Abstract
Electrochemical quartz crystal microbalance, combined with cyclic voltammetric, chronoamperometric, and potentiostatic measurements, was used to study electrodeposition/dissolution phenomena at a gold electrode in solutions containing Na2S. Spontaneous, open-circuit deposition processes as well as dissolution of the deposits in sulfide-free solutions have also been investigated. The potential range, scan rate, sulfide concentration, and pH have been varied. The results of the piezoelectric nanogravimetric studies are elucidated by a rather complex scheme involving underpotential deposition of sulfur at approximately −0.85 V vs. sodium calomel electrode, reductive dissolution of the deposited sulfur-containing layer at potentials more negative than approximately −0.9 V, and formation of a sulfur-containing multilayer at potentials more positive than −0.2 V. During the reduction of sulfur deposited on Au, a mass increase due to the formation of polysulfide species in the surface layer, accompanied by incorporation of Na+ counterions, can be observed that starts at approximately −0.4 V. This is a reversible process, i.e., during the reoxidation, counterions leave the surface layers. Frequency excursions during the electroreduction and reoxidation processes reveal existence of several competitive dissolution–deposition steps. Spontaneous interaction between Au and HS− species results in a surface mass increase at the open-circuit potential, and it also manifests itself in the substantial decrease of the open-circuit potential after addition of Na2S to the supporting electrolyte.
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Acknowledgment
This work is supported by bilateral program cooperation between Republic of Croatia and Hungary CRO-01/2006 as well as by national research projects no. 098-0982934-2717 from the Ministry of Science and Technology of the Republic of Croatia (IC and EB-N) and OTKA K71771 from the National Scientific Research Fund, Hungary (GI).
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Bura-Nakic, E., Róka, A., Ciglenecki, I. et al. Electrochemical nanogravimetric studies of sulfur/sulfide redox processes on gold surface. J Solid State Electrochem 13, 1935–1944 (2009). https://doi.org/10.1007/s10008-008-0742-9
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DOI: https://doi.org/10.1007/s10008-008-0742-9