Abstract
The effect of polyelectrolyte composition on the electrodeposition onto platinum is investigated using a counterion switching approach. Film formation of preformed polyelectrolytes is triggered by oxidation of hexacyanoferrates(II) (ferrocyanide), leading to polyelectrolyte complexes, which are physically crosslinked by hexacyanoferrate(III) (ferricyanide) ions due to preferential ferricyanide/polycation interactions. In this study, the electrodeposition of three different linear polyelectrolytes, namely quaternized poly[2-(dimethylamino)ethyl methacrylate] (i.e., poly{[2-(methacryloyloxy)ethyl]trimethylammonium chloride}; PMOTAC), quaternized poly[2-(dimethylamino)ethyl acrylate] (i.e., poly{[2-(acryloyloxy)ethyl]trimethylammonium chloride}; POTAC), quaternized poly[N-(3-dimethylaminopropyl)methacrylamide] (i.e., poly{[3-(methacrylamido)propyl]trimethylammonium chloride}; PMAPTAC) and different statistical copolymers of these polyelectrolytes with N-(3-aminopropyl)methacrylamide (APMA), are studied. Hydrodynamic voltammetry utilizing a rotating ring disk electrode (RRDE) shows the highest deposition efficiency DE for PMOTAC over PMAPTAC and over POTAC. Increasing incorporation of APMA weakens the preferred interaction of the quaternized units with the hexacyanoferrate(III) ions. At a sufficient APMA content, electrodeposition can thus be prevented. Additional electrochemical quartz crystal microbalance measurements reveal the formation of rigid polyelectrolyte films being highly crosslinked by the hexacyanoferrate(III) ions. Results indicate a different degree of water incorporation into these polyelectrolyte films. Hence, by adjusting the polycation composition, film properties can be tuned, while different chemistries can be incorporated into these electrodeposited thin hydrogel films.
Highlights
Electrodeposition is a powerful and controllable tool for triggering film formation by imposing an electrical signal
We investigated the electrodeposition of differentpolymer systems using hydrodynamic voltammetry and the electrochemical quartz crystal microbalance
We found an enhanced deposition efficiency for the polymer systems containing poly{[2-(methacryloyloxy) ethyl]
Summary
Electrodeposition is a powerful and controllable tool for triggering film formation by imposing an electrical signal. The possibility of electrodepositing inter alia polymers [1,2], metals [3] or polymer-metal compound composites [4,5,6] onto different substrates [7,8,9,10,11,12] provides access to a wide variety of functional films. These films offer exciting applications in material science [13], the biomedical field [8,14,15,16], sensing [16,17], and electronics [18]. Polyelectrolytes, for instance, are often deposited in an electrochemical manner utilizing the possible complex formation of these polymers with oppositely charged compounds
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