Controlling the electrografting of polymers onto transition metal surfaces through solvent vs monomer adsorption

X. Crispin, R. Lazzaroni, V. Geskin, N. Baute, P. Dubois, R. Jérôme, Jean-Luc Bredas*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

45 Scopus citations

Abstract

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.

Original languageEnglish (US)
Pages (from-to)176-187
Number of pages12
JournalJournal of the American Chemical Society
Volume121
Issue number1
DOIs
StatePublished - Jan 13 1999

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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