BIOPSIL Ecofriendly catalytic materials based on ... · 2012, in press; Nanomaterials . 2012, 2,...
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BIOPSIL Ecofriendly catalytic materials based on biopolymers and ionic liquid CP2D 2008 Researchers involved in the project BIOPSIL funded by ANR are: Dr. Isabelle Dez, Pr. Annie-Claude Gaumont, Dr. Eric Guibal and Thierry Vincent. BIOPSIL project was carried out by: Nathalie Clousier (PhD funded by ANR), Claire Jouannin (PhD funded by ANR), Renaud Moucel (PhD) and Dr. Prashant Naik (Post-doc) Combining advantages of homogeneous catalysis (high activity and selectivity) with those of heterogeneous catalysis (easy product/catalyst separation, recycling and reuse of the catalyst) is a high interest for economical and ecological points of view. Our aim was to develop innovative and sustainable catalytic materials by the immobilization of a transition metal catalyst in an ionic liquid (IL) phase supported on a biopolymer. Our BioPSIL (BioPolymer Supported Ionic Liquid) materials were prepared from two marine polysaccharides, alginates and chitosan, using two strategies. BioPSIL materials (beads or scaffolds) were successfully applied for the Pd-catalyzed allylic substitution reaction of allylic acetate or allylic alcohol. CONTACT : Isabelle Dez, LCMT, ENSICAEN, UMR CNRS 6507 [email protected] Project issue First method: confinement of the IL J. Appl. Polym. Sci. 2012, accepted; Separation Science and Technology 2012, in press; Nanomaterials 2012, 2, 31-53; Comptes Rendus Chimie 2011, 14 (7-8), 680-684; Applied Catalysis B: Environmental 2011, 103 (3-4), 444-452; Advanced Synthesis & Catalysis 2010, 352 (2-3), 433-439. Project outcomes Alginates O O - OOC OH OH O O OH OH - OOC O O O - OOC OH HO Chitosan O O O OH O HO NH 2 OH O NHCOCH 3 HO Porous BioPSIL materials were prepared in the form of cylindrical monoliths, discs or beads. The BioPSIL were characterized and successfully applied for the Pd-catalyzed hydrogenation of 4-nitroaniline and nitrophenol in aqueous solution, with complete conversions in 15 min and conversions of 93 % after 4 days in continuous flow systems. This study showed the influence of the nature of the biopolymer support and the nature of the IL on textural properties of the BioPSIL materials and on their catalytic activity. Catalytic Alginate-Cyphos IL-Pd(0) cylindrical monolith BioPSIL cat. cat. cat. Substrate Product IL Substrate Product IL cat. cat. Second method: adsorption of the IL N u OR Pd ( OA c ) 2 ( 0 . 05 e q u i v. ) TPPTS ( 0 . 2 e q u i v. ) [ b m i m ] BF 4 i n Bi o- PSIL N u H R = H or A c R' = H or Ph R' F or so ft nuc l eo p hil es , BSA/ A c OK was use d t o d e p ro t ona t e i n s it u th e nuc l eo p hil e. F or a ll y li c a l co h o l s , p h en y lb oron i c ac id was use d t o ac ti va t e th e - OH g rou p . BioPSIL were proved to be compatible in basic or acidic conditions used to performed the reactions. BioPSIL materials provided high activities and recyclability up to 10 cycles. Both the nature of the biopolymer support and its conditioning influence the BioPSIL materials catalytic properties. First method Second method BioPSIL were proved to be compatible with both Pd-catalyzed reactions, stable in the reaction conditions and reusable. They lead to low leaching of Pd and should be efficient in continuous flow processes.
Transcript of BIOPSIL Ecofriendly catalytic materials based on ... · 2012, in press; Nanomaterials . 2012, 2,...
BIOPSIL Ecofriendly catalytic materials based on biopolymers and ionic liquid CP2D 2008 Researchers involved in the project BIOPSIL funded by ANR are: Dr. Isabelle Dez, Pr. Annie-Claude Gaumont, Dr. Eric Guibal and Thierry Vincent. BIOPSIL project was carried out by: Nathalie Clousier (PhD funded by ANR), Claire Jouannin (PhD funded by ANR), Renaud Moucel (PhD) and Dr. Prashant Naik (Post-doc)
Combining advantages of homogeneous catalysis (high activity and selectivity) with those of heterogeneous catalysis (easy product/catalyst separation, recycling and reuse of the catalyst) is a high interest for economical and ecological points of view. Our aim was to develop innovative and sustainable catalytic materials by the immobilization of a transition metal catalyst in an ionic liquid (IL) phase supported on a biopolymer. Our BioPSIL (BioPolymer Supported Ionic Liquid) materials were prepared from two marine polysaccharides, alginates and chitosan, using two strategies.
BioPSIL materials (beads or scaffolds) were successfully applied for the Pd-catalyzed allylic substitution reaction of allylic acetate or allylic alcohol.
CONTACT : Isabelle Dez,
LCMT, ENSICAEN, UMR CNRS 6507
Project issue
First method: confinement of the IL
J. Appl. Polym. Sci. 2012, accepted; Separation Science and Technology 2012, in press; Nanomaterials 2012, 2, 31-53; Comptes Rendus Chimie 2011, 14 (7-8), 680-684; Applied Catalysis B: Environmental 2011, 103 (3-4), 444-452; Advanced Synthesis & Catalysis 2010, 352 (2-3), 433-439.
Project outcomes
Alginates
OO
-OOC
OH
OHO
O
OH
OH-OOC
O OO
-OOC OHHO
Chitosan
OOO
OHOHO NH2 OH
ONHCOCH3HO
Porous BioPSIL materials were prepared in the form of cylindrical monoliths, discs or beads. The BioPSIL were characterized and successfully applied for the Pd-catalyzed hydrogenation of 4-nitroaniline and nitrophenol in aqueous solution, with complete conversions in 15 min and conversions of 93 % after 4 days in continuous flow systems. This study showed the influence of the nature of the biopolymer support and the nature of the IL on textural properties of the BioPSIL materials and on their catalytic activity.
Catalytic Alginate-Cyphos IL-Pd(0) cylindrical monolith
BioPSIL
cat.
cat.
cat.
Substrate
Product IL
Substrate Product
IL
cat.
cat.
Second method: adsorption of the IL
NuORPd(OAc)2 (0.05 equiv.)
TPPTS (0.2 equiv.)[bmim]BF4 in Bio-PSIL
NuHR = H or AcR' = H or Ph
R'
For soft nucleophiles, BSA/ AcOK was used to deprotonate in situ the nucleophile.For allylic alcohols, phenylboronic acid was used to activate the -OH group.
BioPSIL were proved to be compatible in basic or acidic conditions used to performed the reactions. BioPSIL materials provided high activities and recyclability up to 10 cycles. Both the nature of the biopolymer support and its conditioning influence the BioPSIL materials catalytic properties.
First method Second method
BioPSIL were proved to be compatible with both Pd-catalyzed reactions, stable in the reaction conditions and reusable. They lead to low leaching of Pd and should be efficient in continuous flow processes.
