Journal of The Electrochemical Society · 2006 · 32 citations · 46 references
Natural SciencesChemistryMaterials ScienceChemical KineticsInorganic ChemistryPhysical ChemistryElectroanalytical ChemistryElectrochemical KineticsElectrode KineticsElectrode MaterialsElectrode-electrolyte InterfacesElectrolyte SolutionsAqueous Electrolyte SolutionsDiffusion CoefficientsDiffusivityElectrochemical Reaction KineticsElectrode Reaction KineticsElectrode Reaction MechanismsGold ElectrodesKinetics Of Electrode Reactions
The kinetics and initial stages of electrodeposition on gold from an aqueous electrolyte composed of bismuth and telluryl ions and nitric acid were investigated using voltammetry and chronopotentiometry. For tellurium alone, it is found that the reduction of tellurium ions to tellurium occurs with four exchanging electrons at vs ). At , tellurium reduces to under kinetic control and the following simultaneous diffusion-controlled reaction occurs with one exchange electron per tellurium atom: . Bismuth telluride deposition starts at more positive potential than bismuth and tellurium deposit individually. It is suggested that the electrodeposition of proceeds via a Stransky–Krastanov mechanism. From the Bard correction to the Sand equation, the diffusion coefficients of bismuth and telluryl ions were determined to be and , respectively, in the investigated solutions. Due to the low diffusivity and solubility of telluryl ions, the limiting current density for deposition in the investigated solution is low; it is only . Above the limiting current density, a smooth deposit cannot be obtained without agitation. A smooth deposit can be achieved when the depletion of anions is eliminated.
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