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The research in our group deals with the reproducible preparation of transition metal nanoparticles of controlled size and their applications in polyphasic catalysis. Metal nanocatalysts, generally defined as particles between 1 and 10 nm in size, are obtained by the bottom-up approach and one of the crucial parameters during their preparation to obtain reproducible properties remains their stabilization.

The originality of our chemistry relies on the synthesis in water of colloidal suspensions which could directly be used in biphasic liquid-liquid systems or to deposit nanoparticles on inorganic, magnetic or mesoporous supports. The catalyst recycling is particularly studied.

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Metallic nanoparticles in solution

During the last years, our laboratory has gained an expertise in the preparation and the stabilization of aqueous suspensions of metallic nanoparticles by quaternary ammonium surfactants, modified cyclodextrins or nitrogen ligands. These colloidal suspensions have proved to be active catalysts for various catalytic reactions: arenes hydrogenation (Rh, Ir, Ru), the tandem dehalogenation/hydrogenation reaction (Rh, Pd), the carbon-carbon coupling reaction (Pd) or the asymmetric hydrogenation of activated ketones (Pt).

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Deposit of metallic nanoparticles on support

We have also developed a clean and easy methodology based on simple impregnation to deposit metallic nanospecies on inorganic supports (SiO2, TiO2). Two methodologies could be applied: the wet or dry (fluidized bed) impregnations. These materials have proved to be very active for arene hydrogenation and their application to the degradation of organic pollutants from aqueous effluents is under current investigation.
Moreover, we have prepared nanoparticles on mesoporous supports by a surfactant-assisted method and the materials are active catalysts for arene hydrogenation.

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Alain Roucoux juin2012bis  Pr. Alain ROUCOUX (CV)

 

Alain Roucoux was born in Valenciennes (North of France) in 1963. He received his Ph.D. degree from the University of Lille in 1992 under the supervision of Professor A. Mortreux in the field of the asymmetric hydrogenation catalysis. In 1993, he joined the teaching staff of the Ecole Nationale Supérieure de Chimie de Rennes (ENSCR) before becoming Assistant-Professor (Maître de Conférences) in 1994. In 2001, he received his Habilitation and was promoted Professor in 2003. Since 1997, he develops the synthesis of noble metal nanoparticles in water for polyphasic catalysis. He manages the Nanocatalysis group of the Organometallics: Materials & Catalysis Team  (UMR CNRS 6226) – He is the author of 100 international scientific publications (h=32 with one paper in Chem. Rev. 2002 > 1500 times quoted), 5 book chapters and 9 patents. (update Scopus 06/2018)

KONICA MINOLTA DIGITAL CAMERA  Dr. Audrey DENICOURT-NOWICKI

Audrey Denicourt-Nowicki obtained her PhD degree from the University of Lille under the guidance of Dr F. Agbossou-Niedercorn and Pr A. Mortreux (2003). After working as a post-doctoral fellow with Pr C. Moody at the University of Exeter (United Kingdom), she joined the Ecole Nationale Supérieure de Chimie de Rennes (UMR CNRS 6226,  Institut des Sciences Chimiques de Rennes) as a senior lecturer in 2004. Her research interests include the synthesis of metal nanoparticles, either in solution or on support, for applications in polyphasic catalysis. She is author of 56 publications, 5 book chapters and one patent. (update 10/2016)

  • Marion DUVAL
    Ph.D student 2017-2020 – CIFRE thesis, DRT support
    Terpenes chemistry
  • Raïssa  RAMSSAMY
    Research Engineer – October 2018 – April 2019 – SOLVAY support
    Development of new processes for aliphatic nitrile hydrogenation
  • Zelia VERASTEGUI   
    Research Engineer – October 2018 – juillet 2019  – SOLVAY support
    Selective hydrocarbons oxidation with Manganese species
  • Natalia MORDVINOVA
    Post-doc student – November 2018 – May 2020 – SOLVAY support
    Innovative processes for the oxidation of hydrocarbons
  • Audrey CABROL & Antoine LEJEUNE
    Research Engineers – Maturing project April 2018 – April 2019 – SATT Ouest Valorisation support
    Industrial and indoor air treatment by catalytic oxidation over an innovative support coming from recycled glass wastes
    Collaborative project  with CIP and V&C teams (UMR 6226)
  • Victor DEBOOS
    Master student – January 2019 – July 2019

