ORBi: Crispin Xavier - Controlling the electrografting of polymers onto transition metal surfaces through solvent vs monomer adsorption

Reference : Controlling the electrografting of polymers onto transition metal surfaces through solve...


	Document type :	Scientific journals : Article
	Discipline(s) :	Engineering, computing & technology : Materials science & engineering Physical, chemical, mathematical & earth Sciences : Chemistry
	To cite this reference:	http://hdl.handle.net/2268/4340

Title :	Controlling the electrografting of polymers onto transition metal surfaces through solvent vs monomer adsorption
Language :	English
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 [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 > >]
Publication date :	13-Jan-1999
Journal title :	Journal of the American Chemical Society
Publisher :	Amer Chemical Soc
Volume :	121
Issue/season :	1
Pages :	167-187
Audience :	International
ISSN :	0002-7863
City :	Washington
Keywords :	[en] electropolymerization ; electrografting
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.
Research units :	Center for Education and Research on Macromolecules (CERM)
Funders :	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
Target :	Researchers
Permalink :	http://hdl.handle.net/2268/4340
DOI :	10.1021/ja981730y
Other URL :	http://pubs.acs.org/doi/pdf/10.1021/ja981730y

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