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Although deep eutectic solvents (DES) and ethylene glycol (EG) electrolytes are gaining ground as media for the electrodeposition of metals, the influence of these electrolytes on the electrode and electrodeposits has not been elaborated before. In this work, we investigate how choline chloride: ethylene glycol based (ChCl:EG) electrolytes interact with the glassy carbon (GC) working surface at different potentials and, how these interactions change during the electrodeposition of iron from 1:2 and 1:4 ChCl:EG electrolytes. GC substrates are exposed to both electrolytes in absence of iron in order to study the pure electrolyte-substrate interactions. Linear sweep voltammetry was used to determine the potential range in which the different reactions occur, while time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to detect and identify the molecules adsorbed on the surface. In all systems, there is an accumulation of either choline or its derivatives on the electrode surface, with 1:4 ChCl:EG electrolytes showing different decomposition products from 1:2 ChCl:EG electrolytes. Choline accumulation and decomposition was also found on iron electrodeposits. The electrolyte composition has a major impact on the chemical speciation of iron, and on the deposit's adherence to the substrate. These are two crucial characteristics that define the efficiency of iron deposition from DES.

The interfacial bondings formed between succinic acid and myristic acid, as well as succinic anhydride molecules with a set of differently treated zinc substrates have been investigated using infrared reflection absorption spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The compounds were selected to model typically used carboxylic-based adhesives and coatings. Moreover, the adsorption kinetic has been evaluated by means of chronoamperometry (CA) and chronovoltammetry measurements. XPS results showed a relation between the amount of carboxylates formed by adsorption of succinic acid/myristic acid and the hydroxyl fraction presented on the surfaces as proved by a higher electron transfer in CA. On the other hand a set of oxidative/reductive interactions was detected during the adsorption of succinic anhydride, in turn proving a spontaneous ring opening and adsorption mechanism. A clear relationship between the amount of adsorbents and surface hydroxyls/carbonates was detected for the adsorption of succinic anhydride. The extent to which the formed carboxylates resisted negative potentials was also investigated by cyclic voltammetry (CV) in an aqueous solution. The coordinative bonding of a bifunctional carboxylic acid group to the oxide surface was found to be not stable in the presence of a negative potential, while a monofunctional carboxylic acid group could resist displacement by water for a prolonged period of time. On the other hand, a low double layer capacitance was obtained after the adsorption of succinic anhydride, which was related to a change in potential of zero charge (PZC) upon the adsorption.