PhD Students

  • Anastaisia  LEBEDEVA – Ph.D defense  in 2017 dec  – French ministry support
  • Mariem RAUCHDI  – Ph.D defense  in 2017 dec  – PHC Toubkal  support – ENSCR /Univ of Marrakech
  • Brunno LANGE ALBUQUERQUE – Ph.D student 2014-2015 in ENSCR – Brasilian mobility support – University of Santa Catarina, Florianopolis
  • Monique ANGELO DA SILVA  – PhD defense  in Brasil July 2014 – CAPES-COFECUB program – UFAL / ENSCR
  • Carl-Hugo PELISSON – PhD Defense in 2013 dec – Brittany support
  • Elodie BILE-GUYONNET – PhD defense in 2012 Jan – ANR support
  • Claudie HUBERT- PhD defense in 2010 – Brittany support
  • Bastien LEGER- PhD defense  in 2007 – IFPEN support
  • Vincent MEVELLEC – PhD defense in 2005 – Brittany support
  • Jürgen SCHULZ – PhD defense in 2000 – CNRS support

Post-Doc and Engineer members

  • Kana KUNIHIRO
    Research Engineer – november 2017 / may 2018 – SOLVAY support
    Development of new processes for the oxidation of hydrocarbons
  • Caroline GERNEZ
    Research Engineer – october 2016 / april 2017 – SOLVAY support
    Innovative processes for the oxidation of hydrocarbons
  • Thanh CHAU
    Post-doc position – septembre  2011 /september 2012 –  ANR support
    Ruthenium and Rhodium nanoparticles stabilized with functional chiral cyclodextrins. Investigation in supramolecular asymmetric catalysis
  • Soraya HANDJANI
    Post-doc position – septembre  2010 /september 2011 –  ANR support
    Development of Ruthenium nanoparticles stabilized with functional chiral cyclodextrins. Investigation in supramolecular catalysis
  • Cindy HERMAN
    Research Engineer – December 2010 / May 2011 – ONIDOL support
    Hydrogenation of fatty compounds in aqueous phase by supported Palladium  nanoparticles
  • Aurélien  BELLEC
    Post-doc position – May 2010/Novembre 2010 – ONIDOL support
    Feasability of the hydrogenation of fatty compounds in aqueous phase by metallic nanoparticles

Masters and others students

  • Hélène VIALLIS (1996) – Lecturer, Université de Nantes
  • Sébastien LEVIGNE (1999) – Painter
  • Jean-Marie ORHAND (2000)
  • Mathilde MERLO (2001) – Agence Française de Sécurité Sanitaire des Aliments – Maisons-Alfort
  • Christophe MATTIODA (2002) –
  • Vincent MEVELLEC (2002) – ENSCR – R&D, ALCHIMER
  • Bastien LEGER (2004) – ENSCR – Lecturer, Université d’Artois
  • Yong ZHANG (2005) – Univ. Rennes 1
  • Danièle PRO (2008) – ENSCR –
  • Romain CADIO  (2009) – Univ. Rennes 1
  • Elodie CORTELAZZO-POLISINI (2010) – ENSCR – Agrégation studies
  • Pierre QUATREMARE (2012) – ENSCR – PhD Paris VI
  • Liege OLIVIERA BIESUZ (2012) – UFRGS, Brésil
  • Clément BELLINI (2013) – ENSCR – R&D, ARKEMA
  • Yoann FARRE (2013) –  ENSCR – PhD Univ. Nantes
  • Robin CARDONNET (2014) – Univ. Rennes 1- OPEN group (Nantes)
  • Pierre de la MOTTE ROUGE (2015) – Univ. Rennes 1 – ITGA (Environmental Services, Rennes)
  • Valentin AUDEBERT (2017) – Univ. Rennes 1 – CIP team collaboration
  • Rebecca EL KHAWAJA (2017)  – Lebanese University (EDST) – Pr M. Boutros collaboration – PhD thesis
  • Jason BEAUFREZ (2018) – ENSCR

