. 3. GLOBAL WARMING FAST DROPPING DOWN OF ALL TRADITIONAL FOSSIL FUELS’ RESERVES (AND MORE:SUSTAINABILITY IS MANDATORY) 2. ENERG Y S U S T A I N A B I L I T Y Demographic explosion Growing up of the standard of life and consumption Economic growth of third world countries The energy scenario in front of us

15. “SUSTAINABILITY” "Meeting the needs of the present without compromising the ability of future generations to meet their needs." (The U.N. Brundtland Commission 1987 (WCED) World Commission on Environment and Development)

16. Our Common Future (1987), Oxford: Oxford University Press Gro Harlem Brundtland,Oslo 1939 Minister of environment, Norway 1974 - 1983

17. Sustainability: "Meeting the needs of the present without compromising the ability of future generations to meet their needs." is the goal Green Chemistry: Technologies that are energy efficient, minimise or preferably eliminate the formation of waste, avoid the use of toxic and/or hazardous solvents and reagents and, where possible, utilise renewable, raw, materials. is the mean

18. Safer Reactions • & Reagents Catalysis • Solvent • Replacement Separation Processes Sustainable chemistry Use of Renewable Feedstocks Energy Efficiency Waste Minimisation Process Intensification SUSTAINABLE CHEMISTRY

19. The Twelve Principles of GREEN CHEMISTRY P.T.Anastas & J.C.Warner, Green Chemistry : Theory & Practice, Oxford Univ. Press,New York, 1998 • Prevention • Atom Economy • Less Hazardous Chemical Syntheses • Safer Solvents and Auxiliaries • Design for Energy Efficiency • Use of Renewable Feedstocks • Reduce Derivatives • Catalysis • Design for Degradation • Real-time analysis for Pollution Prevention • Inherently Safer Chemistry for Accident Prevention

20. The Twelve Principles of GREEN CHEMISTRY P.T.Anastas & J.C.Warner, Green Chemistry : Theory & Practice, Oxford Univ. Press,New York, 1998 1. PREVENTION: It is better to prevent waste than to treat or clean up waste after it is formed. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) Because of low polarity of dioxins and furans, like many other organochlorine compounds, are far more soluble in the fatty tissues of animals than they are in water. When these compounds enter the animal they are not readily exerted and tend to accumulate in fatty tissues that we call it bioaccumulation. So can result in an animal having significantly higher concentrations of the organochlorine compound in its body than in the surrounding environment (biomagnification; 100,000 times greater in fish)

21. 2. ATOM ECONOMY Fw of all atoms utilised 100 x = Fw of all reagents/reactants used % ATOM ECONOMY Sintesi catalitica dell‘ammoniaca 100 %

22. ‘Boots‘ process 6 steps Classic Process forIbuprofen 2. ATOM ECONOMY: Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product. Fw of all atoms utilised 100 x = (CH3OC)2O / AlCl3 Fw of all reagents/reactants used % ATOM ECONOMY ClCH2CO2C2H5 / NaOC2H5 H+ / H2O 15 million kg of ibuprofen are produced each year (17.5 million kg of waste) H2NOH H+ / H2O Ibuprofen

23. % Atom Economy = (FW of atoms utilized/FW of all reactants) X 100                                         = (206/514.5) X 100 = 40%

24. A New GreenerProcessforIbuprofen ‘Boots‘ process 6 steps Hoechst process 3 steps (CH3OC)2O / AlCl3 (CH3OC)2O / HF 1961 H2 / Ni Raney ClCH2CO2C2H5 / NaOC2H5 H+ / H2O 1997 Ibuprofen CO / Pd H2NOH H+ / H2O

25. % Atom Economy = (FW of atoms utilized/FW of all reactants) X 100                                         = (206/266) X 100 = 77%

26. Atom Efficiciency: Stoichiometricvs Catalytic Oxidation Atom efficiency = 360 / 860 = 42% Byproducts : Cr2(SO4)3 , H2O Etheor= ca. 1.5 Stoichiometric: The Jones Reagent (Sir Ewart Jones 1911-2002)

27. Atom efficiency = 120/138 = 87% Byproduct: H2O Etheor= ca. 0.1 Atom Efficiciency: Stoichiometricvs Catalytic Oxidation Science 2000, 287, 1636 - 1639Green, Catalytic Oxidation of Alcohols in Water Gerd-Jan ten Brink, Isabel W. C. E. Arends, Roger A. Sheldon

28. Cr(VI): The Organic Chemist’s Favorite Oxidant for over 100 y • “It’s hexavalent chromium, highly toxic, highly carcinogenic. • Gets into your DNA, so you pass the trouble along to your kids.” • 2000 : Julia Roberts in “Erin Brokovich”

29. 9. CATALYSIS: Catalytic reagents (as selective as possible) are superior to stoichiometric reagents. • The role of catalysts is to facilitate a transformation that is desired without being consumed as part of the reaction and without being incorporated in the final product. This facilitation can take several different forms including: • Selectivity enhancement: • Selective catalysis has been achieved to ensure that the degree of reaction that goes on is controlled (e.g. mono additions vs multiple addition), the site of reaction is contolled (e.g. regio-, chemo-selectivity), and the stereochemistry is controlled (e.g. stereo- and enantio-selectivity: RvsSenantiomer).

30. 9. CATALYSIS: Catalytic reagents (as selective as possible) are superior to stoichiometric reagents. Energy minimization by lowering the Eaof a reaction pathway, catalytic systems not only achieve control, but also lower the temperature at which the reaction is accomplished. Catalysts are necessary to effect a reaction. In large scale of commodity chemical process, this energy balance issue can be the single most important factor from both an environmental and economic impact assessment point of view. In comparing catalytic versusstoichiometric process, the advantage of catalysis is that, while a stoichiometric reagent will generate one mole of product for every mole of reagent used, a catalysts will carry out thousands , if not millions, of transformations before it is exhausted (TON = turnover number).

