Surface Organometallic Chemistry for novel heterogeneous catalysts

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1 Bologna, February 13 th -14 th, 2013 Kick-off Meeting SINCHEM - Erasmus Mundus Joint Doctorate Programmes Surface rganometallic Chemistry for novel heterogeneous catalysts E. Alessandra Quadrelli Sustainable Development Chair,CPE Lyon and Centre National de la Recherche Scientifique (CNRS)

2 Lyon main actors for SINCHEM Sustainable Development Chair of

3 Attempt at presenting some French Higher Education institutions Layers UMR 5265 Mixed Unit of research Research team Surface rganometallic Chemistry team 15 permanent staff, 40 non-perm. 2 M /y contracts and research Surface Lyon research federation The Research Unit C2P2 (Chemistry Catalysis, Polymeryzation and Processes) 30 permanent staff 60 master, Ph.D. and post-doc. 2teams Infrastrtcure Steudenst And teaching Doctoral Level Federrative Level salary The doctoral school in chemistry at Université de Lyon (ED 206) one of the most prominent in France 8 research units about 200 Ph.D. supervisors. Ca. 80 Ph.D. theses defended each year : Green and sustainable chemistry /Analytical sciences/chemistry for life sciences/ Environmental Chemistry/Catalysis and processes Some key figures for Université de Lyon: 120,000 students 5,600 PhD students 6,500 academic and research staff 230 research laboratories 17 doctoral schools Among The missions of the University of Lyon are : Research and doctoral training International promotion of its activities

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5 Alessandra QUADRELLI and Chloé THIEULEUX s research contributions rganometallic fragments on Functional nanomaterials M M' M' M' M' M' Inorganic oxides Metal rganic Framework MF Hybrid mesoporous periodic silicas Metallic nanoparticles

6 Alessandra QUADRELLI and Chloé THIEULEUX s research contributions rganometallic fragments on Functional nanomaterials Inorganic oxides Metal rganic Framework MF Hybrid mesoporous periodic silicas Metallic nanoparticles M = Si, Al, Nb, Zr... M = Mge, M T, La Alkane activation Dinitrogen and ammonia activations Ta 1 bar 250 C Ta CHEM. CMM. (2004) SCIENCE (2007)

7 Alessandra QUADRELLI and Chloé THIEULEUX s research contributions rganometallic fragments on Functional nanomaterials Inorganic oxides CP-27-Ni Metal rganic Framework MF Hybrid mesoporous periodic silicas Catalysts or photactive materials Metallic nanoparticles Mo(C) 6 + H + H 2 2 S Ni@MoS 2 for HDS Au NP/Ni-MF for PRX ACS Catalysis (2012) AuCCl Norm.PL intnsity (a.u.) Norm. PL (a.u.) MF Energy (ev) MF+Si (b) 1 radiative channel in Si-doped MF (0.76%w Si) 3 radiative channels in original MF E exc =2.41 ev E exc =2.54 ev E exc =3.62 ev

8 Alessandra QUADRELLI and Chloé THIEULEUX s research contributions rganometallic fragments on Functional nanomaterials Inorganic oxides Metal rganic Framework MF Hybrid mesoporous periodic silicas Metallic nanoparticles Si SiR 2 H 3 C-(H 2 C) 7 N N Cl Ru Cl L (CH 2 ) 7 -CEt TF 65.0 min -1 TN (24h) >15000 Patent W Chem. Eur. J J.Am.Chem.Soc ChemSusChem 2012 M-RuPr R=SiMe 3 H 3 C-(H 2 C) 7 (CH 2 ) 7 -CH 3 C-(H 2 C) 7 (CH 2 ) 7 -CEt

9 Alessandra QUADRELLI and Chloé THIEULEUX s research contributions rganometallic fragments on Functional nanomaterials Inorganic oxides Metal rganic Framework MF Hybrid mesoporous periodic silicas Metallic nanoparticles W1 (W ) Si Si N N Si 1. 5 Au I SiTMS

