Reference : Controlling the electrografting of polymers onto transition metal surfaces through solve...
Scientific journals : Article
Engineering, computing & technology : Materials science & engineering
Physical, chemical, mathematical & earth Sciences : Chemistry
http://hdl.handle.net/2268/4340
Controlling the electrografting of polymers onto transition metal surfaces through solvent vs monomer adsorption
English
Crispin, Xavier [University of Mons-Hainaut (UMH) > > Chemistry of New Materials Department > >]
Lazzaroni, Roberto [University of Mons-Hainaut (UMH) > > Chemistry of New Materials Department > > >]
Geskin, Victor [University of Mons-Hainaut (UMH) > > Chemistry of New Materials Department > >]
Baute, Noëlle [University of Liège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
Dubois, Philippe [University of Liège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
Jérôme, Robert mailto [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
Brédas, Jean-Luc [University of Mons-Hainaut > > Chemistry of New Materials Department > >]
13-Jan-1999
Journal of the American Chemical Society
Amer Chemical Soc
121
1
167-187
Yes (verified by ORBi)
International
0002-7863
Washington
[en] electropolymerization ; electrografting
[en] Electropolymerization of methacrylic monomers opens the possibility of chemically grafting a wide range of polymers onto transition metal surfaces. In this work, the electropolymerization of polyacrylonitrile and polyethyl acrylate is studied in different solvents; we experimentally confirm that the choice of solvent is a critical parameter for obtaining electrografted polymers. A density-functional theory−based study modeling the interaction of solvent (acetonitrile, dimethylformamide, and pyridine) or monomer (acrylonitrile and ethyl acrylate) molecules with the Ni(100) metal surface provides the means to classify the organic molecules with respect to their ability to interact with the surface. The surface binding-energy difference between monomer and solvent is introduced in a Frumkin-type isotherm. This allows us to rationalize the experimental observations in terms of a competitive adsorption at the metal surface between the monomer and the solvent. The first step in the electrografting mechanism thus appears to be the chemisorption of the monomer at the electrode surface before cathodic polarization is applied; the chemisorbed monomer is therefore the first species reduced, giving rise to an adsorbed reactive intermediate, which is thus able to start the polymerization of a grafted chain.
Center for Education and Research on Macromolecules (CERM)
Politique Scientifique Fédérale (Belgique) = Belgian Federal Science Policy ; Fonds pour la formation à la Recherche dans l'Industrie et dans l'Agriculture (Communauté française de Belgique) - FRIA ; Fonds de la Recherche Scientifique (Communauté française de Belgique) - F.R.S.-FNRS ; IBM
Researchers
http://hdl.handle.net/2268/4340
10.1021/ja981730y
http://pubs.acs.org/doi/pdf/10.1021/ja981730y

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