[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.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
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 ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Brédas, Jean-Luc; University of Mons-Hainaut > Chemistry of New Materials Department
Language :
English
Title :
Controlling the electrografting of polymers onto transition metal surfaces through solvent vs monomer adsorption
Publication date :
13 January 1999
Journal title :
Journal of the American Chemical Society
ISSN :
0002-7863
eISSN :
1520-5126
Publisher :
Amer Chemical Soc, Washington, United States - Washington
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