10 Alessandra QUADRELLI and Chloé THIEULEUX s research contributions rganometallic fragments on Functional nanomaterials Inorganic oxides Metal rganic Framework MF Hybrid mesoporous periodic silicas Metallic nanoparticles Chem Comm 2010 J. Am. Chem. Soc Au Pt Si % Au/Ti 2 -WGC Au NPs (0.2%mol) MCH, TBHP (0.05 equiv) Air, 80 C, 24h Reaction time (h) 2 nm 1200 Ce 2 TF C2 - ξ-based surf. Ni ) (mole C2.h -1.mole NiSi x /Ce 2 (D Ni : 54%) Ni N3 /Ce 2 (D Ni : 47%) Ni Ni Ce Time on stream (h) ChemCatChem 2012 J Catal 2011

11 Heterogeneous catalysts

12 Metallic surfaces Molecules and Nanoobjets MLECULAR APPRACH to surfaces Caracterisation & Modelling Ionic Liquids and unconvetional media

13 Surface rganometallic Chemistry Grafting of organometallic compounds onto metals Homogeneous and heterogeneous ionic mediums SMC on zeolites, NMR, HPA, olefine metathesis Surface chemistry, functionalization and characterization C2 chemistry, alcenes metathesis. Nano-objects for the optic SMC onto hybrides materials Nitrogen activation, Molecular models, MF (metal organic frameworks)

14 Polymer Chemistry / colloids Controlled radical polymerizations and Innovative Chemistries Controlled Radical Polymerizations (RAFT/SFRP) controlled architectures for different applications hybrid organic/inorganic materials Frontiers between catalytic and radical polymerization? Functional polyolefins (synthesis, characterisation) Use in (controlled) radical polymerizations for block copolymers New hybrid concepts Polycondensation Polymer Catalysts Fundamental advances in conventional Ziegler-Natta catalysts Development of new high performance solid activators for metallocene catalysts New copolymers of olefins and butadiene produced with novel lanthanide catalysts Catalytic polymerization in dispersed media Functional polyolefins Polymer Reaction Engineering Analyse the different phenomena as well as their interactions Understanding of the process-property relationship Develop new, innovative polymerisation processes and reactor ptimise existing processes to reduce the consumption of raw materials Design new sensors for the in-line monitoring of polymerisation Improve existing models of polymerisation processes

15 FUNDAMENTALS Process intensification Micro-structured reactors Reactor-heat exchanger Kinetics Catalyst deposition / activation Microfluidic Small-scale & distributed production Batch-to-continuous processes Reactor modelling APPLICATINS Hydrogen storage Fischer-Tropsch synthesis Steam reforming Hydrogenation for pharmaceuticals Silicones / Hydrosililation Safe & selective oxidations Bioressources VC abatement Waste water treatments

16 ED Chimie Lyon es unités de recherche membres de l école doctorale sont : L'Institut de Recherche sur la Catalyse et l'environnement IRCELYN L'Institut de Chimie et Biochimie Moléculaire et Supramoléculaire ICBMS L'Institut des Sciences Analytiques ISA Le Laboratoire Matimatériaux et Interfaces LMI Le Laboraoire de Physico-Chimie des Matériaux Luminescents (LPCML) Le Laboratoire Hydrazynes et procédés LHP Le Laboraoire d'automatique et de Génie des Procédés LAGEP Chimie, Catalyse, Polymères et Procédés C2P2 (LCPP, LCMS) Le Laboratoire de Génie des Procédés Catalytiques LGPC Le Laboraoire de Chimie de l' ENS Lyon Le Centre Européen de RMN à Très Haut Champs CRMN Le Laboratoire de Génie Civil et Ingénierie Environnementale LGCIE - INSA Lyon Le Laboratoire d'ecologie des Hydrosystèmes Naturels et Anthropisés LEHA-ENTPE Les laboratoires de l'ifpen Lyon