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Oscillatory Changes of the Heterogeneous Reactive Layer Detected with the Motional Resistance during the Galvanostatic Deposition of Copper in Sulfuric Solution.

Metallic copper was galvanostatically deposited on quartz|gold resonant electrodes by applying a constant current in a 0.5 M CuSO4/0.1 M H2SO4 aqueous solution. Galvanostatic copper deposition is one of the best methodologies to calibrate the electrochemical quartz crystal microbalances (EQCM), a gravimetric sensor to evaluate changes in mass during the electrochemical reactions through the Sauerbrey equation. The simultaneous measurement of mass, current density, and motional resistance by an EQCM with motional resistance monitoring allows us to characterize the processes occurring on the electrode surface and at the interfacial regions with unprecedented detail. During the galvanostatic copper deposition, Cu(H2O)4(OH)2 is accumulated close to the copper surface, generating a passive layer. This passive layer can act as Cu(2+) reservoir for the Cu(2+) → Cu process since the copper deposition is not affected. The analysis of motional resistance evolution in different experimental conditions reveals that the passive layer is formed by the reaction of oxidizing agents generated at the counter electrode with the metallic copper surface. The simplistic Cu(2+) → Cu process is completed with a more detailed mechanism, which includes the passive layer formation/dissolution and the transport of species from the counter electrode surface (Pt) to the working electrode surface. The results further support the calibration procedure of EQCM by the galvanostatic deposition of copper in sulfuric solutions. However, we suggest applying high current densities, separating the counter electrode and quartz|gold resonant electrode about 0.5 cm, and keeping oxygen in solution for the EQCM calibration. Moreover, the better interval time to calculate the Sauerbrey's constant from charge and resonant frequency data is between 150 and 300 s.