CNR & ICCOM CNR A Short overview Maurizio Peruzzini ICCOM CNR Sesto Fiorentino

1. KICK OFF MEETING SusPhos Regensburg, March 18th, 2013 CNR & ICCOM CNR A Short overview Maurizio Peruzzini ICCOM CNR Sesto Fiorentino mperuzzini@iccom.cnr.it

2. 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

3. CNR Consiglio Nazionale delle Ricerche CNR Consiglio Nazionale delle Ricerche To this end, the activities of the organization are divided into 7 macro 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.

4. CNR Consiglio Nazionale delle Ricerche

5. 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

6. Biella: ISMAC Genova: ISMAC ISTM: MolecularSciences & Tehnology MILAN, Padua, Perugia ICRM: MolecularRecognition MILAN, Rome ISMAC: Macromolecules MILAN, Genova, Biella Trieste: ICCOM, IC ICIS: SurfaceChemistry, 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 & CatalysisFIRENZE, Pisa, Bari, Trieste IMC: ChemistryMethodologies, ROME ISMN: Nanomaterials ROME, Bologna, Palermo Sassari: ICB ICTP: Polymers NAPLES, Catania IMCB: Composites and BiomedicalMaterials NAPLES, Pisa ICB: BiomolecularChemistry NAPLES, Sassari, Catania, Padua, Rome ITM: Technologyof the membranes COSENZA, Padua Palermo: ISMN Sections (UOS) Headquarters Catania: ICB, ICTP

7. Expertise and Research LinesICCOM-CNRIstituto di Chimica dei Composti Organometallici Direttore, Maurizio Peruzzini mperuzzini@iccom.cnr.it Responsabile UOS Pisa, Alessandro D’Ulivo dulivo@pi.iccom.cnr.it

9. Area della Ricerca del CNR di Firenze Sesto Fiorentino Area della Ricerca del CNR di Pisa

10. The missionof ICCOM is to developresearch, bothfundamental and applied, and highereducation in the followingscientificareas: a) New sustainablechemicalprocesseswith high efficiency and selectivity. b) Electrocatalysis for applicationsin the energysector (fuelcells).c) Hydrogenchemistry and technology: production, storageand employmentin fuelcells. d) Organic and organometalliccompounds for third generation photovoltaics. e) Technologies for carbon dioxideexploitation and confinement(CCS). f) Organic, inorganic and hybridpolymericmaterialswith functionalproperties. g) Advanced analyticaltechniquesfor environmentalmonitoring and the conservation of the artistic and cultural heritage. h) Theoreticalmodelingof chemicalprocesses and macroscopicproperties. h) Design and development of highlyspecificscientificinstruments. ICCOM General Considerations/ 1 Mission

11. In March 2010, ICCOM wasranked firstamong 24 institutesin the final report of the evaluationpanel for ChemicalSciences (C1), with a 92/100 final score. The Institutewasassigned a high or very high score in each of the excellenceindicatorsconsidered in the evaluation, including the number and quality of scientificpublications and patents, the editorial and educational activity, the outreachactivity and the ongoingprojects and contracts. In 2010, the Institute’s focus movedevenfurthertowards the themesofnewprocesses and newproductsfor a sustainabledevelopment, aswellasofresearchaimed at energy production from renewablesurces. ICCOM iscurrentlybecomingone of CNR leadinginstitutes in the «Sustainability and Energy»field, and a referencepointamongchemistryinstitutes in the internationalscientificcontext. ICCOM General Considerations/ 2 Quality

