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Controlling the electrografting of polymers onto transition metal surfaces through solvent vs monomer adsorption
University of Mons, Belgium;.ORCID iD: 0000-0001-8845-6296
University of Mons, Belgium; .
University of Mons, Belgium; .
University of Liege, Belgium;.
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1999 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 121, no 1, 176-187 p.Article in journal (Refereed) Published
Abstract [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.

Place, publisher, year, edition, pages
American Chemical Society , 1999. Vol. 121, no 1, 176-187 p.
National Category
Engineering and Technology
URN: urn:nbn:se:liu:diva-81304DOI: 10.1021/ja981730yISI: 000078079200022OAI: diva2:551444
Available from: 2012-09-11 Created: 2012-09-11 Last updated: 2013-09-12

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