Larsen, A. G.; Johannsen, K.; Gothelf, K. V.
J. Coll. Int. Sci. 2004, 279, 158–166, doi:10.1016/j.jcis.2004.06.007
Center for Catalysis and Interdisciplinary Nanoscience Center at Aarhus University (iNANO), Department of Chemistry, Aarhus University, DK-8000 Aarhus C, Denmark
Environmental and Materials Department, R&D Division, Haldor Topsøe A/S, Nymøllevej 55, DK-2800 Lyngby, Denmark
The oxidation of tetramethylthiourea (TMTU) at gold electrodes in acetonitrile, leading to dissolution of the electrode, has been studied by electrochemical methods and by an electrochemical quartz crystal microbalance (EQCM). TMTU in acetonitrile readily adsorbs at gold electrodes and an estimated coverage of (30 Å2 per molecule) was measured electrochemically. Nevertheless, the oxidation of TMTU in solution is a diffusion-controlled process and is strongly influenced by the electrode material, as observed by comparison of gold electrodes with glassy carbon and platinum working electrodes. In the absence of TMTU, EQCM cyclic voltammetry experiments showed dissolution of gold through a 1e− oxidation process at potentials more positive than 1.20 V vs saturated calomel electrode (SCE). Potential step and cyclic voltammetry EQCM experiments performed using gold surfaces in the presence of TMTU revealed TMTU-assisted etching of gold at potentials as low as 0.35 V vs SCE. In the potential region from 0.35 to 1.20 V the current response of TMTU oxidation mimics the response expected for a redox-active species in solution, including the presence of a mass-transfer-limited region, which supports the conclusion that the etching process in this potential region is initiated by the oxidation of TMTU at the gold surface. The current efficiency of the TMTU-assisted etching was found to vary between 12 electrons per gold atom dissolved (e /Au) (E=0.50 V vs SCE) and 2 e /Au (0.90 V<E<1.20 V). At potentials <0.90 V the dominant electrochemical process is the formation of TMTU+, whereas at higher potentials the etching of the gold surface by formation of a Au(I)–TMTU+ species becomes equally important. At potentials above 1.20 V the etching is no longer dependent on the diffusion of TMTU and the e/Au value approaches 1.