Herein, we report the potential-driven electrochemical
transformation
carried out in basic media of two Ni2+ salen polymers,
(poly(NiSalen)s), abbreviated as poly(meso-NiSaldMe)
and poly(NiSaltMe). These two polymers, with different configurations
of methyl substituents on the imine bridge, were used as precursors
for the preparation of electrocatalytically active nickel hydroxide
[Ni(OH)2]-type nanoparticles (NPs) anchored in the polymeric
matrix as poly[SalenNi(OH)2]. The use of potentiodynamic
and potentiostatic electropolymerization conditions for the deposition
of polymeric precursors allowed us to control the molecular architecture
of poly(NiSalen)s and NPs derived from them. Thus, we obtained different
arrangements of NPs embedded in morphologically different poly(Salen)
matrixes, indicating their electrocatalytic activity toward ethanol
to different extents. Moreover, we found a direct relationship between
the electrochemical stability of the poly(NiSalen) precursors operating
in the organic solvent-based electrolyte solutions and the easiness
of their transformation into Ni(OH)2 NPs operating in the
aqueous alkaline media. Poly(NiSalen)s and Ni(OH)2-type
NPs were characterized by X-ray photoelectron spectroscopy, scanning
electron microscopy, and transmission electron microscopy.