12. F IRENZE HYDROLAB • ICCOM participation to internationalresearchprojects and European Union networks: • FP7 MARIE CURIE: NANO-HOST & SUSPHOS ITN e IIF-MODUCAT • IDECAT Network ofExcellence"IntegratedDesign of CatalyticNanomaterials for a Sustainable Production" • FP7, NMP-2011-2.2-4 Novel materials for replacement of strategic or scarce raw materials (platinum group metals and rare earths) (FREECATS) • EuropeanResearchInstitute on Catalysis(ERIC) • COSTactionssuchasAction D40 "Hydrogenation and reductionreactions" and the more recent COST Chemistry Action CM0802 "European Phosphorus Sciences Network (PhoSciNet)" (2008 - 2012). • Italy-France-Russia trilateralprojectbetweenCNR, CNRS e RAS, in the GDRE Program framework, focussed on sustainablechemistry"HomogeneousCatalysis for Sustainable Development". • BilateralProjectsthatconnect CNR with foreignresearchagenciesthrough the Department of International Relations (Hungary, Russia, Taiwan, Portugal, France and Spain), the IntegratedActions of the University of Perugia (Spain) and MAE (UnitedStates). • Projectspromoted by the Ministry of Environment (PIRODE), by Regione Toscana (SUMUS, CESARE, EBH2), by MISE(PRIT 2015) and MIUR(FIRB, FISR, PRIN), and by bankfoundations (ECRF: Firenze Hydrolab; CARIPI). ICCOM General Considerations/ 3 International Projects

13. Istituto di Chimica dei Composti Organometallici k€ STAFF ca. 50Researchers ca. 40 Associates 9 Technicians 5 Administratives 50 Notstructured

14. ICCOM CNR isendowedwith a state-of-the-artinstrumentation for the characterization of inorganic, organic and organometallicmaterials, both in solid state and in solution. Verysignificantis the EPR(EPR Varian E112, X-Band located in Pisa) aswellas the NMRinstrumentation (in Pisa, Bari and Firenze), whichincludes a notableseries of NMR spectrometers, comprisingBruker 500, 400, 300 e 200 MHz instruments. The highestfieldinstrumentamongthosepresent in Firenze (400 MHz), aswellas the Bruker AMX 300 devicelocated in Pisa, feature the accessoryneeded to carry out solid state NMR measurements. Moreover, the Pisa unitwillsoonreceive a relaxometer. ICCOM Instruments in Firenze and Pisa / 1

15. ICCOM Instruments in Firenze and Pisa / 2 The instrumentationfor solidmaterialscharacterization, suited to studyboththeirmorphology and theircatalyticactivity, comprises an integrated system for solid-gasreactions (HYDENCATLAB), asingle crystal and a powderdiffractometer, anAFM-STM and a 120 KeVTEMmicroscope, a Micromeriticsporosimeter, a newly-acquiredICP-OESVarian 720 for the dosing of trace metallicelements, a DMTA (dynamicmechanicthermalanalysis)analyzer and a TGA instrumentcoupled to a mass spectrometer. Severalmass spectrometers, GC-MS e LC-MS are available in Firenze, Bari and Pisa. In this last location there are various high quality, advancedinstrumentswhichmake ICCOM’s Pisa UOS a center ofexcellence in the mass spectrometrysector.

16. ICCOM Instruments in Firenze and Pisa / 3 The instrumentationavailable for the study of fuelcells(assembly and performance assessment) is of particularrelevance, while the instrumentsrequired for the study of organic and organometalliccompounds to be applied to third generation photovoltaics(solar simulator) are soon to be acquired. The mobile device for LIBS analysis (MODI)isstate-of-the-art for applications in the sector of laser diagnosticsapplied to the conservation of cultural heritage. In Pisa are located the maincomputationalresources, organized in fourunits (DPM, VILLA, TWIN, SOLE), for a total of 240 cpu, which are connected to a 16 TB storageunit and are managed by a centralized code service.

17. ICCOM CNR Mission Improve the existing (catalytic) processes Design and development, ofnewsynthetic processes(catalytic) Sustainable production ofenergy Energy Hydrogen technology Alternative fuels STRATEGIC OBJECTIVES Reuse and Recycleofwaste materials Efficiency and selectivity Valorization and abatement ofpollutants Process optimization Biorefinery Valorizationof renewable resources Photovoltaic Conversionof renewable feedstock CNR DSCTM project“Innovative products and processes for sustainable chemistry“ 2006 - 2010 SUSTAINABLE CHEMISTRY Environmental issues