Ruthenium trichloride catalyst in water: Ru colloids versus Ru dimer Characterization investigations
A. Lebedeva, B. L. Albuquerque, J. B. Domingos, J-F. Lamonier, J-M. Giraudon, P. Lecante, A. Denicourt-Nowicki, A. Roucoux
Inorg. Chem. 2019, 58, 4141−4151 (DOI: 10.1021/acs.inorgchem.8b03144)
Novel access to verbenone via ruthenium nanoparticles-catalyzed oxidation of a-pinene in neat water
M. Rauchdi, M. Ait Ali, A. Roucoux and A. Denicourt-Nowicki
Appl. Catal. A, General , 2018, 550, 266–273 (Doi.org/10.1016/j.apcata.2017.11.016)
Graphical abstract: Active hydrogenation Rh nanocatalysts protected by new self-assembled supramolecular complexes of cyclodextrins and surfactants in water Active hydrogenation Rh nanocatalysts protected by new self-assembled supramolecular complexes of cyclodextrins and surfactants in water
N.T. T. Chau, S. Menuel, S. Colombel-Rouen, M. Guerrero, E. Monflier, K. Philippot, A. Denicourt-Nowicki and A. Roucoux
RSC Adv., 2016, 6, 108125–108131 (DOI: 10.1039/c6ra21851b)
ChemRecord Odyssey in polyphasic catalysis by metal nanoparticles
A. Denicourt-Nowicki, A. Roucoux
The Chemical Record, 2016, 16, 2127-2141 (doi: 10.1002/tcr.201600050)
Water Soluble Polymer-Surfactant Complexes-Stabilized Pd(0) Nanocatalysts: Characterization and Structure-Activity Relationships in Biphasic Hydrogenation of Alkenes and α,β-Unsaturated Ketones
B.L. Albuquerque, A. Denicourt-Nowicki, C. Mériadec, J. B. Domingos, A. Roucoux
J. Catal., 2016, 340, 144–153 (http://dx.doi.org/10.1016/j.jcat.2016.05.015)
ACS SusChemEng2016 Magnetically retrievable Rh(0) nanocomposite as relevant catalyst for mild hydrogenation of functionalized arenes in water
C-H. Pélisson, A. Denicourt-Nowicki, A. Roucoux
ACS Sustainable Chem. Eng.,2016, 4, 1834−1839 (DOI: 10.1021/acssuschemeng.6b00045)
C.Eng.J. 2016  Efficient catalytic ozonation by ruthenium nanoparticles supported on SiO2 or TiO2. Towards the use of a non-woven fiber paper as original support.
P-F. Biard, B. Werghi, I. Soutrel, R Orhand, A. Couvert, A. Denicourt-Nowicki, A. Roucoux,
Chem. Eng. J., 2016, 289, 374-381
(doi:10.1016/j.cej.2015.12.051) Corrigendum Chem.Eng. J., 2017, 315, 639
CRC Toluene total oxidation over Pd and Au nanoparticles supported on hydroxyapatiteD. Chlala, M. Labaki, J-M. Giraudon, O. Gardoll, A. Denicourt-Nowicki, Alain Roucoux, J-F. Lamonier
C. R. Chimie, 2016, in press (doi:10.1016/j.crci.2015.07.015)
JCatal2016_FL Experimental and theoretical evidences of the influence of hydrogen bonding on the catalytic activity of a series of 2-hydroxy substituted quaternary ammonium salts in the styrene oxide/CO2 coupling reaction.
C. Carvalho Rocha, T. Onfroy, J. Pilmé, A. Denicourt-Nowicki, A. Roucoux, F. Launay,
J. Catal, 2016, 333, 29–39 (DOI: 10.1016/j.jcat.2015.10.014)
ChemCatChem2015ox  

Highly selective cycloalkanes oxidation in neat water with Ruthenium nanoparticles
A. Denicourt-Nowicki, A. Lebedeva, C. Bellini, A. Roucoux,
ChemCatChem, 2016, 8, 357-362 (DOI: 10.1002/cctc.201500805)

ChemCatChem2015  

Magnetically recoverable Palladium(0) nanocomposite as pertinent catalyst for hydrogenation reactions in water
C-H. Pélisson, A. Denicourt-Nowicki, C. Meriadec, J-M. Geneche, A. Roucoux
ChemCatChem, 2015,7,309-315 (DOI: 10.1002/cctc.201402761R1)

CatalToday2015  

From hydroxycetylammonium salts to their chiral counterparts. A library of efficient stabilizers of Rh(0) nanoparticles for catalytic hydrogenation in water
A. Denicourt-Nowicki, A. Roucoux
Catal Today, 2015, 247, 90–95 (DOI :10.1016/j.cattod.2014.05.031)

Brevet  

Nanoparticules métalliques supportées pour la catalyse
P.-F. Biard, A. Couvert, R. Lebullenger, A. Denicourt, A. Roucoux.
Fr Demande N° 15/59695 du 12/10/2015
PCT/FR2016/052634 du 12/10/2016

 

 

 