31. Homogeneous Catalysis Bio Catalysis Photo Catalysis Electro Catalysis Heterogeneous Catalysis Fine Chemicals Health Basic Chemicals Molecular Biology New materials CATALYSIS Food and Agricolture Environmental Technologies Energy

32. “HOW FAR WE ARE FROM A TRUE SUSTAINABLE DEVELOPMENT ?”

33. 1) Are we exceeding the carrying capacity of the earth? • Questions ! • (Not only for • Chemists) 2) Are we using resources and creating waste faster that the earth can take our wastes and convert them back into resources?

34. Resources • What Humans do Consumption Waste

35. What Nature does Recycling Resources Consumption Waste

36. 3 Rs The waste hierarchy refers to the "3 Rs" reduce, reuse and recycle, which classify waste managementstrategies according to their sustainability. It has remained the cornerstone of most waste minimisation strategies.

37. We must consider our ecological footprint • What Scientists • (Chemists) • can do? Chemists must place a Major Focus on theEnvironmental consequences of chemical productsand the processes by which these products are made

38. 1 acre = 4 046.86 m2 There exists about 4.5 acres/person (ca. 1.8 ha) of biologically productive space on the earth • http://www.FootprintNetwork.org IF EVERYONE LIVED LIKE ME, WE WOULD NEED 5.6 PLANETS

39. “SUSTAINABILITY” • What should • be improved ?

40. Humanity’s top problems for next years • Enhanced global warming • Depletion of resources (not only fuels!) • Food shortages • Shortages of potable water • Population growth • Waste& pollution … and CNR Researchers are workingtoachievethis goal! the Chemistryis part of the solution!

41. 1923 CNR Consiglio Nazionale delle Ricerche The National Research Council (CNR) is the greatest scientific public organization of our country. It was founded on 18 November 1923 and in 1945 it was transformed into a public body; it has mainly carried out training, promotion, and research coordination activities in every scientific and technological sector. In 2003, CNR became a "national public organization committed to carry out, promote, spread, transfer and improve research activities in the main sectors of knowledge growth and of its applications for the scientific, technological, economic and social development of the Country”. Vito Volterra Guglielmo Marconi 2012 Luigi Nicolais

42. CNR Consiglio Nazionale delle Ricerche CNR Consiglio Nazionale delle Ricerche To this end, the activities of the organization are divided into 11macro areas of interdisciplinary scientific and technological research, concerning several sectors: bio(techno)logy, medicine, materials, environment and land, information and communications, advanced systems of production, judicial and socio-economic sciences, classical studies and arts.

43. CNR Consiglio Nazionale delle Ricerche

44. CNR – NATIONAL RESEARCH COUNCIL Earth & Environment Agrofood Biomedical Sciences Physical Sciences and technologies of matter Chemical Sciences and technologies of materials Materials & Devices, ICT, Energy & transports Human Sciences & Cultural Heritage House of Chemists and Chemical Engineers at CNR dd

45. Biella: ISMAC Genova: ISMAC ISTM: Molecular Sciences & Tehnology MILAN, Padua, Perugia ICRM: Molecular Recognition MILAN, Rome ISMAC: Macromolecules MILAN, Genova, Biella Trieste: ICCOM, IC ICIS: Surface Chemistry, PADUA; ITM, ICB Ferrara: ISOF ISTEC: Ceramics FAENZA ISOF: Organic and Photochemistry BOLOGNA, Ferrara Perugia: ISTM PISA: ICCOM, IMCB IC: Crystallography BARI, Rome, Trieste; ICCOM ICCOM: Organometallic Chemistry & Catalysis FIRENZE, Pisa, Bari, Trieste IMC: Chemistry Methodologies, ROME ISMN: Nanomaterials ROME, Bologna, Palermo Sassari: ICB ICTP: Polymers NAPLES, Catania IMCB: Composites and Biomedical Materials NAPLES, Pisa ICB: Biomolecular Chemistry NAPLES, Sassari, Catania, Padua, Rome ITM: Technology of the membranes COSENZA, Padua Palermo: ISMN Sections (UOS) Headquarters Catania: ICB, ICTP

46. AREAS OF PRIMARY IMPORTANCE • Natural Biomolecules • Biopharmaceutical properties • Drug delivery • Drug discovery • Biomaterials & Tissues • Biosensors • Theragnostic • Computational modeling • New catalysts • Enzimatic reactions • Hydrogen generation and storage • Renewable energy sources • CO2 sequestration and valorization • Processes with low • environmental risk • Nanostructures, nanomaterials • Photonics, optoelectronics • Polymer composites • Ceramics • Materials technologies • Surface technologies • Computational modeling • Sensors Health Sustainability Converging Technologies Molecular Design for Social and EconomicNeeds Pharmaceuticals Food Cultural Heritage Transports Industrial Processes Next Manufacturing

47. HEALTH Biopharmaceuticalproperties NaturalProducts and biomolecules Drugdiscovery & delivery Biomaterials & Tissues Biosensors Bionformatics and modeling(in silico)

48. SUSTAINABILITY New catalysts & new reactions media Enzymatic reactions (white biotechnology) Hydrogen generation & storage Renewable energy sources Processes with low environmental risks CCS & CCU (Carbon dioxide)

49. CONVERGING TECHNOLOGIES Computational chemistry Nanostructures and Nanomaterials Photonics and Optoelectronics BiobasedPolymers / PolymerComposites Material and Surface Technologies Ceramics, Sensors

50. Progetti dipartimentali Il DSCTM, la Chimica (sostenibile) e l’energia x x x x x