A COMBINED THEORETICAL AND EXPERIMENTAL-STUDY OF THE ELECTROCHEMICALLY INDUCED CHEMISORPTION OF ACRYLONITRILE ON NICKEL, COPPER, AND ZINC

We report a combined theoretical and experimental study of the interac tion between a series of transition metals (Ni, Cu, Zn) and acrylonitr ile. We demonstrate experimentally that the transition metal has a sel ective role in the grafting of electropolymerized acrylonitrile. Nicke l and copper substrates support the formation of a polyacrylonitrile f ilm, while zinc does not. Quantum chemical calculations indicate that acrylonitrile molecules form pi-d bonds with Ni and Cu atoms, but do n ot react chemically with a Zn atom, in qualitative agreement with the experiment. Computational results also show that the electron affinity is significantly increased upon chemisorption, promoting radical anio n species at the metal surface as initiators for polymerization.