2014

Simple procedure for vacant POMs-stabilized Palladium (0) nanoparticles in water: structural and dispersive effects of lacunary polyoxometalates
R. Villanneau, A. Roucoux, P. Beaunier, D. Brouri and A. Proust
RSC Adv., 2014, 4, 264591-26498 (DOI: 10.1039/C4RA03104K)

Tunable hydroxylated surfactants: An efficient toolbox towards anisotropic gold nanoparticles
M. G. Angelo da Silva, M. R. Meneghetti, A. Denicourt-Nowicki and A. Roucoux
RSC Adv., 2014, 4, 25875-25879 (DOI: 10.1039/C4RA03550J)

Calcium Trifluoroacetate as an Efficient Catalyst for Ring opening of Epoxides by Amines under Solvent-free Conditions
R. Outouch, M. Rauchdi, B. Boualy, L. El Firdoussi,a A. Roucoux, M. Ait Ali
Acta Chim. Slov., 2014, 61, 67-72

Cyclodextrin-based systems for the stabilization of metallic(0) nanoparticles and their versatile applications in catalysis
S. Noël, B. Léger, A. Ponchel, K. Philippot, A. Denicourt-Nowicki, A. Roucoux, E. Monflier
Catal.Today, 2014, 235, 20-32 (DOI:10.1016/j.cattod.2014.03.030)

AmBook2014_ARXmonium surfactant-capped Rh(0) nanoparticles for biphasic hydrogenation  in  Metal Nanoparticles for Catalysis: Advances and Applications
A. Denicourt-Nowicki, A. Roucoux
Franklin (Feng) Tao (Ed.), Royal Society of Chemistry, 2014, 99-111

Asymmetric Allylic Alkylation, O. Baslé, A. Denicourt-Nowicki, C. Crevisy, M. Mauduit in  Copper-Cyan:Magenta:Yellow:Blackcatalyzed Asymmetcric Synthesis  Chapter 4, p85-125, Eds A. Alexakis, N. Krause, S. Woodward, Wiley-VCH Verlag GmbH & Co. KGaA, January 2014

2013

β-Cyclodextrins grafted with chiral amino acids: a promising supramolecular stabilizer of nanoparticles for asymmetric hydrogenation ?
N. T. T. Chau,J.-P. Guégan, S. Menuel, M. Guerrero, F. Hapiot, E. Monflier, K. Philippot, A. Denicourt-Nowicki, Alain Roucoux
Applied Catalysis A: General, 2013, 467, 497-503 (DOI: 10.1016/j.apcata.2013.08.011)

Efficient RutheniumNanocatalysts in Liquid-Liquid Biphasic Hydrogenation Catalysis: towards a Supramolecular Control via a Sulfonated Diphosphine / Cyclodextrin Smart Combination
M. Guerrero, Y. Coppel, N. T. T. Chau, A. Roucoux, A. Denicourt-Nowicki, E. Monflier, H. Bricout, P. Lecante, K. Philippot
ChemCatChem, 2013, 5, 3802-3811(DOI: 10.1002/cctc.201300467)

New and tunable hydroxylated driving agents for the production of tailor-made gold nanorods
M. G. Angelo da Silva, M. R. Meneghetti, A. Denicourt-Nowicki and A. Roucoux
RSC Adv., 2013, 3, 18292-18295 (DOI:10.1039/C3RA42949K)

Advances in methylated β-cyclodextrins-capped ruthenium nanoparticles: synthesis strategies, characterization and application in hydrogenation reactions
N. T. T. Chau, S. Handjani, J.-P. Guegan, M. Guerrero, E. Monflier, K. Philippot, A. Denicourt-Nowicki, A. Roucoux,
ChemCatChem, 2013, 5, 1497-1503 (DOI: 10.1002/cctc.201200718)

From hydroxyalkylammonium salts to protected-Rh(0) nanoparticles for catalysis in water: comparative studies of the polar heads
C-H. Pélisson, C. Hubert, A. Denicourt-Nowicki, A. Roucoux
Topics in catalysis, 2013, 56, 1220-1227 (DOI 10.1007/s11244-013-0088-0)
Special issue « Metal nanocatalysts in solution: characterization and reactivity », B. Chaudret, M. Gomez, K. Philippot (Eds)

About the Use of Rhodium Nanoparticles in Hydrogenation and Hydroformylation reactions
M. Guerrero, N. T. T. Chau, S. Noël, A. Denicourt-Nowicki, F. Hapiot, A. Roucoux, E. Monflier, K. Philippot
Current Organic Chemistry, 2013, 17(4), 364-399 (DOI 10.2174/1385272811317040006)
Special issue « Nanoscale Catalysts as Tools for Synthesis », Martin Prechtl (Ed.)