18. ICCOM Scientific Expertises • Sustainableprocessesforfine-chemicals production P. Barbaro, F. Liguori • Catalysis in Water and Biphasic Media L. Gonsalvi, M. Peruzzini • Methodsofmagneticresonance L. Colucci, C. Forte, C. Pinzino • Analytical methodologies for the environment A. D’Ulivo, E. Bramanti, E. Pitzalis, • Physical and chemical hydrogen storage L. Gonsalvi, A. Rossin, A. Ienco, M. Peruzzini, • Dyesensitizedsolarcells G. Reginato, A. Mordini, L. Zani • White PhosphorusChemicalActivation M. Caporali, L. Gonsalvi, A. Ienco, M. Peruzzini • Group of Catalysis and Materials G. Giambastiani, A. Rossin • CO2functionalization and storage M. Peruzzini, L. Ferrari, F. Mani • Chemistry at high pressure M. Ceppatelli • PrecursorsofactivepharmaceuticalsF. Machetti, A. Mordini. G. Reginato • Laboratory of materials for energy M. Bevilacqua, W. Oberhauser, A. Lavacchi, A. Marchionni, H. Miller, S. Moneti, F. Vizza • 13. Functionalpolymerbasedmaterials E. Cicogna, S. Coiai, E. Passaglia • InstrumentalAnalyticalChemistry E. Bramanti, A. D’Ulivo, E. Pitzalis • Applied Laser Spectroscopy Laboratory S. Legnaioli, V. Palleschi • Theoretical and ComputationalChemistry A. Ferretti, A. Lami, S. Monti, R. Santoro, G. Villani, F. Bloino, A. Ienco, C. Mealli, G. La Penna • Advanced Mass Spectrometry A. Raffaelli

19. ICCOM WHITE PHOSPHORUS d(Fe-P) = 2.2343(7)Å d(P3-P4) =2.1664(10) Å d(P4-P5) =2.2363(11) Å WHITE PHOSPHORUS COORDINATION

20. ICCOM WHITE PHOSPHORUS M.Peruzzini, P. Mastrorilli, D. Gudatet al. Chem. Eur. J. in press 31P{1H} EXSY spectrum of a solution containing LReP4+, L2Re2P4 2+ and free P4 (CD2Cl2, 298 K, tm = 0.100 s) WHITE PHOSPHORUS DYNAMICS

21. M.Peruzzini, P. Mastrorilli, D. Gudatet al. Chem. Eur. J. 2012, 18, 11238 - 11250

22. WHITE PHOSPHORUS REACTIVITY

23. The questforH3P=O Peruzzini, Caporali, Gonsalvi, Mirabello, Schipper, Stoppioni, Latypov, Rizvanov, Sinyashin, Yakhvarov, Angew. Chem. Int. Ed. 2011, 50, 5370–5373

24. Peruzzini, Caporali, Gonsalvi, Mirabello, Schipper, Stoppioni, Latypov, Rizvanov, Sinyashin, Yakhvarov, Angew. Chem. Int. Ed. 2011, 50, 5370–5373 The quest for H3PO Electrolytic generation

25. Peruzzini, Caporali, Gonsalvi, Mirabello, Schipper, Stoppioni, Latypov, Rizvanov, Sinyashin, Yakhvarov, Angew. Chem. Int. Ed. 2011, 50, 5370–5373

26. Phosphine oxide Phosphinous acid Peruzzini, Caporali, Gonsalvi, Mirabello, Schipper, Stoppioni, Latypov, Rizvanov, Sinyashin, Yakhvarov, Angew. Chem. Int. Ed. 2011, 50, 5370–5373

27. 1913 N2 + 3 H2 2 NH3 HaberProcess, BASF AG, Ludwigshafen, Germany ? P4 + 6 H2 4 PH3 P4Hydrogenation A first step?

28. ChemicalReviews, 2010, 110, 4178 - 4235

30. European Community: 4th RFP: INCO COPERNICUS 5th RFP: MCRTN Hydrochem 6th RFP: MCRTN Aquachem 7th RFP: MCITN SusPHOS COST Chemistry(Phoscinet) OtherFundingAgencies and Partners INTAS, Brussels, Belgium BASF AG, Ludwigshafen, Germany Thermphos, Vlissingen, The Netherlands NATO, Brussels, Belgium CNR, Rome, Italy Ente Cassa di Risparmio Firenze Regione Toscana MIUR, Rome, Italy (PRIN) F IRENZE HYDROLAB Funding € $ ¥ ₤

31. Grazie! Danke! mperuzzini@iccom.cnr.it maria.caporali@iccom.cnr.it