Book2013_ARXMetal nanoparticles in neat water for catalytic applications
A. Denicourt-Nowicki, A. Roucoux
in Nanomaterials in Catalysis, 2013, p 55-95
Ph Serp and K. Philippot (Eds.), Wiley-VCH, Weinheim.

2011-2012

Cyclodextrins as growth controlling agents for enhancing the catalytic activity of PVP-stabilized Ru(0) nanoparticles
R. Herbois, S. Noel, B. Leger, L. Bai, A. Roucoux, E. Monflier, A. Ponchel.
Chem. Commun., 2012, 48, 3451-3453  (DOI: 10.1039/C2CC17355G

)PTA-stabilized ruthenium and platinum nanoparticles: characterization and investigation in aqueous biphasic hydrogenation catalysis
P.-J. Debouttière,Y. Coppel, A. Denicourt-Nowicki, A. Roucoux, B. Chaudret, K. Philippot
Eur. J. Org. Chem., 2012, 5301-5306 (DOI: 10.1002/ejoc.201200479)

Chiral Ammonium Capped-Rh(0) nanocatalysts : Synthesis, Characterization, and Advances in Asymmetric Hydrogenation in Neat Water
E. Guyonnet Bilé, E. Cortelazzo-Polisini, A. Denicourt-Nowicki, R. Sassine, F. Launay, A. Roucoux
ChemSusChem, 2012,  5, 91-101 (DOI: 10.1002/cssc.201100364)  – Special Issue “Green Chemistry by Nanocatalysis”, V. Polshettiwar; J-M. Basset, D. Astruc (Edts),

Alkyl sulfonated diphosphines-stabilized ruthenium nanoparticles as efficient nanocatalysts in hydrogenation reactions in biphasic media
M. Guerrero, A. Roucoux, A. Denicourt-Nowicki, H. Bricout, E. Monflier, K. Fajerwerg, K. Philippot
Catal.Today, 2012, 183, 34-41 (DOI 10.1016/j.cattod.2011.09.012)

Moving from surfactant-stabilized aqueous rhodium (0) colloidal suspension to heterogeneous magnetite-supported rhodium nanocatalysts: synthesis, characterization and catalytic performance in hydrogenation reactions.
C.-H. Pelisson, L. L. R. Vono, C. Hubert, A. Denicourt-Nowicki, L. M. Rossi, A. Roucoux
Catal.Today, 2012, 183, 124-129 (DOI 10.1016/j.cattod.2011.08.046)

N-donor ligands based on bipyridine and ionic liquids: an efficient partnership to stabilize rhodium colloids. Focus on oxygen-containing compounds hydrogenation
A. Denicourt-Nowicki, B. Léger and A. Roucoux
Phys. Chem. Chem.  Phys.,2011, 13, 13510-1351

New ammonium surfactant-stabilized Rh(0) colloidal suspensions : Influence of novel counter-anions on physico-chemical and catalytic properties
E. Guyonnet Bilé, R. Sassine, A. Denicourt-Nowicki, F. Launay and A. Roucoux
Dalton Trans., 2011, 40, 6524-6531

Rh(0) colloids supported on TiO2 : a highly active and pertinent tandem in neat water for the hydrogenation of aromatics
C. Hubert, E. Guyonnet Bilé, A. Denicourt-Nowicki and A. Roucoux
Green Chem., 2011, 13, 1766-1771

Tandem dehalogenation-hydrogenation reaction of halogenoarenes as model substrates of endocrine disruptors in water: Rhodium nanoparticles in suspension vs on silica support
C. Hubert, E. Guyonnet-Bilé, A. Denicourt-Nowicki, A. Roucoux
Applied Catalysis A, 2011, 394, 215-219

Using Click Chemistry to Access Mono- and Ditopic ß-Cyclodextrin Hosts Substituted by Chiral Amino Acids
D. Ngan Tran, C. Blazkiewicz, S. Menuel, A. Roucoux, K. Philippot, F. Hapiot, E. Monflier.
Carbohydrate Research, 2011, 346, 210-218

Chemically modified cyclodextrins as supramolecular tools to generate carbon-supported ruthenium nanoparticles: an application towards gas phase hydrogenation
F. Wyrwalski , B. Léger , C. Lancelot , A. Roucoux, E. Monflier, A. Ponchel
Applied Catalysis A, 2011,  391,  334-341

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